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Sample records for oxyhydroxides lepidocrocite gamma-feooh

  1. Novel iron oxyhydroxide lepidocrocite nanosheet as ultrahigh power density anode material for asymmetric supercapacitors.

    Science.gov (United States)

    Chen, Ying-Chu; Lin, Yan-Gu; Hsu, Yu-Kuei; Yen, Shi-Chern; Chen, Kuei-Hsien; Chen, Li-Chyong

    2014-09-24

    A simple one-step electroplating route is proposed for the synthesis of novel iron oxyhydroxide lepidocrocite (γ-FeOOH) nanosheet anodes with distinct layered channels, and the microstructural influence on the pseudocapacitive performance of the obtained γ-FeOOH nanosheets is investigated via in situ X-ray absorption spectroscopy (XAS) and electrochemical measurement. The in situ XAS results regarding charge storage mechanisms of electrodeposited γ-FeOOH nanosheets show that a Li(+) can reversibly insert/desert into/from the 2D channels between the [FeO6 ] octahedral subunits depending on the applied potential. This process charge compensates the Fe(2+) /Fe(3+) redox transition upon charging-discharging and thus contributes to an ideal pseudocapacitive behavior of the γ-FeOOH electrode. Electrochemical results indicate that the γ-FeOOH nanosheet shows the outstanding pseudocapacitive performance, which achieves the extraordinary power density of 9000 W kg(-1) with good rate performance. Most importantly, the asymmetric supercapacitors with excellent electrochemical performance are further realized by using 2D MnO2 and γ-FeOOH nanosheets as cathode and anode materials, respectively. The obtained device can be cycled reversibly at a maximum cell voltage of 1.85 V in a mild aqueous electrolyte, further delivering a maximum power density of 16 000 W kg(-1) at an energy density of 37.4 Wh kg(-1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Local environments and lithium adsorption on the iron oxyhydroxides lepidocrocite (gamma-FeOOH) and goethite (alpha-FeOOH): A 2H-2 and 7Li solid-state MAS NMR study

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Grey, Clare P.; Paik, Jonkim

    2008-01-01

    2H and 7LiMAS NMR spectroscopy techniques were applied to study the local surface and bulk environments of iron oxyhydroxide lepiclocrocite (gamma-FeOOH). 2H variable-temperature (VT) MAS NMR experiments were performed, showing the presence of short-range, strong antiferromagnetic correlations......, even at temperatures above the Neel temperature, TN, 77 K. The formation of a Li+ inner-sphere complex on the surface of lepiclocrocite was confirmed by the observation of a signal with a large 7Li hyperfine shift in the 7Li  MAS NMR spectrum. The effect of pH and relative humidity (RH...

  3. Radiolytic formation of iron oxyhydroxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sutherland, T.; Wren, J.C., E-mail: tsuther4@uwo.ca [The Univ. of Western Ontario, London, ON (Canada)

    2014-07-01

    The formation of iron oxyhydroxide nanoparticles under gamma irradiation of ferrous ion solutions is a process in the infancy of its understanding. Herein we present work to probe the mechanism by which these nanoparticles are formed. These results can be used to better understand the activity transport processes occurring within a reactor environment which may pose both environmental and safety concerns. Initial ferrous concentrations and solution pH were modified and found to have little effect on final particle size and composition. The nanoparticles were formed in the presence of scavengers and it was found that hydroxyl radicals promote the particle formation while solvated electrons diminish it. Post-synthesis heating was found to shift the initially-formed lepidocrocite particles towards a mixture of goethite and maghemite. (author)

  4. Comparison study on transformation of iron oxyhydroxides: Based on theoretical and experimental data

    International Nuclear Information System (INIS)

    Lu Bin; Guo Hui; Li Ping; Liu Hui; Wei Yu; Hou Denglu

    2011-01-01

    We have investigated the catalytic transformation of ferrihydrite, feroxyhyte, and lepidocrocite in the presence of Fe(II). In this paper, the transformation from akaganeite and goethite to hematite in the presence of trace Fe(II) was studied in detail. The result indicates that trace Fe(II) can accelerate the transformation of akaganeite and goethite. Compared with the transformation of other iron oxyhydroxides (e.g., ferrihydrite, feroxyhyte, lepidocrocite, and akaganeite), a complete transformation from goethite to hematite was not observed in the presence of Fe(II). On the basis of our earlier and present experimental results, the transformation of various iron oxyhydroxides was compared based on their thermodynamic stability, crystalline structure, transformation mechanism, and transformation time. - Graphical abstract: The transformation of various iron oxyhydroxides in the presence of trace Fe(II) was compared based on experimental results, thermodynamic stability, crystalline structure, and transformation mechanism. Highlights: → Fe(II) can accelerate the transformation from akaganeite to hematite. → Small particles of goethite can transform to hematite in the presence of Fe(II). → Some hematite particles were found to be embedded within the crystal of goethite. → The relationship between structure and transformation mechanism was revealed.

  5. Two-phase transformation of lepidocrocite to maghemite

    Science.gov (United States)

    Dekkers, M. J.; Gapeev, A. K.; Gendler, T. S.; Gribov, S. K.; Shcherbakov, V. P.

    2003-04-01

    A detailed investigation of CRM acquired at different stages of the transformation lepidocrocite -> maghemite -> hematite is carried out. Apparently, at least two-stage lepidocrocite maghemite transformation was revealed from: a) the two-peak Ms(T) curve; b) the observation of constricted hysteresis loops appearing after annealing fresh lepidocrocite samples at elevated temperatures; c) continuous monitoring (for 500 hrs) of CRM acquisition at elevated temperatures. For the latter two sets of CRM acquisition experiments at 12 temperatures from 175C to 550C in the presence of 0.1 mT magnetic field were performed: 1) with fine dispersed natural lepidocrocite grains in a kaolin matrix (about 1 volume % of lepidocrocite), 2) for lepidocrocite peaces 3x3x3 mm in size. In both cases the CRM was detected already at 175C after 1 day of annealing. Note that this temperature is lower than the temperature of the TGA peak of the lepidocrocite -> maghemite transformation. Mossbauer spectra obtained from the peaces after annealing at 225C during 6 and 14 hours, respectively, revealed significantly different patterns. Unexpectadly, fine dispersed maghemite grains formed due the lepidocrocite dehydration in the first peace (6 hrs of annealing) occurred to be more ordered than those of from the second peace. The samples are subjected to the X-ray analysis in an attempt to clarify the observed difference. The observed phenomena can be explained by the two-phase conception of the transformation lepidocrocite -> maghemite. First the precipitation of small superparamagnetic particles of maghemite takes place growing with time. Second, these grains coalesce with each other resulting in appearance of the antiphase boundaries decreasing the susceptibility, slowing down the process of CRM acquisition and generating the constricted hysteresis loops. The work is supported by INTAS 99-1273.

  6. FeII induced mineralogical transformations of ferric oxyhydroxides into magnetite of variable stoichiometry and morphology

    International Nuclear Information System (INIS)

    Usman, M.; Abdelmoula, M.; Hanna, K.

    2012-01-01

    The Mössbauer spectroscopy was used to monitor the mineralogical transformations of ferrihydrite (F), lepidocrocite (L) and goethite (G) into magnetite as a function of aging time. Ferric oxyhydroxides were reacted with soluble Fe II and OH – in stoichiometric amounts to form magnetite at an initial pH of ∼9.7. Observed transformation extent into magnetite followed the order: F>L>G with almost 30% of untransformed G after 1 month. The departure from stoichiometry, δ, of magnetite (Fe 3−δ O 4 ) generated from F (δ∼0.04) and L (δ∼0.05) was relatively low as compared to that in magnetite from G (δ∼0.08). The analysis by transmission electron microscopy and BET revealed that generated magnetite was also different in terms of morphology, particle size and surface area depending on the nature of initial ferric oxyhydroxide. This method of preparation is a possible way to form nano-sized magnetite. - Graphical abstract: Mössbauer spectrum of the early stage of magnetite formation formed from the interaction of adsorbed Fe II species with goethite. Highlights: ► Ferric oxides were reacted with hydroxylated Fe II to form magnetite. ► Magnetite formation was quantified as a function of aging time. ► Complete transformation of ferrihydrite and lepidocrocite was achieved. ► Almost 70% of initial goethite was transformed. ► Resulting magnetites have differences in stoichiometry and morphological properties.

  7. Magnetic comparison of abiogenic and biogenic alteration products of lepidocrocite

    Science.gov (United States)

    Till, J. L.; Guyodo, Y.; Lagroix, F.; Ona-Nguema, G.; Brest, J.

    2014-06-01

    Lepidocrocite is a potentially important Fe-bearing precursor phase for the production of nanoscale Fe-oxide particles in the environment. We present a detailed magnetic characterization of various alteration products of lepidocrocite resulting from thermal dehydroxylation reactions and bacterially induced bioreduction and remineralization, accompanied by characterization with x-ray diffraction (XRD) and transmission electron microscopy. Dehydroxylation during annealing at moderate temperatures produces a topotactic transformation from lepidocrocite to maghemite when heated in an oxidizing atmosphere, or to magnetite when heated in a reducing atmosphere. The abiotic Fe-oxide products form an oriented framework of strongly interacting superparamagnetic crystallites and are characterized by a distinctive porous nanostructure observed by electron microscopy. Lepidocrocite bioreduction by the iron-reducing bacterium Shewanella putrefaciens ATCC 8071 produces nanoscale particles of a strongly magnetic phase. This Fe(II)-bearing mineral produced by bioreduction is highly crystalline and euhedral in shape, with a broad grain size distribution and is indicated by magnetic and XRD measurements to be a cation-excess magnetite. We highlight the distinguishing microscopic characteristics of magnetite from both abiotic and bacterially induced mineralization that should allow them to be identified in natural settings. Moreover, both mechanisms of alteration represent potential pathways for the direct formation of strongly magnetic fine-grained Fe-oxide particles in sedimentary environments.

  8. Kinetics of reductive bulk dissolution of lepidocrocite, ferrihydrite, and geothite

    DEFF Research Database (Denmark)

    Larsen, O.; Postma, Diederik Jan

    2001-01-01

    of the reduction experiments, lepidocrocite crystals were subsampled and the change in crystal habit and size distribution was studied by transmission electron microscopy. The rate of complete dissolution was described by the function J/m0 5 k9(m/m0)g where J is the overall rate of dissolution (mol/s), m0...... for lepidocrocite showed strong etch-pitting of the crystals parallel to the c-axis resulting ultimately in disintegration of the crystals. For the different iron oxides, the initial rate was independent of the specific surface area, emphasizing the importance of the crystal structure for the dissolution rate....... However, among the lepidocrocites the initial rate was proportional to the specific surface area. The exponent, g was found to vary from a value near 1.0 for one of the 2-line ferrihydrites, two of the lepidocrocites and the goethite, to values close to 2.3 for the other 2-line ferrihydrite and the 6-line...

  9. The swelling transition of lepidocrocite-type protonated layered titanates into anatase under hydrothermal treatment

    OpenAIRE

    Yuan, Huiyu; Besselink, Rogier; Liao, Zhaoliang; ten Elshof, Johan E.

    2014-01-01

    The common facets of anatase crystals are the (001) and (101) planes. However, the phase transformation from lepidocrocite-type titanate into anatase by hydrothermal processing yields an anatase microstructure with high concentration of exposed (010) planes. The phase transformation of a lepidocrocite-type protonated layered titanate (HTO) into anatase was studied using XRD, TEM, FTIR, and measurement of pH and zeta potential. It was found that HTO is proton-deficient. The phase transformatio...

  10. Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite

    International Nuclear Information System (INIS)

    Liu Hui; Li Ping; Zhu Meiying; Wei Yu; Sun Yuhan

    2007-01-01

    The transformation of Fe(II)-adsorbed ferrihydrite was studied. Data tracking the formation of products as a function of pH, temperature and time is presented. The results indicate that trace of Fe(II) adsorbed on ferrihydrite can accelerate its transformation obviously. The products are lepidocrocite and/or goethite and/or hematite, which is different from those without Fe(II). That is, Fe(II) not only accelerates the transformation of ferrihydrite but also leads to the formation of lepidocrocite by a new path. The behavior of Fe(II) is shown in two aspects-catalytic dissolution-reprecipitation and catalytic solid-state transformation. The results indicate that a high temperature and a high pH(in the range from 5 to 9) are favorable to solid-state transformation and the formation of hematite, while a low temperature and a low pH are favorable to dissolution-reprecipitation mechanism and the formation of lepidocrocite. Special attentions were given to the formation mechanism of lepidocrocite and goethite. - Graphical abstract: Fe(II)-adsorbed ferrihydrite can rapidly transform into lepidocrocite or/and goethite or/and hematite. Which product dominates depends on the transformation conditions of ferrihydrite such as temperature, pH, reaction time, etc. In the current system, there exist two transformation mechanisms. One is dissolution/reprecipitation and the other is solid-state transformation. The transformation mechanisms from Fe(II)-adsorbed ferrihydrite to lepidocrocite and goethite were investigated

  11. Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.; Emerson, David; Banfield, Jillian F.

    2010-06-22

    Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence ({mu}XRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolated from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.

  12. The swelling transition of lepidocrocite-type protonated layered titanates into anatase under hydrothermal treatment

    Science.gov (United States)

    Yuan, Huiyu; Besselink, Rogier; Liao, Zhaoliang; Ten Elshof, Johan E.

    2014-04-01

    The common facets of anatase crystals are the (001) and (101) planes. However, the phase transformation from lepidocrocite-type titanate into anatase by hydrothermal processing yields an anatase microstructure with high concentration of exposed (010) planes. The phase transformation of a lepidocrocite-type protonated layered titanate (HTO) into anatase was studied using XRD, TEM, FTIR, and measurement of pH and zeta potential. It was found that HTO is proton-deficient. The phase transformation process begins after uptake of a sufficient number of protons into the lepidocrocite-type structure. With the uptake of protons new hydroxyl groups form on the internal surfaces of the layered titanate and result in a bilayer state of HTO. The phase transformation reaction is a topotactic dehydration reaction in which anatase forms and water is expelled by syneresis.

  13. The swelling transition of lepidocrocite-type protonated layered titanates into anatase under hydrothermal treatment.

    Science.gov (United States)

    Yuan, Huiyu; Besselink, Rogier; Liao, Zhaoliang; Ten Elshof, Johan E

    2014-04-03

    The common facets of anatase crystals are the (001) and (101) planes. However, the phase transformation from lepidocrocite-type titanate into anatase by hydrothermal processing yields an anatase microstructure with high concentration of exposed (010) planes. The phase transformation of a lepidocrocite-type protonated layered titanate (HTO) into anatase was studied using XRD, TEM, FTIR, and measurement of pH and zeta potential. It was found that HTO is proton-deficient. The phase transformation process begins after uptake of a sufficient number of protons into the lepidocrocite-type structure. With the uptake of protons new hydroxyl groups form on the internal surfaces of the layered titanate and result in a bilayer state of HTO. The phase transformation reaction is a topotactic dehydration reaction in which anatase forms and water is expelled by syneresis.

  14. The swelling transition of lepidocrocite-type protonated layered titanates into anatase under hydrothermal treatment

    NARCIS (Netherlands)

    Yuan, H.; Besselink, R.; Liao, Zhaoliang; ten Elshof, Johan E.

    2014-01-01

    The common facets of anatase crystals are the (001) and (101) planes. However, the phase transformation from lepidocrocite-type titanate into anatase by hydrothermal processing yields an anatase microstructure with high concentration of exposed (010) planes. The phase transformation of a

  15. Synthesis of beta alumina from aluminum hydroxide and oxyhydroxide precursors

    CSIR Research Space (South Africa)

    Van Zyl, A

    1993-02-01

    Full Text Available Two aluminium oxyhydroxides, boehmite and pseudoboehmite, and two aluminium hydroxides, bayerite and gibbsite, have been investigated as precursors for the synthesis of the solid electrolyte, beta alumina. Reaction pathways and products have been...

  16. Sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides

    Directory of Open Access Journals (Sweden)

    R.V. Smotraiev

    2016-05-01

    Full Text Available The actual problem of water supply in the world and in Ukraine, in particular, is a high level of pollution in water resources and an insufficient level of drinking water purification. With industrial wastewater, a significant amount of pollutants falls into water bodies, including suspended particles, sulfates, iron compounds, heavy metals, etc. Aim: The aim of this work is to determine the impact of aluminum and manganese ions additives on surface and sorption properties of zirconium oxyhydroxide based sorbents during their production process. Materials and Methods: The sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were prepared by sol-gel method during the hydrolysis of metal chlorides (zirconium oxychloride ZrOCl2, aluminum chloride AlCl3 and manganese chloride MnCl2 with carbamide. Results: The surface and sorption properties of sorbents based on xerogels of zirconium, aluminum and manganese oxyhydroxides were investigated. X-ray amorphous structure and evolved hydroxyl-hydrate cover mainly characterize the obtained xerogels. The composite sorbents based on xerogels of zirconium oxyhydroxide doped with aluminum oxyhydroxide (aS = 537 m2/g and manganese oxyhydroxide (aS = 356 m2/g have more developed specific surface area than single-component xerogels of zirconium oxyhydroxide (aS = 236 m2/g and aluminum oxyhydroxide (aS = 327 m2/g. The sorbent based on the xerogel of zirconium and manganese oxyhydroxides have the maximum SO42--ions sorption capacity. It absorbs 1.5 times more SO42–-ions than the industrial anion exchanger AN-221. The sorbents based on xerogels of zirconium oxyhydroxide has the sorption capacity of Fe3+-ions that is 1.5…2 times greater than the capacity of the industrial cation exchanger KU-2-8. The Na+-ions absorption capacity is 1.47…1.56 mmol/g for each sorbent. Conclusions: Based on these data it can be concluded that the proposed method is effective for sorbents production based on

  17. Effects of Cd on reductive transformation of lepidocrocite by Shewanella oneidensis MR-1

    Institute of Scientific and Technical Information of China (English)

    Chaolei Yuan; Fangbai Li; Rui Han; Tongxu Liu; Weimin Sun; Weilin Huang

    2017-01-01

    We investigated the reduction of lepidocrocite (γ-FeOOH) by Shewanella oneidensis MR-1 in the presence and absence of Cd.The results showed that Cd2+ retarded microbial reduction of γ-FeOOH and avoided formation of magnetite.The inhibitory effect on γ-FeOOH transformation may not result from Cd2+ toxicity to the bacterium;it rather was probably due to competitive adsorption between Cd2+ and Fe2+ on γ-FeOOH as its surface reduction catalyzed by adsorbed Fe2+ was eliminated by adsorption of Cd2+.

  18. Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

    Energy Technology Data Exchange (ETDEWEB)

    Maluangnont, Tosapol, E-mail: tosapol.ma@kmitl.ac.th [College of Nanotechnology, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Catalytic Chemistry Research Unit, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Arsa, Pornanan [Catalytic Chemistry Research Unit, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Department of Chemistry, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong [Department of Chemistry, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Gotoh, Kazuma [Graduate School of Natural Science & Technology, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530 (Japan); Sooknoi, Tawan, E-mail: kstawan@gmail.com [Catalytic Chemistry Research Unit, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand); Department of Chemistry, Faculty of Science, King Mongkut' s Institute of Technology Ladkrabang, Bangkok 10520 (Thailand)

    2016-06-15

    While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O{sup 2−} sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} as an example. The low basicity (0.04 mmol CO{sub 2}/g) and low desorption temperature (50–300 °C) shown by CO{sub 2}− TPD suggests that O{sup 2−} sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO{sub 2}. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C{sub 16} acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O{sup 2−} sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast {sup 1}H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C{sub 31} ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at Ti{sup IV} sites was also illustrated. - Graphical abstract: Interlayer basic sites in lepidocrocite titanate, K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4}, lead to an intercalation of palmitic acid with a layer expansion. Display Omitted - Highlights: • K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} intercalates palmitic acid, forming the occluded potassium salt. • The interlayer expansion is evidenced by PXRD patterns and TEM image. • Two types of basic sites are deduced from ultrafast

  19. Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

    International Nuclear Information System (INIS)

    Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

    2016-01-01

    While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O 2− sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K 0.8 Zn 0.4 Ti 1.6 O 4 as an example. The low basicity (0.04 mmol CO 2 /g) and low desorption temperature (50–300 °C) shown by CO 2 − TPD suggests that O 2− sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO 2 . The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C 16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O 2− sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1 H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C 31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at Ti IV sites was also illustrated. - Graphical abstract: Interlayer basic sites in lepidocrocite titanate, K 0.8 Zn 0.4 Ti 1.6 O 4 , lead to an intercalation of palmitic acid with a layer expansion. Display Omitted - Highlights: • K 0.8 Zn 0.4 Ti 1.6 O 4 intercalates palmitic acid, forming the occluded potassium salt. • The interlayer expansion is evidenced by PXRD patterns and TEM image. • Two types of basic sites are deduced from ultrafast 1 H MAS NMR. • Lepidocrocite titanate catalyses ketonization of palmitic acid to palmitone and

  20. Efficient Overall Water-Splitting Electrocatalysis Using Lepidocrocite VOOH Hollow Nanospheres

    KAUST Repository

    Shi, Huanhuan

    2016-11-29

    Herein we report the control synthesis of lepidocrocite VOOH hollow nanospheres and further their applications in electrocatalytic water splitting for the first time. By tuning the surface area of the nanospheres, the optimal performance can be achieved with low overpotentials of 270 mV for the oxygen evolution reaction (OER) and 164 mV for the hydrogen evolution reaction (HER) at 10 mA cm-2 in 1 m KOH, respectively. Furthermore, when used as both the anode and cathode for overall water splitting, a low cell voltage of 1.62 V is required to reach the current density of 10 mA cm-2 , making the VOOH hollow nanospheres an efficient alternative to water splitting.

  1. Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

    Science.gov (United States)

    Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

    2016-06-01

    While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

  2. Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

    Science.gov (United States)

    Balistrieri, L.S.; Chao, T.T.

    1990-01-01

    This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites

  3. Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

    Science.gov (United States)

    Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S

    2015-09-01

    Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

  4. Redox Reactions of Reduced Flavin Mononucleotide (FMN), Riboflavin (RBF), and Anthraquinone-2,6-disulfonate (AQDS) with Ferrihydrite and Lepidocrocite

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhi [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zachara, John M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shi, Liang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moore, Dean A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kennedy, David W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Fredrickson, Jim K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2012-09-17

    Flavins are secreted by the dissimilatory iron-reducing bacterium Shewanella and can function as endogenous electron transfer mediators (ETM). In order to assess the potential importance of flavins in Fe(III) bioreduction, we investigated the redox reaction kinetics of reduced flavins (FMNH2 and RBFH2) with ferrihydrite and lepidocrocite. The organic reductants rapidly reduced and dissolved ferrihydrite and lepidocrocite in the pH range 4-8. The rate constant k for 2-line ferrihydrite reductive dissolution by FMNH2 was 87.5 ± 3.5 M-1∙s-1 at pH 7.0 in batch reactors, and the k was similar for RBFH2. For lepidocrocite, the k was 500 ± 61 M-1∙s-1 for FMNH2, and 236 ± 22 M-1∙s-1 for RBFH2. The surface area normalized initial reaction rates (ra) were between 0.08 and 77 μmoles∙m-2∙s-1 for various conditions in stopped-flow experiments. Initial rates (ro) were first-order with respect to Fe(III) oxide concentration, and ra increased with decreasing pH. Poorly crystalline 2-line ferrihydrite yielded the highest ra, followed by more crystalline 6-line ferrihydrite, and crystalline lepidocrocite. Compared to a previous whole-cell study with Shewanella oneidensis strain MR-1, our findings suggest that ETM reduction by the Mtr pathway coupled to lactate oxidation are rate limiting, rather than heterogeneous electron transfer to the Fe(III) oxide.

  5. On the reaction of iron oxides and oxyhydroxides with tannic and phosphoric acid and their mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Beltran, J. J., E-mail: jjbj08@yahoo.com; Novegil, F. J.; Garcia, K. E.; Barrero, C. A. [Universidad de Antioquia, Sede de Investigacion Universitaria, Grupo de Estado Solido, Instituto de Fisica (Colombia)

    2010-01-15

    The actions of tannic acid, phosphoric acid and their mixture on lepidocrocite, goethite, superparamagnetic goethite, akaganeite, magnetite, hematite and maghemite for 1 day and 1 month were explored. It was found that these acids form iron tannates and phosphates. Lepidocrocite and magnetite were the iron phases more easily transformed with the mixture of the acids after 1 month of reaction, whereas hematite was the most resistant phase. In the case of goethite, our results suggest that in order to understand properly the action of these acids, we have to take into account its stoichiometry, surface area and degree of crystallinity.

  6. P-V-T equation of state of rhodium oxyhydroxide

    Science.gov (United States)

    Suzuki, Akio

    2018-04-01

    A high pressure X-ray diffraction study of RhOOH was carried out up to 17.44 GPa to investigate the compression behavior of an oxyhydroxide with an InOOH-related structure. A fit to the third-order Birch-Murnaghan equation of state gave K0 = 208 ± 6 GPa, and K‧ = 9.4 ± 1.3. The temperature derivative of the bulk modulus was found to be ∂K/∂T = -0.06 ± 0.02 GPa K-1. The refined parameters for volume thermal expansion were α0 = 2.7 ± 0.3 × 10-5 K-1; α1 = 1.7 ± 1.1 × 10-8 K-2 in the polynomial form (α(T) = α0 + α1(T-300)). Our results show that RhOOH is very incompressible, and has a higher bulk modulus than other InOOH-structured oxyhydroxides (e.g. δ-AlOOH, ε-FeOOH, and γ-MnOOH).

  7. The calculated solubilities of hematite, magnetite and lepidocrocite in steam generator feedtrains

    International Nuclear Information System (INIS)

    Jobe, D.

    1997-05-01

    The solubility of three iron oxides [hematite (α-Fe 2 O 3 (s)), magnetite (Fe 3 O 4 (s)) and lepidocrocite (γ-FeOOH(s))] under representative steam generator feedtrain conditions were calculated using a thermodynamic database for these oxides and the associated aqueous species. Using this database, we calculated the solubility of iron for both Fe 3 O 4 (s) in equilibrium with other iron oxides and for the individual oxides in the presence of various oxygen partial pressures. The results indicate that the solubility of iron is strongly dependent on redox conditions, represented either by dissolved H 2 or O 2 concentration, or by the presence of other iron oxides (stable or metastable). The solubility behaviour of these oxides can be explained by changes in the aqueous-phase speciation of iron with temperature and pH. Similar calculations for the individual oxides in the presence Of O 2 (g) are also presented and were used to construct temperature-dependent phase diagrams for these oxides in equilibrium (including metastable conditions) with 1 ppb (ppb - μg·kg -1 ) of soluble iron. Calculations were also performed for feedtrain solutions containing 5 ppb of dissolved oxygen and pH buffered using mixtures of amines. From these calculations it was concluded that, relative to the oxidation potential and temperature of the feedtrain solution, changing the pH-buffer has only a minor effect on iron solubility. The effect of the variation in iron solubility along the feedtrain with solution pH, temperature and redox potential on corrosion-product transport to the boiler is also discussed. (author)

  8. Iron (III) oxyhydroxide in isopropyl alcohol preparation, characterization and solvothermal treatment

    International Nuclear Information System (INIS)

    Carvalho, E.L.C.N.; Jafelicci Junior, M.

    1989-01-01

    Iron (III) nitrate hydrolysis was carried out in isopropyl alcohol solution by an aqueous amonia gas stream resulting in iron (III) oxyhydroxide sol. It has been investigated in this work the solvothermal treatment of this colloidal system at 120 0 C and 24 hours. Iron (III) oxyhydroxide freshly obtained and solvothermally treated. Samples were dryed by lyophilization. Products obtained were characterized by the following techniques: spectrophotometric iron analysis by 1,10-orthophenantroline complexation method, powder X-ray diffraction, vibrational infrared spectra and differential thermal analysis. After solvothermal treatment resulting product was crystallized into hematite, while freshly iron (III) oxyhydroxide was non crystalline. Both of them are very active powder, showing high water adsorption [pt

  9. Electron small polarons and their mobility in iron (oxyhydr)oxide nanoparticles

    DEFF Research Database (Denmark)

    Katz, Jordan E; Zhang, Xiaoyi; Attenkofer, Klaus

    2012-01-01

    Electron mobility within iron (oxyhydr)oxides enables charge transfer between widely separated surface sites. There is increasing evidence that this internal conduction influences the rates of interfacial reactions and the outcomes of redox-driven phase transformations of environmental interest....... To determine the links between crystal structure and charge-transport efficiency, we used pump-probe spectroscopy to study the dynamics of electrons introduced into iron(III) (oxyhydr)oxide nanoparticles via ultrafast interfacial electron transfer. Using time-resolved x-ray spectroscopy and ab initio...

  10. Long-term effects of the iron-based phosphate binder, sucroferric oxyhydroxide, in dialysis patients.

    Science.gov (United States)

    Floege, Jürgen; Covic, Adrian C; Ketteler, Markus; Mann, Johannes F E; Rastogi, Anjay; Spinowitz, Bruce; Chong, Edward M F; Gaillard, Sylvain; Lisk, Laura J; Sprague, Stuart M

    2015-06-01

    Hyperphosphatemia necessitates the use of phosphate binders in most dialysis patients. Long-term efficacy and tolerability of the iron-based phosphate binder, sucroferric oxyhydroxide (previously known as PA21), was compared with that of sevelamer carbonate (sevelamer) in an open-label Phase III extension study. In the initial Phase III study, hemo- or peritoneal dialysis patients with hyperphosphatemia were randomized 2:1 to receive sucroferric oxyhydroxide 1.0-3.0 g/day (2-6 tablets/day; n = 710) or sevelamer 2.4-14.4 g/day (3-18 tablets/day; n = 349) for 24 weeks. Eligible patients could enter the 28-week extension study, continuing the same treatment and dose they were receiving at the end of the initial study. Overall, 644 patients were available for efficacy analysis (n = 384 sucroferric oxyhydroxide; n = 260 sevelamer). Serum phosphorus concentrations were maintained during the extension study. Mean ± standard deviation (SD) change in serum phosphorus concentrations from extension study baseline to Week 52 end point was 0.02 ± 0.52 mmol/L with sucroferric oxyhydroxide and 0.09 ± 0.58 mmol/L with sevelamer. Mean serum phosphorus concentrations remained within Kidney Disease Outcomes Quality Initiative target range (1.13-1.78 mmol/L) for both treatment groups. Mean (SD) daily tablet number over the 28-week extension study was lower for sucroferric oxyhydroxide (4.0 ± 1.5) versus sevelamer (10.1 ± 6.6). Patient adherence was 86.2% with sucroferric oxyhydroxide versus 76.9% with sevelamer. Mean serum ferritin concentrations increased over the extension study in both treatment groups, but transferrin saturation (TSAT), iron and hemoglobin concentrations were generally stable. Gastrointestinal-related adverse events were similar and occurred early with both treatments, but decreased over time. The serum phosphorus-lowering effect of sucroferric oxyhydroxide was maintained over 1 year and associated with a lower pill burden, compared with sevelamer

  11. Extending the basic function of lattice oxygen in lepidocrocite titanate - The conversion of intercalated fatty acid to liquid hydrocarbon fuels

    Science.gov (United States)

    Maluangnont, Tosapol; Arsa, Pornanan; Sooknoi, Tawan

    2017-12-01

    We report herein the basicity of the external and internal lattice oxygen (OL) in lepidocrocite titanates with respect to CO2 and palmitic acid, respectively. Several compositions have been tested with different types of the metal M aliovalently (co)substituted for Ti, K0.8[MyTi2-y]O4 (M = Li, Mg, Fe, Co, Ni, Cu, Zn, Cu/Ni and Cu/Zn). The low CO2 desorption peak temperature (70-100 °C) suggests that the external OL sites are weakly basic similar to TiO2. However, the internal OL sites are sufficiently basic to deprotonate palmitic acid, forming the intercalated potassium palmitate at the interlayer spaces. The latter serves as a two-dimensional (2D) molecular reactor for the production of liquid hydrocarbon fuels via deoxygenation under atmospheric N2. A relationship has been observed between the yield of the liquid products vs the partial charge of the lattice oxygen (δO). Since the deoxygenation pathway is highly dependent on the metal substitution, the redox-active sites might also play some roles. The co-substituted K0.8[Cu0.2Ni0.2]Ti1.6O4 produced 68.0% yield of the liquid products, with 51% saturated and 15% unsaturated C15 hydrocarbons at 350 °C.

  12. Synthesis of aluminum oxy-hydroxide nanofibers from porous anodic alumina

    Energy Technology Data Exchange (ETDEWEB)

    Jha, Himendra; Kikuchi, Tatsuya; Sakairi, Masatoshi; Takahashi, Hideaki [Laboratory of Interface Microstructure Analysis (LIMSA), Division of Materials Science and Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)], E-mail: himendra@eng.hokudai.ac.jp

    2008-10-01

    A novel method for the synthesis of aluminum oxy-hydroxide nanofibers from a porous anodic oxide film of aluminum is demonstrated. In the present method, the porous anodic alumina not only acts as a template, but also serves as the starting material for the synthesis. The porous anodic alumina film is hydrothermally treated for pore-sealing, which forms aluminum oxy-hydroxide inside the pores of the oxide film as well as on the surface of the film. The hydrothermally sealed porous oxide film is immersed in the sodium citrate solution, which selectively etches the porous aluminum oxide from the film, leaving the oxy-hydroxide intact. The method is simple and gives highly uniform aluminum oxy-hydroxide nanofibers. Moreover, the diameter of the nanofibers can be controlled by controlling the pore size of the porous anodic alumina film, which depends on the anodizing conditions. Nanofibers with diameters of about 38-85 nm, having uniform shape and size, were successfully synthesized using the present method.

  13. Kinetics of microbial Fe(III) oxyhydroxide reduction : The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, S.C.

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  14. Synthesis of aluminum oxy-hydroxide nanofibers from porous anodic alumina

    International Nuclear Information System (INIS)

    Jha, Himendra; Kikuchi, Tatsuya; Sakairi, Masatoshi; Takahashi, Hideaki

    2008-01-01

    A novel method for the synthesis of aluminum oxy-hydroxide nanofibers from a porous anodic oxide film of aluminum is demonstrated. In the present method, the porous anodic alumina not only acts as a template, but also serves as the starting material for the synthesis. The porous anodic alumina film is hydrothermally treated for pore-sealing, which forms aluminum oxy-hydroxide inside the pores of the oxide film as well as on the surface of the film. The hydrothermally sealed porous oxide film is immersed in the sodium citrate solution, which selectively etches the porous aluminum oxide from the film, leaving the oxy-hydroxide intact. The method is simple and gives highly uniform aluminum oxy-hydroxide nanofibers. Moreover, the diameter of the nanofibers can be controlled by controlling the pore size of the porous anodic alumina film, which depends on the anodizing conditions. Nanofibers with diameters of about 38-85 nm, having uniform shape and size, were successfully synthesized using the present method

  15. Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

    Energy Technology Data Exchange (ETDEWEB)

    Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.; Wirth, Richard; Chan, Clara S.; McCollom, Thomas; Bach, Wolfgang; Edwards, Katrina J.

    2008-05-22

    Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and highresolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe1-xS, 0<_ x<_ 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe mu EXAFS spectroscopy and mu XRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O6 octahedral linkages. Double corner-sharing Fe-O6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that

  16. Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

    International Nuclear Information System (INIS)

    Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.; Wirth, Richard; Chan, Clara S.; McCollom, Thomas; Bach, Wolfgang; Edwards, Katrina J.

    2008-01-01

    Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and high-resolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe 1-x S, 0 (le) x (le) 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe mu EXAFS spectroscopy and mu XRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O 6 octahedral linkages. Double corner-sharing Fe-O 6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that

  17. Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

    Science.gov (United States)

    Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

    2018-04-01

    Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

  18. The desorption of Phosphorous (32 P) fixed on iron and aluminum oxy-hydroxide surfaces by the soil microbial biomass

    International Nuclear Information System (INIS)

    Araujo, Lilian Maria Cesar de.

    1995-02-01

    This work determines whether the soil microbial biomass, with an ample supply of available C, can utilize P adsorber in the surfaces of oxy-hydroxides of Fe or Al of soil-P deficient soils. To simulate the surfaces of the natural Fe and Al compounds, synthetic oxy-hydroxides of Fe and Al, impregnated in strips of filter paper, and containing P tagged with 32 P, were used. (author). 60 refs., 7 figs., 7 tabs

  19. Study the properties of activated carbon and oxyhydroxide aluminum as sorbents for removal humic substances from natural waters

    International Nuclear Information System (INIS)

    Shiyan, L N; Machekhina, K I; Gryaznova, E N

    2016-01-01

    The present work relates to the problem of high-quality drinking water supply using processes of adsorption on activated carbon and aluminum oxyhydroxide for removal humic- type organic substances. Also the paper reports on sorbtion properties of the activeted carbon Norit SA UF and oxyhydroxide aluminum for removal humic substances. It was found out that the maximum adsorption capacity of activated carbon to organic substances is equal to 0.25 mg/mg and aluminum oxyhydroxide is equal to 0.3 mg/mg. It is shown that the maximum adsorption capacity of activated carbon Norit SA UF to iron (III) ions is equal to 0.0045 mg/mg and to silicon ions is equal to 0.024 mg/mg. Consequently, the aluminum oxyhydroxide has better adsorption characteristics in comparison with the activated carbon for removal of humic substances, iron and silicon ions. It is associated with the fact that activated carbon has a large adsorption surface, and this is due to its porous structure, but not all molecules can enter into these pores. Therefore, the fibrous structure of aluminum oxyhydroxide promotes better sorption capacity. The presented results suggest that activated carbon Norit SA UF and aluminum oxyhydroxide can be used as sorbents for removal humic substances or other organic substances from groundwater and natural waters. (paper)

  20. Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

    Science.gov (United States)

    Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

    2017-01-01

    The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

  1. One-year efficacy and safety of the iron-based phosphate binder sucroferric oxyhydroxide in patients on peritoneal dialysis.

    Science.gov (United States)

    Floege, Jürgen; Covic, Adrian C; Ketteler, Markus; Mann, Johannes; Rastogi, Anjay; Spinowitz, Bruce; Rakov, Viatcheslav; Lisk, Laura J; Sprague, Stuart M

    2017-11-01

    Sucroferric oxyhydroxide is a noncalcium, iron-based phosphate binder that demonstrated sustained serum phosphorus control, good tolerability and lower pill burden compared with sevelamer carbonate (sevelamer) in a Phase 3 study conducted in dialysis patients. This subanalysis examines the efficacy and tolerability of sucroferric oxyhydroxide and sevelamer in the peritoneal dialysis (PD) patient population. The initial study (NCT01324128) and its extension (NCT01464190) were multicenter, Phase 3, open-label, randomized (2:1), active-controlled trials comparing sucroferric oxyhydroxide (1.0-3.0 g/day) with sevelamer (2.4-14.4 g/day) in dialysis patients over 52 weeks in total. In the overall study, 84/1055 (8.1%) patients received PD and were eligible for efficacy analysis (sucroferric oxyhydroxide, n = 56; sevelamer, n = 28). The two groups were broadly comparable to each other and to the overall study population. Serum phosphorus concentrations decreased comparably with both phosphate binders by week 12 (mean change from baseline - 0.6 mmol/L). Over 52 weeks, sucroferric oxyhydroxide effectively reduced serum phosphorus concentrations to a similar extent as sevelamer; 62.5% and 64.3% of patients, respectively, were below the Kidney Disease Outcomes Quality Initiative target range (≤1.78 mmol/L). This was achieved with a lower pill burden (3.4 ± 1.3 versus 8.1 ± 3.7 tablets/day) with sucroferric oxyhydroxide compared with sevelamer. Treatment adherence rates were 91.2% with sucroferric oxyhydroxide and 79.3% with sevelamer. The proportion of patients reporting at least one treatment-emergent adverse event was 86.0% with sucroferric oxyhydroxide and 93.1% with sevelamer. The most common adverse events with both treatments were gastrointestinal: diarrhea and discolored feces with sucroferric oxyhydroxide and nausea, vomiting and constipation with sevelamer. Sucroferric oxyhydroxide is noninferior to sevelamer for controlling serum

  2. Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.; Vörös, Márton; Galli, Giulia; Stahl, Shannon S.; Hammes-Schiffer, Sharon

    2017-03-06

    NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.

  3. Characterization and comparison of iron oxyhydroxide precipitates from biotic and abiotic groundwater treatments

    DEFF Research Database (Denmark)

    Arturi, Katarzyna R.; Bender Koch, Christian; Søgaard, Erik G.

    2017-01-01

    Removal of iron is an important step in groundwater treatment for drinking water production. It is performed to prevent organoleptic issues and clogging in water supply systems. Iron can be eliminated with a purely physico-chemical (abiotic) method or biotically with the help of iron......-oxidizing bacteria (FeOB). Each of the purification methods requires different operating conditions and results in formation of iron oxyhydroxide (FeOOH) precipitates. Knowledge about the differences in composition and properties of the biotic and abiotic precipitates is desirable from a technical, but also...

  4. The gas phase oxide and oxyhydroxide chemistry of trace amounts of rhenium

    International Nuclear Information System (INIS)

    Eichler, R.; Eichler, B.; Jost, D.T.; Dressler, R.; Tuerler, A.; Gaeggeler, H.W.

    1999-01-01

    In preparation of experiments to investigate the chemical properties of bohrium (Bh, element 107) the behaviour of Re, its lighter homologue in group 7, was studied in different oxidizing chemical systems. The adsorption data of Re oxide and oxyhydroxide compounds on quartz surfaces were evaluated from results of thermochromatography experiments and confirmed in isothermal gas chromatography experiments applying 1 cm as standard state for the simple gas adsorption process: X(g) ↔ X(ads) (X = ReO 3 , HReO 4 ) ΔH ads (ReO 3 ) = -190 ± 10 kJ/mol; ΔS ads (ReO 3 ) = -179±30 J/mol K; ΔH ads (HReO 4 ) = -77 ± 5 kJ/mol; ΔS ads (HReO 4 ) = -187±50 J/mol K. An on-line separation method for oxides and oxyhydroxides of short lived Re isotopes using isothermal high temperature gas-solid adsorption chromatography was developed. Separation yields and times of group 7 elements from lanthanides (model for actinides), polonium and bismuth were determined using the model isotopes 169,170,174,176 Re, 152-155 Er, 151-154 Ho, 218 Po, and 214 Bi. An updated correlation function between the microscopic adsorption enthalpy and the macroscopic sublimation enthalpy was calculated from the experimental adsorption data of this work and literature data. (orig.)

  5. On the use of Mossbauer spectroscopy for characterisation of iron oxides and oxyhydroxides in soils

    DEFF Research Database (Denmark)

    Mørup, Steen; Ostenfeld, Christopher Worsøe

    2001-01-01

    An empirical expression for the dependence of the magnetic hyperfine field on the aluminium content and the particle size in iron oxides and oxyhydroxides is often used in Mossbauer studies of soil samples. According to this expression, the reduction of the hyperfine field in nanometer-sized part...... on the magnetic hyperfine splitting in Mossbauer spectra of magnetic nanoparticles. Therefore, an analysis of data, based on the empirical expression, which only takes into account the particle size and the aluminium content, can give erroneous results.......An empirical expression for the dependence of the magnetic hyperfine field on the aluminium content and the particle size in iron oxides and oxyhydroxides is often used in Mossbauer studies of soil samples. According to this expression, the reduction of the hyperfine field in nanometer...... discrepancy in the case of non-interacting hematite nanoparticles (accidentally) can be explained by the size dependence of the magnetic anisotropy constant. However, it is also pointed out that a third parameter, namely the strength of the inter-particle interactions, can have a significant influence...

  6. Multilayered films of cobalt oxyhydroxide nanowires/manganese oxide nanosheets for electrochemical capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Huajun [State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014 (China); ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Tang, Fengqiu; Mukherji, Aniruddh; Yan, Xiaoxia; Wang, Lianzhou (Max) Lu, Gao Qing [ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Lim, Melvin [Division of Environmental and Water Resources Engineering, School of Civil and Environmental Engineering, Nanyang Technological University, 639798 (Singapore)

    2010-01-15

    Multilayered films of cobalt oxyhydroxide nanowires (CoOOHNW) and exfoliated manganese oxide nanosheet (MONS) are fabricated by potentiostatic deposition and electrostatic self-assembly on indium-tin oxide coated glass substrates. The morphology and chemical composition of these films are characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS) and the potential application as electrochemical supercapacitors are investigated using cyclic voltammetry and charge-discharge measurements. These ITO/CoOOHNW/MONS multilayered film electrodes exhibit excellent electrochemical capacitance properties, including high specific capacitance (507 F g{sup -1}) and long cycling durability (less 2% capacity loss after 5000 charge/discharge cycles). These characteristics indicate that these newly developed films may find important application for electrochemical capacitors. (author)

  7. Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles

    DEFF Research Database (Denmark)

    Gilbert, Benjamin; Katz, Jordan E.; Huse, Nils

    2013-01-01

    photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported....... We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(iii)–dye complex. Following light absorption, excited state relaxation times of the dye of 115...... a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer...

  8. Formation of magnetic aluminium oxyhydroxide nanorods and use for hyperthermal effects

    International Nuclear Information System (INIS)

    Jha, Himendra; Schmidt-Stein, Felix; Shrestha, Nabeen K; Schmuki, Patrik; Kettering, Melanie; Hilger, Ingrid

    2011-01-01

    In the present work, we show that a porous alumina template can easily be filled with magnetic nanoparticles and then be sealed by a hot water treatment (by forming an aluminium oxyhydroxide (AlOOH) sealant layer). The porous layer then can be separated from the substrate by an etch to form free magnetic AlOOH nano-capsules. The process allows for a straightforward and highly defined size control of the magnetic units and can easily be scaled up. Furthermore, as AlOOH is biocompatible and has been used as a drug adjuvant for human use, the nanorod shaped capsules are highly promising for biomedical applications such as hyperthermal effects (heating in alternating magnetic fields).

  9. Effects of Gold Substrates on the Intrinsic and Extrinsic Activity of High-Loading Nickel-Based Oxyhydroxide Oxygen Evolution Catalysts

    DEFF Research Database (Denmark)

    Chakthranont, Pongkarn; Kibsgaard, Jakob; Gallo, Alessandro

    2017-01-01

    We systematically investigate the effects of Au substrates on the oxygen evolution activities of cathodically electrodeposited nickel oxyhydroxide (NiOOH), nickel–iron oxyhydroxide (NiFeOOH), and nickel–cerium oxyhydroxide (NiCeOOH) at varying loadings from 0 to 2000 nmol of metal/cm2. We determi...... high geometric current densities on flat substrates. By investigating the mass and site specific activities as a function of loading, we bridge the practical geometric activity to the fundamental intrinsic activity....

  10. The secret behind the success of doping nickel oxyhydroxide with iron.

    Science.gov (United States)

    Fidelsky, Vicky; Toroker, Maytal Caspary

    2017-03-15

    Discovering better catalysts for water splitting is the holy grail of the renewable energy field. One of the most successful water oxidation catalysts is nickel oxyhydroxide (NiOOH), which is chemically active only as a result of doping with Fe. In order to shed light on how Fe improves efficiency, we perform Density Functional Theory +U (DFT+U) calculations of water oxidation reaction intermediates of Fe substitutional doped NiOOH. The results are analyzed while considering the presence of vacancies that we use as probes to test the effect of adding charge to the surface. We find that the smaller electronegativity of the Fe dopant relative to Ni allows the dopant to have several possible oxidation states with less energy penalty. As a result, the presence of vacancies which alters local oxidation states does not affect the low overpotential of Fe-doped NiOOH. We conclude that the secret to the success of doping NiOOH with iron is the ability of iron to easily change oxidation states, which is critical during the chemical reaction of water oxidation.

  11. Synthesis of LiFePO{sub 4}/polyacenes using iron oxyhydroxide as an iron source

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Guiling; Zhang, Xianfa; Liu, Jing; He, Xingguang; Wang, Jiawei; Xie, Haiming; Wang, Rongshun [Institute of Functional Materials, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024 (China); LIB Engineering Laboratory, Materials Science and Technology Center, Changchun, Jilin 130024 (China)

    2010-02-15

    LiFePO{sub 4}/polyacenes (PAS) composite is synthesized by iron oxyhydroxide as a new raw material and phenol-formaldehyde resin as both reducing agent and carbon source. The mechanism of the reaction is outlined by the analysis of XRD, FTIR as well as TG/DSC. The results show that the formation of LiFePO{sub 4} is started at 300 C, and above 550 C, the product can be mainly ascribed to olivine LiFePO{sub 4}. The electrochemical properties of the synthesized composites are investigated by charge-discharge tests. It is found that the prepared sample at 750 C (S750) has a better electrochemical performance than samples prepared at other temperatures. A discharge capacity of 158 mAh g{sup -1} is delivered at 0.2 C. Under high discharge rate of 10 C, a discharge capacity of 145 mAh g{sup -1} and good capacity retention of 93% after 800 cycles are achieved. The morphology of S750 and PAS distribution in it are investigated by SEM and TEM. (author)

  12. Quantitative characterization of the atomic-scale structure of oxyhydroxides in rusts formed on steel surfaces

    International Nuclear Information System (INIS)

    Saito, M.; Suzuki, S.; Kimura, M.; Suzuki, T.; Kihira, H.; Waseda, Y.

    2005-01-01

    Quantitative X-ray structural analysis coupled with anomalous X-ray scattering has been used for characterizing the atomic-scale structure of rust formed on steel surfaces. Samples were prepared from rust layers formed on the surfaces of two commercial steels. X-ray scattered intensity profiles of the two samples showed that the rusts consisted mainly of two types of ferric oxyhydroxide, α-FeOOH and γ-FeOOH. The amounts of these rust components and the realistic atomic arrangements in the components were estimated by fitting both the ordinary and the environmental interference functions with a model structure calculated using the reverse Monte Carlo simulation technique. The two rust components were found to be the network structure formed by FeO 6 octahedral units, the network structure itself deviating from the ideal case. The present results also suggest that the structural analysis method using anomalous X-ray scattering and the reverse Monte Carlo technique is very successful in determining the atomic-scale structure of rusts formed on the steel surfaces

  13. Galvanic Corrosion of Lead by Iron (Oxyhydr)Oxides: Potential Impacts on Drinking Water Quality.

    Science.gov (United States)

    Trueman, Benjamin F; Sweet, Gregory A; Harding, Matthew D; Estabrook, Hayden; Bishop, D Paul; Gagnon, Graham A

    2017-06-20

    Lead exposure via drinking water remains a significant public health risk; this study explored the potential effects of upstream iron corrosion on lead mobility in water distribution systems. Specifically, galvanic corrosion of lead by iron (oxyhydr)oxides was investigated. Coupling an iron mineral cathode with metallic lead in a galvanic cell increased lead release by 531 μg L -1 on average-a 9-fold increase over uniform corrosion in the absence of iron. Cathodes were composed of spark plasma sintered Fe 3 O 4 or α-Fe 2 O 3 or field-extracted Fe 3 O 4 and α-FeOOH. Orthophosphate immobilized oxidized lead as insoluble hydroxypyromorphite, while humic acid enhanced lead mobility. Addition of a humic isolate increased lead release due to uniform corrosion by 81 μg L -1 and-upon coupling lead to a mineral cathode-release due to galvanic corrosion by 990 μg L -1 . Elevated lead in the presence of humic acid appeared to be driven by complexation, with 208 Pb and UV 254 size-exclusion chromatograms exhibiting strong correlation under these conditions (R 2 average = 0.87). A significant iron corrosion effect was consistent with field data: lead levels after lead service line replacement were greater by factors of 2.3-4.7 at sites supplied by unlined cast iron distribution mains compared with the alternative, lined ductile iron.

  14. Sequestration of non-pure carbon dioxide streams in iron oxyhydroxide-containing saline repositories

    Science.gov (United States)

    Garcia, S.; Rosenbauer, Robert J.; Palandri, James L.; Maroto-Valer, M. Mercedes

    2012-01-01

    Iron oxyhydroxide, goethite (α-FeOOH), was evaluated as a potential formation mineral reactant for trapping CO2 in a mineral phase such as siderite (FeCO3), when a mixture of CO2-SO 2 flue gas is injected into a saline aquifer. Two thermodynamic simulations were conducted, equilibrating a CO2-SO2 fluid mixture with a NaCl-brine and Fe-rich rocks at 150 °C and 300 bar. The modeling studies evaluated mineral and fluid composition at equilibrium and the influence of pH buffering in the system. Results show siderite precipitates both in the buffered and unbuffered system; however, the presence of an alkaline pH buffer enhances the stability of the carbonate. Based on the model, an experiment was designed to compare with thermodynamic predictions. A CO2-SO2 gas mixture was reacted in 150 ml of NaCl-NaOH brine containing 10 g of goethite at 150 °C and 300 bar for 24 days. Mineralogical and brine chemistry confirmed siderite as the predominant reaction product in the system. Seventy-six mg of CO2 are sequestered in siderite per 10 g of goethite.

  15. The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Tresintsi, S. [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Simeonidis, K., E-mail: ksime@physics.auth.gr [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Department of Mechanical Engineering, University of Thessaly, 38334 Volos (Greece); Pliatsikas, N.; Vourlias, G.; Patsalas, P. [Laboratory of Applied Physics, Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Mitrakas, M. [Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

    2014-05-01

    This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted in distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.

  16. Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

    Science.gov (United States)

    Wang, Dengjun; Bradford, Scott A.; Harvey, Ronald W.; Gao, Bin; Cang, Long; Zhou, Dongmei

    2012-01-01

    Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0–10 mg L–1), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0–0.75), and pH (6.0–10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L–1, greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.

  17. Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

    International Nuclear Information System (INIS)

    Cances, Benjamin; Benedetti, Marc; Farges, Francois; Brown, Gordon E. Jr.

    2007-01-01

    Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite

  18. Adsorption equilibrium of uranium on iron oxyhydroxide-PVA hydrogel spheres

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Armindo; Campos, Victor B.; Ribeiro, Luciana S.; Escanio, Camila A.; Silva, Edilaine F.; Oliveira, Felipe W., E-mail: santosa@cdtn.br, E-mail: vbc@cdtn.br, E-mail: lsr@cdtn.br, E-mail: cae@cdtn.br, E-mail: efd@cdtn.br, E-mail: fwfo@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2015-07-01

    Uranium and its compounds are considered strategic mineral resources due to its usage as an energy source and war material. They are harmful to human health. Thus, liquid waste containing low uranium content (≤100 mgU/L), from the mining and/or uranium reprocessing plants or even of the research center activities require the development of methods for their treatment, in a way to reduce its content to 15 μgU/L. Adsorption is one of these methods; it requires the synthesis of preferably spherical adsorbents, chemically and physically stable and with high adsorptive capacity. The sol-gel process can synthesize adsorbents having such characteristics, prioritizing the nanostructuring of iron oxyhydroxide in a hydrophilic PVA (polyvinyl alcohol) polymer network, which had an accessible pore structure (micro-, meso- and macropores + macroholes). We successfully obtained iron-PVA hydrogel spheres with (3433 ± 63 μm) and without (2833 ± 69 μm) macroholes. Both types of spheres have good mechanical strength and chemical stability in the 2-9 pH range. Adsorptive capacity: 413.22 mgU/g (with macroholes; Freundlich model) and 249.38 mgU/g (without macroholes; Langmuir and Freundlich models), at pH 5-6, 30 °C, and 6 h. With 280 mL of with-macrohole hydrogel spheres, we can treat 1 L of liquid waste (100 mgU/L) and reduce uranium content to 20 μgU/L. (author)

  19. Adsorption equilibrium of uranium on iron oxyhydroxide-PVA hydrogel spheres

    International Nuclear Information System (INIS)

    Santos, Armindo; Campos, Victor B.; Ribeiro, Luciana S.; Escanio, Camila A.; Silva, Edilaine F.; Oliveira, Felipe W.

    2015-01-01

    Uranium and its compounds are considered strategic mineral resources due to its usage as an energy source and war material. They are harmful to human health. Thus, liquid waste containing low uranium content (≤100 mgU/L), from the mining and/or uranium reprocessing plants or even of the research center activities require the development of methods for their treatment, in a way to reduce its content to 15 μgU/L. Adsorption is one of these methods; it requires the synthesis of preferably spherical adsorbents, chemically and physically stable and with high adsorptive capacity. The sol-gel process can synthesize adsorbents having such characteristics, prioritizing the nanostructuring of iron oxyhydroxide in a hydrophilic PVA (polyvinyl alcohol) polymer network, which had an accessible pore structure (micro-, meso- and macropores + macroholes). We successfully obtained iron-PVA hydrogel spheres with (3433 ± 63 μm) and without (2833 ± 69 μm) macroholes. Both types of spheres have good mechanical strength and chemical stability in the 2-9 pH range. Adsorptive capacity: 413.22 mgU/g (with macroholes; Freundlich model) and 249.38 mgU/g (without macroholes; Langmuir and Freundlich models), at pH 5-6, 30 °C, and 6 h. With 280 mL of with-macrohole hydrogel spheres, we can treat 1 L of liquid waste (100 mgU/L) and reduce uranium content to 20 μgU/L. (author)

  20. Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth.

    Science.gov (United States)

    Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F

    2013-02-01

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L(2,3) absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

  1. Geochemical study of evaporite and clay mineral-oxyhydroxide samples from the Waste Isolation Pilot Plant site

    International Nuclear Information System (INIS)

    Brookins, D.G.

    1993-06-01

    Samples of clay minerals, insoluble oxyhydroxides, and their host evaporites from the WIPP site have been studied for their major and minor elements abundances, x-ray diffraction characteristics, K-Ar ages, and Rb-Sr ages. This study was undertaken to determine their overall geochemical characteristics and to investigate possible interactions between evaporates and insoluble constituents. The evaporite host material is water-soluble, having Cl/Br ratios typical of marine evaporites, although the Br content is low. Insoluble material (usually a mixture of clay minerals and oxyhydroxide phases) yields very high Cl/Br ratios, possibly because of Cl from admixed halide minerals. This same material yields K/Rb and Th/U ratios in the normal range for shales; suggesting little, if any, effect of evaporite-induced remobilization of U, K, or Rb in the insoluble material. The rare-earth element (REE) data also show normal REE/chondrite (REE/CHON) distribution patterns, supporting the K/Rb and Th/U data. Clay minerals yield K-Ar dates in the range 365 to 390 Ma and a Rb-Sr isochron age of 428 ± 7 Ma. These ages are well in excess of the 220- to 230-Ma formational age of the evaporites, and confirm the detrital origin of the clays. The ages also show that any evaporite or clay mineral reactions that might have occurred at or near the time of sedimentation and diagenesis were not sufficient to reset the K-Ar and Rb-Sr systematics of the clay minerals. Further, x-ray data indicate a normal evaporitic assemblage of clay minerals and Fe-rich oxyhydroxide phases. The clay minerals and other insoluble material appear to be resistant to the destructive effects of their entrapment in the evaporites, which suggests that these insoluble materials would be good getters for any radionuclides (hypothetically) released from the storage of radioactive wastes in the area

  2. Structural Properties of the Cr(III)-Fe(III) (Oxy)Hydroxide Compositional Series: Insights for a Nanomaterial 'Solid Solution'

    International Nuclear Information System (INIS)

    Tang, Y.; Zhang, L.; Michel, F.M.; Harrington, R.; Parise, J.B.; Reeder, R.J.

    2010-01-01

    Chromium(III) (oxy)hydroxide and mixed Cr(III)-Fe(III) (oxy)hydroxides are environmentally important compounds for controlling chromium speciation and bioaccessibility in soils and aquatic systems and are also industrially important as precursors for materials and catalyst synthesis. However, direct characterization of the atomic arrangements of these materials is complicated because of their amorphous X-ray properties. This study involves synthesis of the complete Cr(III)-Fe(III) (oxy)hydroxide compositional series, and the use of complementary thermal, microscopic, spectroscopic, and scattering techniques for the evaluation of their structural properties. Thermal analysis results show that the Cr end member has a higher hydration state than the Fe end member, likely associated with the difference in water exchange rates in the first hydration spheres of Cr(III) and Fe(III). Three stages of weight loss are observed and are likely related to the loss of surface/structural water and hydroxyl groups. As compared to the Cr end member, the intermediate composition sample shows lower dehydration temperatures and a higher exothermic transition temperature. XANES analysis shows Cr(III) and Fe(III) to be the dominant oxidation states. XANES spectra also show progressive changes in the local structure around Cr and Fe atoms over the series. Pair distribution function (PDF) analysis of synchrotron X-ray total scattering data shows that the Fe end member is nanocrystalline ferrihydrite with an intermediate-range order and average coherent domain size of ∼27 (angstrom). The Cr end member, with a coherent domain size of ∼10 (angstrom), has only short-range order. The PDFs show progressive structural changes across the compositional series. High-resolution transmission electron microscopy (HRTEM) results also show the loss of structural order with increasing Cr content. These observations provide strong structural evidence of chemical substitution and progressive structural

  3. Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

    Science.gov (United States)

    Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

    2018-01-01

    Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where

  4. Rapid sedimentation of iron oxyhydroxides in an active hydrothermal shallow semi-enclosed bay at Satsuma Iwo-Jima Island, Kagoshima, Japan

    Science.gov (United States)

    Kiyokawa, Shoichi; Ueshiba, Takuya

    2015-04-01

    Hydrothermal activity is common in the fishing port of Nagahama Bay, a small semi-enclosed bay located on the southwest coast of Satsuma Iwo-Jima Island (38 km south of Kyushu Island, Japan). The bay contains red-brown iron oxyhydroxides and thick deposits of sediment. In this work, the high concentration and sedimentation rates of oxyhydroxide in this bay were studied and the sedimentary history was reconstructed. Since dredging work in 1998, a thickness of 1.0-1.5 m of iron oxyhydroxide-rich sediments has accumulated on the floor of the bay. To estimate the volume of iron oxyhydroxide sediments and the amount discharged from hydrothermal vents, sediment traps were operated for several years and 13 sedimentary core samples were collected to reconstruct the 10-year sedimentary history of Nagahama Bay. To confirm the timing of sedimentary events, the core data were compared with meteorological records obtained on the island, and the ages of characteristic key beds were thus identified. The sedimentation rate of iron oxyhydroxide mud was calculated, after correcting for sediment input from other sources. The sediments in the 13 cores from Nagahama Bay consist mainly of iron oxyhydroxide mud, three thick tephra beds, and a topmost thick sandy mud bed. Heavy rainfall events in 2000, 2001, 2002, and 2004-2005 coincide with tephra beds, which were reworked from Iwo-Dake ash deposits to form tephra-rich sediment. Strong typhoon events with gigantic waves transported outer-ocean-floor sediments and supplied quartz, cristobalite, tridymite, and albite sands to Nagahama Bay. These materials were redeposited together with bay sediments as the sandy mud bed. Based on the results from the sediment traps and cores, it is estimated that the iron oxyhydroxide mud accumulated in the bay at the relatively rapid rate of 33.3 cm/year (from traps) and 2.8-4.9 cm/year (from cores). The pore water contents within the sediment trap and core sediments are 73%-82% and 47%-67%, respectively

  5. Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: a potential material for the treatment of various toxic heavy metals and its toxicity.

    Science.gov (United States)

    Chung, Seung-Gun; Ryu, Jae-Chun; Song, Mi-Kyung; An, Byungryul; Kim, Song-Bae; Lee, Sang-Hyup; Choi, Jae-Woo

    2014-02-28

    The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1mgg(-1)) and arsenic (71.9mgg(-1)) compared with other adsorbents, such as DABs (158.1 and 0.0mgg(-1)), SZIB (42.9 and 0.0mgg(-1)) and SZMIOIB (54.0 and 5.9mgg(-1)) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer-Emmett-Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for heavy metal treatment than the powdered form. This research provides promising results for the application of MIOIBs as an adsorbent for various heavy metals from wastewater and sewage. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Defect Chemistry of a Zinc-Doped Lepidocrocite Titanate CsxTi2−x/2Znx/2O4 (x = 0.7) and its Protonic Form

    DEFF Research Database (Denmark)

    Gao, Tao; Fjellvåg, Helmer; Norby, Poul

    2009-01-01

    A zinc-doped layered titanate CsxTi2−x/2Znx/2O4 (x = 0.7) with lepidocrocite (γ-FeOOH)-type layered structure was prepared via solid-state calcination. A complete extraction of both lattice Zn atoms and interlayer Cs ions was observed upon acid exchange, producing a protonic form H2xTi2−x/2x/2O4·H2....... The protonic titanate H2xTi2−x/2x/2O4·H2O readily underwent delamination to produce its molecular single sheets Ti1−δδO24δ− (δ = 0.175) with distinctive two-dimensional morphology and small thickness (1 nm), suggesting promising applications in the assembly of functional nanostructures....

  7. Mechanism of pyrrhotite formation from ferric oxyhydroxide catalyst; Kokoritsu sekitan ekika shokubai no kaihatsu (Okishi suisankatetsu shokubai karano pyrrhotite seisei kyodo)

    Energy Technology Data Exchange (ETDEWEB)

    Tazawa, K.; Koyama, T.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    It is thought that iron-based catalysts for coal liquefaction exercise their catalytic activity by forming pyrrhotite (Fe(1-x)S). However, there are still a lot of unknown problems remained concerning the formation and agglomeration behaviors of pyrrhotite. These make a difficulty for improving the activity of iron-based catalysts. In this study, sulfiding behaviors of {alpha}-iron oxyhydroxide ({alpha}-FeOOH) and {gamma}-iron oxyhydroxide ({gamma}-FeOOH) were investigated to reveal the formation and agglomeration behaviors of pyrrhotite. It was found that pyrrhotite was easily converted from ferric oxyhydroxide catalysts having large specific surface areas at the sulfiding temperature below 250{degree}C, and fine crystallites of pyrrhotite were formed at the initial stage of sulfiding. Crystal growth of pyrrhotite at the sulfiding temperature over 350{degree}C depended on the catalyst forms. It was also found that smaller crystallites of pyrrhotite were formed from {gamma}-FeOOH than from {alpha}-FeOOH and amorphous iron oxyhydroxide. 5 refs., 7 figs., 1 tab.

  8. Nanoscale Titanium Dioxide (nTiO2) Transport in Water-Saturated Natural Sediments: Influence of Soil Organic Matter and Fe/Al Oxyhydroxides

    Science.gov (United States)

    Fisher-Power, L.; Cheng, T.

    2017-12-01

    Transport of engineered nanoparticles (ENP) in subsurface environments has important implications to water quality and soil contamination. Although extensive research has been conducted to understand the effects of water chemistry on ENP transport, less attention has been paid to influences from the transport medium/matrix. The objective of this research is to investigate the effects of natural organic matter (NOM) and Fe/Al oxyhydroxides in a natural sediment on ENP transport. A sediment was collected and separated into four portions, one of which was unmodified, and the others treated to remove specific components (organic matter, Fe/Al oxyhydroxides, or both organic matter and Fe/Al oxyhydroxides). Transport of nanoscale titanium dioxide (nTiO2) in columns packed with quartz sand and each of the four types of the sediment under water-saturated conditions was studied. Our results showed that nTiO2 transport was strongly influenced by pH and sediment composition. When influent pH = 5, nTiO2 transport in all the sediments was low, as positively-charged nTiO2 was attracted to negatively charged NOM, quartz, and other minerals. nTiO2 transport was slightly enhanced in columns packed with untreated sediment or Fe/Al oxyhydroxides removed sediment due to dissolved organic matter generated by the partial dissolution of NOM, which adsorbed onto nTiO2 surface and reversed its zeta potential to negative. When influent pH = 9, nTiO2 transport was generally high since negatively-charged nTiO2 was repelled by negatively charged transport medium. However, in columns packed with the organic matter removed sediment or the Fe/Al oxyhydroxides removed sediment, nTiO2 transport was low. This was attributable to pH buffering by the sediment, which decreased pore water pH in the column, resulting in zeta potential change and electrostatic attraction between Fe/Al oxyhydroxides and nTiO2. This research demonstrates that electrostatic forces between nTiO2 and mineral/organic components

  9. Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: A potential material for the treatment of various toxic heavy metals and its toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Seung-Gun [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Ryu, Jae-Chun; Song, Mi-Kyung [Center for Integrated Risk Research, Cellular and Molecular Toxicology Laboratory, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); An, Byungryul [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Kim, Song-Bae [Environmental Functional Materials and Biocolloids Laboratory, Seoul National University, Seoul 151-921 (Korea, Republic of); Lee, Sang-Hyup [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Graduate School of Convergence Green Technology and Policy, Korea University, Seoul 136-701 (Korea, Republic of); Choi, Jae-Woo, E-mail: plead36@kist.re.kr [Center for Water Resource Cycle Research, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2014-02-01

    Graphical abstract: - Highlights: • Meso-iron-oxyhydroxide was found to be efficient for anion heavy metal adsorption. • The composite bead can simultaneously remove the cations and anions of heavy metals. • Powdered form had stronger cytotoxicity than did the granular form. • Adsorbent recovery is facilitated by granulation process of powder-type. - Abstract: The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1 mg g{sup −1}) and arsenic (71.9 mg g{sup −1}) compared with other adsorbents, such as DABs (158.1 and 0.0 mg g{sup −1}), SZIB (42.9 and 0.0 mg g{sup −1}) and SZMIOIB (54.0 and 5.9 mg g{sup −1}) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer–Emmett–Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for

  10. Textural and mineralogical characteristics of microbial fossils associated with modern and ancient iron (oxyhydr)oxides: terrestrial analogue for sediments in Gale Crater.

    Science.gov (United States)

    Potter-McIntyre, Sally L; Chan, Marjorie A; McPherson, Brian J

    2014-01-01

    Iron (oxyhydr)oxide microbial mats in modern to ∼100 ka tufa terraces are present in a cold spring system along Ten Mile Graben, southeastern Utah, USA. Mats exhibit morphological, chemical, and textural biosignatures and show diagenetic changes that occur over millennial scales. The Jurassic Brushy Basin Member of the Morrison Formation in the Four Corners region of the USA also exhibits comparable microbial fossils and iron (oxyhydr)oxide biosignatures in the lacustrine unit. Both the modern spring system and Brushy Basin Member represent alkaline, saline, groundwater-fed systems and preserve diatoms and other similar algal forms with cellular elaboration. Two distinct suites of elements (1. C, Fe, As and 2. C, S, Se, P) are associated with microbial fossils in modern and ancient iron (oxyhydr)oxides and may be potential markers for biosignatures. The presence of ferrihydrite in ∼100 ka fossil microbial mats and Jurassic rocks suggests that this thermodynamically unstable mineral may also be a potential biomarker. One of the most extensive sedimentary records on Mars is exposed in Gale Crater and consists of non-acidic clays and sulfates possibly of lacustrine origin. These terrestrial iron (oxyhydr)oxide examples are a valuable analogue because of similar iron- and clay-rich host rock compositions and will help (1) understand diagenetic processes in a non-acidic, saline lacustrine environment such as the sedimentary rocks in Gale Crater, (2) document specific biomediated textures, (3) demonstrate how biomediated textures might persist or respond to diagenesis over time, and (4) provide a ground truth library of textures to explore and compare in extraterrestrial iron (oxyhydr)oxides, where future explorations hope to detect past evidence of life.

  11. Magnetic properties of some selected, soil-related iron oxides and oxyhydroxides as probed by 57Fe Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    DeGrave, E.; Vandenberghe, R.E.; Bowen, L.H.

    1990-01-01

    In the last decade, Mossbauer spectroscopy has become an increasingly important and applied analytical tool for the characterization of environmental Fe-containing material. One of the most fastly growing application area of this technique is undoubtedly that of soils and sediments. Since such systems are commonly complex mixtures of various and mostly poorly crystalline compounds, much emphasis has been displayed towards the Mossbauer spectra of the pure constituents which, in the case of oxides and oxyhydroxides, usually concern well characterized synthetic samples. Many excellent and fairly complete review papers in that respect have been published in the recent literature and it is not the aim of the present authors to come up with still another one covering the same period. Only those results reported since 1985 and which have provided basically new insight concerning structural and/or magnetic properties have been selected. In addition, it has been attempted to collect some of the less-frequently dealt-with magnetic characteristics which more often have a fundamental importance rather than an analytical one, and which are therefore at the moment less-directly related and restricted to soil studies. A particular aspect that has received considerable attention in this paper is the effect on the Mossbauer spectra of the application of strong magnetic fields

  12. In situ fabrication of Ni-Co (oxy)hydroxide nanowire-supported nanoflake arrays and their application in supercapacitors.

    Science.gov (United States)

    Zheng, Xiaoyu; Quan, Honglin; Li, Xiaoxin; He, Hai; Ye, Qinglan; Xu, Xuetang; Wang, Fan

    2016-09-29

    Three-dimensional (3D) hybrid nanostructured arrays grown on a flexible substrate have recently attracted great attention owing to their potential application as supercapacitor electrodes in portable and wearable electronic devices. Here, we report an in situ conversion of Ni-Co active electrode materials for the fabrication of high-performance electrodes. Ni-Co carbonate hydroxide nanowire arrays on carbon cloth were initially synthesized via a hydrothermal method, and they were gradually converted to Ni-Co (oxy)hydroxide nanowire-supported nanoflake arrays after soaking in an alkaline solution. The evolution of the supercapacitor performance of the soaked electrode was investigated in detail. The areal capacitance increases from 281 mF cm -2 at 1 mA cm -2 to 3710 and 3900 mF cm -2 after soaking for 36 h and 48 h, respectively. More interestingly, the electrode also shows an increased capacitance with charge/discharge cycles due to the long-time soaking in KOH solution, suggesting novel cycling durability. The enhancement in capacitive performance should be related to the formation of a unique nanowire-supported nanoflake array architecture, which controls the agglomeration of nanoflakes, making them fully activated. As a result, the facile in situ fabrication of the hybrid architectural design in this study provides a new approach to fabricate high-performance Ni/Co based hydroxide nanostructure arrays for next-generation energy storage devices.

  13. Construction and evaluation of As(V) selective electrodes based on iron oxyhydroxide embedded in silica gel membrane

    International Nuclear Information System (INIS)

    Rodriguez, J.A.; Barrado, E.; Vega, M.; Prieto, F.; Lima, J.L.F.C.

    2005-01-01

    Two As(V) selective electrodes (with and without inner reference solution) have been developed using selective membranes based on iron oxyhydroxide embedded on silica gel mixed with ultrapure graphite at a 2/98 (w/w) ratio. The active component of the membrane was synthesised by means of the sol-gel technique and characterized by X-ray and FTIR spectroscopy. This compound shows a great affinity towards As(V) ions adsorbing 408 mg g -1 . Using 1 mol l -1 phosphate buffer (at a 1/1, v/v ratio) to adjust the pH and the ionic strength to 7 and 0.5 mol l -1 , respectively, the calibration curve is linear from 1.0 x 10 -1 to 1.0 x 10 -6 mol l -1 As(V), with a practical detection limit of 4 x 10 -7 mol l -1 (0.03 mg l -1 ) and a slope close to 30 mV decade -1 . The effect of potentially interfering ions was investigated. The accuracy and precision of the procedure have been tested on arsenic-free drinking water samples spiked with known amounts of arsenic and on groundwater samples containing high levels of arsenic. Total arsenic in these samples was determined after oxidation of As(III) with iodine at pH 7. The results of total As were comparable to those generated by ET-AAS

  14. Efficient photocatalytic degradation of perfluorooctanoic acid by a wide band gap p-block metal oxyhydroxide InOOH

    Science.gov (United States)

    Xu, Jingjing; Wu, Miaomiao; Yang, Jingwen; Wang, Zhengmei; Chen, Mindong; Teng, Fei

    2017-09-01

    In this work, we prepared a new wide band gap semiconductor, p-block metal oxyhydroxide InOOH, which exhibits efficient activity for perfluorooctanoic acid (PFOA) degradation under mild conditions and UV light irradiation. The apparent rate constant for PFOA degradation by InOOH is 27.6 times higher than that for P25 titania. Results show that ionized PFOA (C7F15COO-) can be adsorbed much more efficiently on the surface of InOOH than P25. Then, the adsorbed C7F15COO- can be decomposed directly by photo-generated holes to form C7F15COOrad radicals. This process is the key step for the photocalytic degradation of PFOA. Major degradation intermediates, fluoride ions and perfluorinated carboxylic acids (PFCAs) with shorter chain lengths were detected during PFOA degradation. A possible pathway for photocatalytic degradation of PFOA is proposed based on the experimental results. Therefore, this studies indicates a potential new material and method for the efficient treatment of PFCA pollutants under mild conditions.

  15. Iron oxyhydroxide nanorods with high electrochemical reactivity as a sensitive and rapid determination platform for 4-chlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuanyuan [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Britton Chance Center for Biomedical Photonics at Wuhan, National Laboratory for Optoelectronics-Hubei Bioinformatics & Molecular Imaging Key Laboratory, Systems Biology Theme, Department of Biomedical Engineering, College of Life Science and Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Cheng, Qin; Zheng, Meng [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Xin [Britton Chance Center for Biomedical Photonics at Wuhan, National Laboratory for Optoelectronics-Hubei Bioinformatics & Molecular Imaging Key Laboratory, Systems Biology Theme, Department of Biomedical Engineering, College of Life Science and Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Wu, Kangbing, E-mail: kbwu@hust.edu.cn [Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2016-04-15

    Highlights: • Prepared FeOOH nanorods exhibited high reactivity toward the oxidation of 4-CP. • Response signals and detection sensitivity of 4-CP increased greatly by FeOOH. • Highly-sensitive and rapid determination platform was developed for 4-CP. • Practical application in water samples was studied, and the accuracy was good. - Abstract: Iron oxyhydroxide (FeOOH) nanorods were prepared through solvothermal reaction, and characterized using Raman spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and scanning electron microscopy. Thereafter, the prepared FeOOH nanorods were used as sensing material to construct a novel detection platform for 4-chlorophenol (4-CP). The electrochemical behaviors of 4-CP were studied, and the oxidation peak currents increased greatly on the surface of FeOOH nanorods. The signal enhancement mechanism was studied for 4-CP, and it was found that the prepared FeOOH nanorods remarkably improved the electron transfer ability and surface adsorption efficiency of 4-CP. The influences of pH value, amount of FeOOH nanorods and accumulation time were examined. As a result, a highly-sensitive electrochemical method was developed for the rapid determination of 4-CP. The linear range was from 10 to 500 nM, and the detection limit was 3.2 nM. It was used in different water samples, and the results consisted with the values that obtained by high-performance liquid chromatography.

  16. Effects of Sucroferric Oxyhydroxide Compared to Lanthanum Carbonate and Sevelamer Carbonate on Phosphate Homeostasis and Vascular Calcifications in a Rat Model of Chronic Kidney Failure

    Directory of Open Access Journals (Sweden)

    Olivier Phan

    2015-01-01

    Full Text Available Elevated serum phosphorus, calcium, and fibroblast growth factor 23 (FGF23 levels are associated with cardiovascular disease in chronic renal disease. This study evaluated the effects of sucroferric oxyhydroxide (PA21, a new iron-based phosphate binder, versus lanthanum carbonate (La and sevelamer carbonate (Se, on serum FGF23, phosphorus, calcium, and intact parathyroid hormone (iPTH concentrations, and the development of vascular calcification in adenine-induced chronic renal failure (CRF rats. After induction of CRF, renal function was significantly impaired in all groups: uremic rats developed severe hyperphosphatemia, and serum iPTH increased significantly. All uremic rats (except controls then received phosphate binders for 4 weeks. Hyperphosphatemia and increased serum iPTH were controlled to a similar extent in all phosphate binder-treatment groups. Only sucroferric oxyhydroxide was associated with significantly decreased FGF23. Vascular calcifications of the thoracic aorta were decreased by all three phosphate binders. Calcifications were better prevented at the superior part of the thoracic and abdominal aorta in the PA21 treated rats. In adenine-induced CRF rats, sucroferric oxyhydroxide was as effective as La and Se in controlling hyperphosphatemia, secondary hyperparathyroidism, and vascular calcifications. The role of FGF23 in calcification remains to be confirmed.

  17. Clay minerals, metallic oxides and oxy-hydroxides and soil organic carbon distribution within soil aggregates in temperate forest soils

    Science.gov (United States)

    Gartzia-Bengoetxea, Nahia; Fernández-Ugalde, Oihane; Virto, Iñigo; Arias-González, Ander

    2017-04-01

    Soil mineralogy is of primary importance for key environmental services provided by soils like carbon sequestration. However, current knowledge on the effects of clay mineralogy on soil organic carbon (SOC) stabilization is based on limited and conflicting data. In this study, we investigated the relationship between clay minerals, metallic oxides and oxy-hydroxides and SOC distribution within soil aggregates in mature Pinus radiata D.Don forest plantations. Nine forest stands located in the same geographical area of the Basque Country (North of Spain) were selected. These stands were planted on different parent material (3 on each of the following: sandstone, basalt and trachyte). There were no significant differences in climate and forest management among them. Moreover, soils under these plantations presented similar content of clay particles. We determined bulk SOC storage, clay mineralogy, the content of Fe-Si-Al-oxides and oxyhydroxides and the distribution of organic C in different soil aggregate sizes at different soil depths (0-5 cm and 5-20 cm). The relationship between SOC and abiotic factors was investigated using a factor analysis (PCA) followed by stepwise regression analysis. Soils developed on sandstone showed significantly lower concentration of SOC (29 g C kg-1) than soils developed on basalts (97 g C kg-1) and trachytes (119 g C kg-1). The soils on sandstone presented a mixed clay mineralogy dominated by illite, with lesser amounts of hydroxivermiculite, hydrobiotite and kaolinite, and a total absence of interstratified chlorite/vermiculite. In contrast, the major crystalline clay mineral identified in the soils developed on volcanic rocks was interstratified chlorite/vermiculite. Nevertheless, no major differences were observed between basaltic and trachytic soils in the clay mineralogy. The selective extraction of Fe showed that the oxalate extractable iron was significantly lower in soils on sandstone (3.7%) than on basalts (11.2%) and

  18. Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

    Science.gov (United States)

    Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

    2017-08-01

    Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

  19. From 3D to 2D Co and Ni Oxyhydroxide Catalysts: Elucidation of the Active Site and Influence of Doping on the Oxygen Evolution Activity

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs

    2017-01-01

    Layered oxyhydroxides (ox-hys) of Ni and Co are among the most active catalysts for oxygen evolution in alkaline media. Their activities can be further tuned by delamination into single-layer oxide sheets or by means of doping. The active site for the reaction and how doping and delamination...... investigate the role of terrace and edge sites and use stability, catalytic activity, and electronic conductivity as evaluation criteria to pinpoint the best catalysts. We arrive at several important conclusions: the ox-hy surface is fully oxidized under oxygen evolution conditions, bulk terraces...

  20. The distribution of rare earth and other elements and the mineralogy of the iron oxyhydroxide phase in marine ferromanganese concretions from within Slupsk Furrow in the southern Baltic

    International Nuclear Information System (INIS)

    Ali, A.; Ikuta, K.; Latka, K.; Goerlich, E.A.; Kunzendorf, H.; Glasby, G.P.; Szefer, P.

    1998-01-01

    Rare earth element concentrations in ferromanganese concretions sampled from Slupsk Furrow in the Polish Exclusive Economic Zone are similar to those of concretions from the Gulf of Bothnia. The lack of positive Ce anomalies in the concretions from Slupsk Furrow indicates that they are formed under less oxidizing conditions than spheroidal concretions from the Gulf of Bothnia. Moessbauer studies indicate that poorly crystalline lepidocrosite is the principal iron oxyhydroxide mineral present in these concretions. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  1. Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces

    KAUST Repository

    Chassé , Alexander W.; Ohno, Tsutomu; Higgins, Steven R.; Amirbahman, Aria; Yildirim, Nadir; Parr, Thomas B.

    2015-01-01

    © 2015 American Chemical Society. The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

  2. Chemical Force Spectroscopy Evidence Supporting the Layer-by-Layer Model of Organic Matter Binding to Iron (oxy)Hydroxide Mineral Surfaces

    KAUST Repository

    Chassé, Alexander W.

    2015-08-18

    © 2015 American Chemical Society. The adsorption of dissolved organic matter (DOM) to metal (oxy)hydroxide mineral surfaces is a critical step for C sequestration in soils. Although equilibrium studies have described some of the factors controlling this process, the molecular-scale description of the adsorption process has been more limited. Chemical force spectroscopy revealed differing adhesion strengths of DOM extracted from three soils and a reference peat soil material to an iron (oxy)hydroxide mineral surface. The DOM was characterized using ultrahigh-resolution negative ion mode electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometry. The results indicate that carboxyl-rich aromatic and N-containing aliphatic molecules of DOM are correlated with high adhesion forces. Increasing molecular mass was shown to decrease the adhesion force between the mineral surface and the DOM. Kendrick mass defect analysis suggests that mechanisms involving two carboxyl groups result in the most stable bond to the mineral surface. We conceptualize these results using a layer-by-layer "onion" model of organic matter stabilization on soil mineral surfaces.

  3. Synthesis, Characterization and Application of Nano Lepidocrocite ...

    African Journals Online (AJOL)

    NICO

    Degradation of halogenated organic compounds using nanoparticles is one of the innovative ... way as the synthesis of nano zero-valent iron by using sodium .... +. −. 2и High. 2и Low. FWHM. Crystallite. /counts. /counts. /degree. /degree.

  4. Efficiency of Iron-Based Oxy-Hydroxides in Removing Antimony from Groundwater to Levels below the Drinking Water Regulation Limits

    Directory of Open Access Journals (Sweden)

    Konstantinos Simeonidis

    2017-02-01

    Full Text Available This study evaluates the efficiency of iron-based oxy-hydroxides to remove antimony from groundwater to meet the requirements of drinking water regulations. Results obtained by batch adsorption experiments indicated that the qualified iron oxy-hydroxide (FeOOH, synthesized at pH 4 for maintaining a high positive charge density (2.5 mmol OH−/g achieved a residual concentration of Sb(III below the EU drinking water regulation limit of 5 μg/L by providing an adsorption capacity of 3.1 mg/g. This is more than twice greater compared either to similar commercial FeOOHs (GFH, Bayoxide or to tetravalent manganese feroxyhyte (Fe-MnOOH adsorbents. In contrast, all tested adsorbents failed to achieve a residual concentration below 5 μg/L for Sb(V. The higher efficiency of the qualified FeOOH was confirmed by rapid small-scale column tests, since an adsorption capacity of 3 mg Sb(III/g was determined at a breakthrough concentration of 5 μg/L. However, it completely failed to achieve Sb(V concentrations below 5 μg/L even at the beginning of the column experiments. The results of leaching tests classified the spent qualified FeOOH to inert wastes. Considering the rapid kinetics of this process (i.e., 85% of total removal was performed within 10 min, the developed qualified adsorbent may be promoted as a prospective material for point-of-use Sb(III removal from water in vulnerable communities, since the adsorbent’s cost was estimated to be close to 30 ± 3.4 €/103 m3 for every 10 μg Sb(III/L removed.

  5. Preparation of nanoscale iron (oxide, oxyhydroxides and zero-valent) particles derived from blueberries: Reactivity, characterization and removal mechanism of arsenate.

    Science.gov (United States)

    Manquián-Cerda, Karen; Cruces, Edgardo; Angélica Rubio, María; Reyes, Camila; Arancibia-Miranda, Nicolás

    2017-11-01

    The application of iron nanoparticles (FeNPs) to the removal of various pollutants has received wide attention over the last few decades. A synthesis alternative to obtain these nanoparticles without using harmful chemical reagents, such as NaBH 4 , is the use of extracts from different natural sources that allow a lesser degree of agglomeration, in a process known as green synthesis. In this study, FeNPs were synthesized by 'green' (hereafter, BB-Fe NPs) and 'chemical' (hereafter, nZVI) methods. Extracts of leaves and blueberry shoots (Vaccinium corymbosum) were used as reducing agents for FeCl 3 ·6H 2 O solution in the green synthesis method. FeNPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), electrophoretic migration, Brunauer-Emmett-Teller (BET) surface area analysis and X-ray diffraction (XRD) and evaluated for the removal of As(V) from aqueous systems. In both synthesis methods, XRD analysis confirmed the presence of the different kinds of iron nanoparticles. SEM analysis showed that the average size of BB-Fe NPs was 52.4nm and that a variety of nanoparticles of different forms and associated structures, such as lepidocrocite, magnetite, and nZVI, were present, while the dimensions of nZVI were 80.2nm. Comparatively significant differences regarding the electrophoretic mobility were found between both materials pre- and post-sorption of As(V). The velocity of As(V) removal by BB-Fe NPs was slower than that by nZVI, reaching equilibrium at 120min compared to 60min for nZVI. The removal kinetics of As(V) were adequately described by the pseudo-second-order kinetic model, and the maximum adsorbed amounts of this analyte are in close accordance with the experimental results. The Langmuir-Freundlich model is in good agreement with our experimental data, where the sorption capacity of nZVI and BB-Fe NPs was found to be 52.23 ± 6.06 and 50.40 ± 5.90 (mg·g -1 ), respectively. The use of leaves of Vaccinium

  6. Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

    Science.gov (United States)

    Leybourne, Matthew I.; Johannesson, Karen H.

    2008-12-01

    We have collected ˜500 stream waters and associated bed-load sediments over an ˜400 km 2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into "dissolved" (primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO 2/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.

  7. Synthesis of Nano sized Zinc-Doped Cobalt Oxyhydroxide Parties by a Dropping Method and Their Carbon Monoxide Gas Sensing Properties

    International Nuclear Information System (INIS)

    Wang, J.W.; Kuo, Y.M.

    2013-01-01

    Two nano structures of cobalt oxyhydroxide (CoOOH) and Zinc-(Zn-) doped CoOOH (1–4% Zn) are prepared from Co(NO 3 ) 2 solution via microtitration with NaOH and oxidation in air. The X-ray diffraction (XRD) analysis results show that a pure state of nano-CoOOH can be obtained at an alkalinity (OH−/Co + ) of 5 with 40°C heat treatment after 6 h. The Zn ions preferentially substitute Co ions in the CoOOH structure, resulting in a decrease of its crystallinity. The disc-like CoOOH nano structure exhibits good sensitivity to carbon monoxide (CO) in a temperature range of 40–110°C with maximum sensitivity to CO at around 70–80°C. When CoOOH nano structure is doped with 1% Zn, its sensitivity and selectivity for CO gas are improved at 70–80°C; further Zn doping to 2% degraded the CO sensing properties of nano-CoOOH. The results of a cross-sensitivity investigation of the sensor to various gases coexisting at early stages of a fire show that the sensitivity of Zn-doped nano-CoOOH is the highest toward CO. Zn-doped nano-CoOOH film exhibits a high sensitivity to CO at room temperature, making it a promising sensor for early-stage fire detection.

  8. Hard X-ray total scattering study on the structure of Si-dopped ferric oxyhydroxides and products of their transformation

    Science.gov (United States)

    Pieczara, Gabriela; Borkiewicz, Olaf; Manecki, Maciej; Rzepa, Grzegorz

    2016-04-01

    Here we report the results of a detailed structural investigation, using synchrotron-based pair distribution function analyses (PDF) and high-resolution X-ray diffraction (HR-XRD), on a series of Si-bearing synthetic analogues of ferrihydrite with a range of Si/Fe ratio relevant to geological environments and on products of their thermal transformation. Hard X-ray total scattering data suitable for PDF analyses have been collected at the PDF-dedicated beamline 11-ID-B and the HR-XRD data at beamline 11-BM of the Advanced Photon Source (APS) at Argonne National Laboratory (ANL). Ferrihydrite is a poorly crystalline, nano-sized hydrous ferric oxyhydroxide with a nominal/ideal formula Fe5HO8•4H2O. Its chemical composition however, can vary significantly and the atomic structure is yet to be fully understood despite multitude of structural studies undertaken over the past two decades (Michel et al., 2007; Manceau, 2009). One of the most commonly discussed and still unsettled contention points regarding the structural arrangements of ferrihydrite is related to the presence or absence of tetraherdally coordinated iron(III) within its structure. The majority of experimental work carried out to date focused on pure, synthetic ferrihydrite analogues with chemical composition close to ideal/nominal. This approach is clearly a significant oversimplification of natural ferrihydrite which always contains substantial amounts of admixtures, with Si, C, P, As, Ca, S and Al being the most common. One of the most important and the most commonly encountered impurities is Si, in the form of silicate ion that has strong affinity for ferrihydrite. SiO2content in natural ferrihydrites can vary substantially but generally falls with the range of 2.6-31.5 wt% (Cismasu et al., 2011). In certain environments however, such as modern seafloor hydrothermal vents, higher Si/Fe ratios (up to ca. 3) have been reported (Sun et al., 2013). The results of previous reports indicate that silicate

  9. Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study

    International Nuclear Information System (INIS)

    Pinakidou, Fani; Kaprara, Efthimia; Katsikini, Maria; Paloura, Eleni C.; Simeonidis, Konstantinos; Mitrakas, Manassis

    2016-01-01

    The feasibility of implementing a Sn(II) oxy-hydroxide (Sn_6O_4(OH)_4) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn_6O_4(OH)_4 for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn_6O_4(OH)_4 can decrease Cr(VI) concentration below the upcoming regulation limit of 10 μg/L for drinking water. Moreover, an uptake capacity of 7.2 μg/mg at breakthrough concentration of 10 μg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH)_3 precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO_2, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ("2C) and monodentate ("1V) geometries, at the expense of the present bidentate mononuclear ("2E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn_6O_4(OH)_4 in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the "2C and "1V configurations, which enhances the safe disposal of spent adsorbents. - Highlights: • Effective Cr(VI) removal from drinking water by Sn_6O_4(OH)_4 • Sn_6O_4(OH)_4 transformation to SnO_2 after Cr(VI) reduction to Cr(III) • Strong Cr(III) sorption onto SnO_2 by formation of inner sphere complexes • Cr(III) sorption

  10. Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study.

    Science.gov (United States)

    Pinakidou, Fani; Kaprara, Efthimia; Katsikini, Maria; Paloura, Eleni C; Simeonidis, Konstantinos; Mitrakas, Manassis

    2016-05-01

    The feasibility of implementing a Sn(II) oxy-hydroxide (Sn6O4(OH)4) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn6O4(OH)4 for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn6O4(OH)4 can decrease Cr(VI) concentration below the upcoming regulation limit of 10μg/L for drinking water. Moreover, an uptake capacity of 7.2μg/mg at breakthrough concentration of 10μg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH)3 precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO2, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ((2)C) and monodentate ((1)V) geometries, at the expense of the present bidentate mononuclear ((2)E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn6O4(OH)4 in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the (2)C and (1)V configurations, which enhances the safe disposal of spent adsorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Zero-valent iron/iron oxide-oxyhydroxide/graphene as a magnetic sorbent for the enrichment of polychlorinated biphenyls, polyaromatic hydrocarbons and phthalates prior to gas chromatography-mass spectrometry.

    Science.gov (United States)

    Karamani, Anna A; Douvalis, Alexios P; Stalikas, Constantine D

    2013-01-04

    A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe(0)/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study

    Energy Technology Data Exchange (ETDEWEB)

    Pinakidou, Fani; Kaprara, Efthimia [Aristotle University of Thessaloniki, School of Chemical Engineering, Analytical Chemistry Laboratory, 54124 Thessaloniki (Greece); Katsikini, Maria; Paloura, Eleni C.; Simeonidis, Konstantinos [Aristotle University of Thessaloniki, School of Physics, Department of Solid State Physics, 54124 Thessaloniki (Greece); Mitrakas, Manassis, E-mail: manasis@eng.auth.gr [Aristotle University of Thessaloniki, School of Chemical Engineering, Analytical Chemistry Laboratory, 54124 Thessaloniki (Greece)

    2016-05-01

    The feasibility of implementing a Sn(II) oxy-hydroxide (Sn{sub 6}O{sub 4}(OH){sub 4}) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn{sub 6}O{sub 4}(OH){sub 4} for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn{sub 6}O{sub 4}(OH){sub 4} can decrease Cr(VI) concentration below the upcoming regulation limit of 10 μg/L for drinking water. Moreover, an uptake capacity of 7.2 μg/mg at breakthrough concentration of 10 μg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH){sub 3} precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO{sub 2}, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ({sup 2}C) and monodentate ({sup 1}V) geometries, at the expense of the present bidentate mononuclear ({sup 2}E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn{sub 6}O{sub 4}(OH){sub 4} in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the {sup 2}C and {sup 1}V configurations, which enhances the safe disposal of spent adsorbents. - Highlights: • Effective Cr(VI) removal from drinking water by Sn{sub 6}O{sub 4}(OH){sub 4} • Sn{sub 6}O{sub 4}(OH){sub 4} transformation to SnO{sub 2} after Cr

  13. Scaled-up solvothermal synthesis of nanosized metastable indium oxyhydroxide (InOOH) and corundum-type rhombohedral indium oxide (rh-In{sub 2}O{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Schlicker, Lukas; Bekheet, Maged F.; Gurlo, Aleksander [Technische Univ. Berlin (Germany). Fachgebiet Keramische Werkstoffe

    2017-03-01

    Phase pure metastable indium oxyhydroxide (InOOH) with crystallite size in the range ca. 2-7 nm is synthesized by a nonaqueous solvothermal synthesis route in ethanol. The influence of synthesis parameters such as temperature, basicity (pH), synthesis time, and water content is carefully addressed. T-pH maps summarize the impact of synthesis temperature and pH and reveal that phase pure InOOH is obtained in water-free solutions at mild temperatures (150-180 C) in highly basic conditions (pH>12). Subsequent calcination of InOOH at 375-700 C in ambient air atmosphere results in metastable nanoscaled rhombohedral indium oxide (rh-In{sub 2}O{sub 3}). The synthesis protocol for phase pure nanocrystalline InOOH material was successfully upscaled allowing for obtaining ca. 3 g of phase-pure InOOH with a yield of ca. 78%. The upscaled InOOH and rh-In{sub 2}O{sub 3} batches are now available for a detailed in-situ characterization of the mechanism of decomposition of InOOH to rh-In{sub 2}O{sub 3} to c-In{sub 2}O{sub 3} as well as for the characterization of the functional properties of InOOH and rh-In{sub 2}O{sub 3} materials.

  14. Síntese e caracterização de óxido hidróxido de manganês do tipo manganita (γ -MnOOH Synthesis and characterization of manganese oxyhydroxide manganite (γ -MnOOH type

    Directory of Open Access Journals (Sweden)

    B. A. M. Figueira

    2008-06-01

    Full Text Available Óxido hidróxido de manganês (γ - MnOOH do tipo da manganita foi sintetizado por uma rota simples, em que a chave precursora K-birnessita foi preparada pelo método sol-gel. O tratamento hidrotermal da estrutura lamelar do tipo da birnessita favorece a obtenção de estruturas em túnel, sendo que o tamanho destes túneis depende das condições empregadas na síntese (pH, temperatura e tempo. A comprovação da formação de manganita sob as condições de síntese empregadas foi verificada pelas técnicas de difração de raios X, microscopia eletrônica de varredura, análises termogravimétrica e térmica diferencial e espectroscopia de infravermelho.Manganese oxyhydroxide (g - MnOOH of the manganite type has been synthesized by a simple route with K-birnessite prepared by the sol-gel method. The hydrothermal treatment of the lamellar birnessite type structure facilitates the formation of tunnel structures where the size of the tunnels depends on the synthesis conditions (pH, temperature and time. The evidence of manganite formation under the synthesis conditions were made by X-ray diffraction, scanning electron microscopy, thermogravimetry, differential thermal analysis and infrared spectroscopy.

  15. Surface characteristics of the iron-oxyhydroxide layer formed during brick coatings by ESEM/EDS, {sup 23}Na and {sup 1}H MAS NMR, and ToF-SIMS

    Energy Technology Data Exchange (ETDEWEB)

    Allahdin, O. [Chaire Unesco « Sur la gestion de l' eau », Laboratoire Hydrosciences Lavoisier, Université de Bangui, Faculté des Sciences, B.P. 908 (Central African Republic); Wartel, M. [Université Lille1, Laboratoire LASIR (UMR CNRS 8516), Equipe Physico-chimie de l' Environnement, Bât. C8, 2" è" m" e étage, 59655 Villeneuve d' Ascq cedex (France); Mabingui, J. [Chaire Unesco « Sur la gestion de l' eau », Laboratoire Hydrosciences Lavoisier, Université de Bangui, Faculté des Sciences, B.P. 908 (Central African Republic); Revel, B. [Université Lille1, Service RMN, Bât. C4, 59655 Villeneuve d' Ascq cedex (France); Nuns, N. [Université Lille1, Institut Chevreul, 59655 Villeneuve d' Ascq cedex (France); Boughriet, A., E-mail: abdel.boughriet@univ-lille1.fr [Université Lille1, Laboratoire LASIR (UMR CNRS 8516), Equipe Physico-chimie de l' Environnement, Bât. C8, 2" è" m" e étage, 59655 Villeneuve d' Ascq cedex (France)

    2015-09-01

    Brick made locally by craftsmen in Bangui (Central African Republic) was modified first by HCl activation and second by iron-oxyhydroxide impregnation through the precipitation of ferric ions by NaOH at various fixed pH values (ranging from 3 to 13). The elemental analyses of synthesized compounds were performed using ICP-AES, and their surface chemistry/properties were investigated by environmental scanning electron microscopy (ESEM/EDS), {sup 1}H and {sup 23}Na MAS NMR spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The evidence of different {sup 23}Na chemical environments and the coexistence of Si and Al bound to ferrihydrite were made. The surface properties of this material which was found to be dependent upon synthesis pH, contributed to enhance metal uptake from water. - Highlights: • HCl-activated brick was coated at different Fe(III)-precipitation pH. • Surface properties were determined by ESEM, NMR and ToF-SIMS. • Al- and Si-bearing ferrihydrite and different Na environments were detected. • The pH used for modified-brick synthesis influenced metal uptake from water.

  16. Syntheses, Structures, and Magnetic Properties of Nickel-Doped Lepidocrocite Titanates

    DEFF Research Database (Denmark)

    Gao, Tao; Norby, Poul; Okamoto, Hiroshi

    2009-01-01

    Ni-doped titanate CsxTi2−x/2Nix/2O4 and its protonic derivative HxTi2−x/2Nix/2O4·xH2O (x = 0.7) were synthesized and characterized by means of synchrotron X-ray diffraction, Raman scattering, X-ray photoelectron spectroscopy (XPS), and magnetic measurements. CsxTi2−x/2Nix/2O4 crystallizes......H2O. Ni- and Mg-codoped titanates CsxTi2−x/2(NiyMg1−y)x/2O4 (x = 0.7, 0 ≤ y ≤ 1) were also reported. The crystal structure, interlayer chemistry, and magnetic properties of the titanates depend on the Ni substitution levels, indicating opportunities for tuning of the properties by controlling...

  17. Efficient Overall Water-Splitting Electrocatalysis Using Lepidocrocite VOOH Hollow Nanospheres

    KAUST Repository

    Shi, Huanhuan; Liang, Hanfeng; Ming, Fangwang; Wang, Zhoucheng

    2016-01-01

    be achieved with low overpotentials of 270 mV for the oxygen evolution reaction (OER) and 164 mV for the hydrogen evolution reaction (HER) at 10 mA cm-2 in 1 m KOH, respectively. Furthermore, when used as both the anode and cathode for overall water splitting

  18. Some consequences of a liquid water saturated regolith in early Martian history

    Science.gov (United States)

    Fuller, A. O.; Hargraves, R. B.

    1978-01-01

    Flooding of low-lying areas of the Martian regolith may have occurred early in the planet's history when a comparatively dense primitive atmosphere existed. If this model is valid, the following are some pedogenic and mineralogical consequences to be expected. Fluctuation of the water table in response to any seasonal or longer term causes would have resulted in precipitation of ferric oxyhydroxides with the development of a vesicular duricrust (or hardpan). Disruption of such a crust by scarp undercutting or frost heaving accompanied by wind deflation of fines could account for the boulders visible on Utopia Planitia in the vicinity of the second Viking lander site. Laboratory and field evidence on earth suggests that under weakly oxidizing conditions lepidocrocite (rather than goethite) would have preferentially formed in the Martian regolith from the weathering of ferrous silicates, accompanied by montmorillonite, nontronite, and cronstedtite. Maghemite may have formed as a low-temperature dehydrate of lepidocrocite or directly from ferrous precursors.

  19. The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the anionic media

    International Nuclear Information System (INIS)

    Liu Hui; Guo Hui; Li Ping; Wei Yu

    2008-01-01

    The transformation from ferrihydrite to various iron oxides and iron oxyhydroxides has been given much attention not only in environmental science and geochemistry but also in biology and material science. This laboratory study attempted to investigate Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium. The results indicate that the transformation in sulfate-rich medium differs from that in Cl - medium in the species, the amount and the morphology of products and transformation rate. Lepidocrocite is a main ingredient in the product in Cl - medium at room temperature (RT), while goethite is the only product in SO 4 2- medium at RT. Goethite particles obtained in Cl - medium are star-like but rod-like in SO 4 2- medium. The transformation rate in the latter medium is obviously slower than that in the former medium. The formation of lepidocrocite depends on both the ionic strength of the system and the dissolution rate of ferrihydrite. - Graphical abstract: Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium was studied. Lepidocrocite is a main ingredient in the product in Cl - medium at room temperature (RT), while goethite is the only product in SO 4 2- medium. Goethite particles obtained in Cl - medium are star-like but rod-like in SO 4 2- medium

  20. Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

    Science.gov (United States)

    Jones, Adele M.; Collins, Richard N.; Waite, T. David

    2017-12-01

    The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe

  1. Adsorption of antimony onto iron oxyhydroxides: Adsorption behavior and surface structure

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xuejun; Wu, Zhijun [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); He, Mengchang, E-mail: hemc@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Meng, Xiaoguang [Center for Environmental Systems, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Jin, Xin [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Qiu, Nan; Zhang, Jing [Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2014-07-15

    Graphical abstract: - Highlights: • Antimony adsorption depended on the Sb species, pH, and the type of iron oxides. • Sb(V) adsorption favored at acidic pH, Sb(III) adsorption optimized in wider pH. • Antimony was adsorbed onto the iron oxides by the inner-sphere surface complex. • Bidentate mononuclear ({sup 2}E) was the dominant form of Sb incorporated into HFO. • XAFS and XPS indicated Sb(III) adsorbed was slowly oxidized to Sb(V). - Abstract: Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl{sub 3}, was oxidized into Sb(V) probably due to the involvement of O{sub 2} in the long duration of sample preservation. Only one Sb–Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0–1.9 attributed to bidentate mononuclear edge-sharing ({sup 2}E) between Sb and HFO.

  2. Development of a reactive force field for iron-oxyhydroxide systems.

    Science.gov (United States)

    Aryanpour, Masoud; van Duin, Adri C T; Kubicki, James D

    2010-06-03

    We adopt a classical force field methodology, ReaxFF, which is able to reproduce chemical reactions, and train its parameters for the thermodynamics of iron oxides as well as energetics of a few iron redox reactions. Two parametrizations are developed, and their results are compared with quantum calculations or experimental measurements. In addition to training, two test cases are considered: the lattice parameters of a selected set of iron minerals, and the molecular dynamics simulation of a model for alpha-FeOOH (goethite)-water interaction. Reliability and limitations of the developed force fields in predicting structure and energetics are discussed.

  3. Gold-supported two-dimensional cobalt oxyhydroxide (CoOOH) and multilayer cobalt oxide islands

    DEFF Research Database (Denmark)

    Fester, Jakob; Walton, Alexander; Li, Zheshen

    2017-01-01

    In the present study, we investigate the facile conversion of Co-O bilayer islands on a Au(111) surface into preferentially O-Co-O trilayers in an oxygen atmosphere and O-Co-O-Co-O multilayers at elevated temperature. We characterize and compare the island morphologies with scanning tunneling...... microscopy, X-ray photoemission spectroscopy (XPS) and valence band spectroscopy, and show that the cobalt oxidation state changes from Co2+ in bilayers to purely Co3+ in trilayers and a mixture of Co2+ and Co3+ in the multilayer morphology. In contrast to bilayers and multilayers, the trilayer structure...

  4. Ferrous Iron Oxidation under Varying pO2 Levels: The Effect of Fe(III)/Al(III) Oxide Minerals and Organic Matter.

    Science.gov (United States)

    Chen, Chunmei; Thompson, Aaron

    2018-01-16

    Abiotic Fe(II) oxidation by O 2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al 2 O 3 ) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO 2 at pH 6. We tracked Fe dynamics by adding 57 Fe(II) to 56 Fe-labeled goethite and γ-Al 2 O 3 and characterized the resulting solids using 57 Fe Mössbauer spectroscopy. We found Fe(II) oxidation was slower at low pO 2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II) (aq) alone, both goethite and γ-Al 2 O 3 surfaces increased Fe(II) oxidation rates regardless of pO 2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al 2 O 3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe(II) aq alone favored lepidocrocite. SRFA reduced oxidation rates in all treatments except the mineral-free systems at 21% pO 2 , and SRFA decreased Fe(III) phase crystallinity, facilitating low-crystalline ferrihydrite in the absence of mineral sorbents, low-crystalline lepidocrocite in the presence of γ-Al 2 O 3 , but either crystalline goethite or ferrihydrite when goethite was present. This work highlights that the oxidation rate, the types of mineral surfaces, and OM control Fe(III) precipitate composition.

  5. Impact of natural organic matter coatings on the microbial reduction of iron oxides

    Science.gov (United States)

    Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg

    2018-03-01

    Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that

  6. Microstructural characterisation and corrosion performance of old railway girder bridge steel and modern weathering structural steel

    International Nuclear Information System (INIS)

    Tewary, N.K.; Kundu, A.; Nandi, R.; Saha, J.K.; Ghosh, S.K.

    2016-01-01

    Highlights: • Microstructure and corrosion performance are compared for two structural steels. • Microstructure evolution shows primarily ferrite-pearlite in both the steels. • Steels show higher corrosion rate in 1% HCl solution than in 3.5% NaCl solution. • The corrosion products show the presence of oxide, hydroxide and oxy-hydroxides. • The corroded surface reveals morphologies like flowery, cotton balls and rosette. - Abstract: A comparison on microstructure and corrosion performance has been made between the two structural steels used in old railway girder bridge (Sample A) and modern grades of weathering structural steel (Sample B). The microstructures, viewed under optical microscope and scanning electron microscope (SEM), show mainly ferrite-pearlite phase constituents in both the steels, A and B. The phase fraction analysis shows higher amount of pearlite in steel A compared to that of steel B. The grain size of steel A is larger than that of steel B under identical processing condition. The immersion corrosion test in 3.5% NaCl shows that the corrosion rate of steel A increases with time, while the same for steel B decreases with time. On the other hand, corrosion test in 1% HCl shows that the corrosion rate of both steel A and B is higher as compared to that of NaCl which always decreases with time. The XRD analysis of corrosion products show the presence of many oxides, hydroxide and oxy-hydroxide like Lepidocrocite (γ-FeOOH), Goethite (α-FeOOH), Akaganeite (β-FeOOH), Magnetite (Fe_3O_4) and Maghemite (γ-Fe_2O_3) in both the steels. The SEM images of corroded surfaces reveal different morphologies like flowery, cotton balls and rosette etc. which indicate that the corrosion products primarily contain Lepidocrocite (γ-FeOOH), Goethite (α-FeOOH) and Akaganeite (β-FeOOH).

  7. The nanosphere iron mineral(s) in Mars soil

    Science.gov (United States)

    Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

    1993-01-01

    A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

  8. Shape evolution of new-phased lepidocrocite VOOH from single-shelled to double-shelled hollow nanospheres on the basis of programmed reaction-temperature strategy.

    Science.gov (United States)

    Wu, Changzheng; Zhang, Xiaodong; Ning, Bo; Yang, Jinlong; Xie, Yi

    2009-07-06

    Solid templates have been long regarded as one of the most promising ways to achieve single-shelled hollow nanostructures; however, few effective methods for the construction of multishelled hollow objects from their solid template counterparts have been developed. We report here, for the first time, a novel and convenient route to synthesizing double-shelled hollow spheres from the solid templates via programming the reaction-temperature procedures. The programmed temperature strategy developed in this work then provides an essential and general access to multishelled hollow nanostructures based on the designed extension of single-shelled hollow objects, independent of their outside contours, such as tubes, hollow spheres, and cubes. Starting from the V(OH)(2)NH(2) solid templates, we show that the relationship between the hollowing rate and the reaction temperature obey the Van't Hoff rule and Arrhenius activation-energy equation, revealing that it is the chemical reaction rather than the diffusion process that guided the whole hollowing process, despite the fact that the coupled reaction/diffusion process is involved in the hollowing process. Using the double-shelled hollow spheres as the PCM (CaCl(2).6H(2)O) matrix grants much better thermal-storage stability than that for the nanoparticles counterpart, revealing that the designed nanostructures can give rise to significant improvements for the energy-saving performance in future "smart house" systems.

  9. The nanophase iron mineral(s) in Mars soil

    Science.gov (United States)

    Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

    1993-01-01

    A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism

  10. Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

    Science.gov (United States)

    Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The tr...

  11. Formation, aggregation and reactivity of amorphous ferric oxyhydroxides on dissociation of Fe(III)-organic complexes in dilute aqueous suspensions

    Science.gov (United States)

    Bligh, Mark W.; Waite, T. David

    2010-10-01

    While chemical reactions that take place at the surface of amorphous ferric oxides (AFO) are known to be important in aquatic systems, incorporation of these reactions into kinetic models is hindered by a lack of ability to reliably quantify the reactivity of the surface and the changes in reactivity that occur over time. Long term decreases in the reactivity of iron oxides may be considered to result from changes in the molecular structure of the solid, however, over shorter time scales where substantial aggregation may occur, the mechanisms of reactivity loss are less clear. Precipitation of AFO may be described as a combination of homogeneous and heterogeneous reactions, however, despite its potentially significant role, the latter reaction is usually neglected in kinetic models of aquatic processes. Here, we investigate the role of AFO in scavenging dissolved inorganic ferric (Fe(III)) species (Fe') via the heterogeneous precipitation reaction during the net dissociation of organically complexed Fe(III) in seawater. Using sulfosalicylic acid (SSA) as a model ligand, AFO was shown to play a significant role in inducing the net dissociation of the Fe-SSA complexes with equations describing both the heterogeneous precipitation reaction and the aging of AFO being required to adequately describe the experimental data. An aggregation based mechanism provided a good description of AFO aging over the short time scale of the experiments. The behaviour of AFO described here has implications for the bioavailability of iron in natural systems as a result of reactions involving AFO which are recognised to occur over time scales of minutes, including adsorption of Fe' and AFO dissolution, precipitation and ageing.

  12. Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

    Science.gov (United States)

    Seredych, Mykola; Mabayoje, Oluwaniyi; Bandosz, Teresa J

    2012-01-17

    Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions. © 2011 American Chemical Society

  13. Investigating the effect of ascorbate on the Fe(II)-catalyzed transformation of the poorly crystalline iron mineral ferrihydrite.

    Science.gov (United States)

    Xiao, Wei; Jones, Adele M; Collins, Richard N; Waite, T David

    2018-05-09

    The inorganic core of the iron storage protein, ferritin, is recognized as being analogous to the poorly crystalline iron mineral, ferrihydrite (Fh). Fh is also abundant in soils where it is central to the redox cycling of particular soil contaminants and trace elements. In geochemical circles, it is recognized that Fh can undergo Fe(II)-catalyzed transformation to form more crystalline iron minerals, vastly altering the reactivity of the iron oxide and, in some cases, the redox poise of the system. Of relevance to both geochemical and biological systems, we investigate here if the naturally occurring reducing agent, ascorbate, can effect such an Fe(II)-catalyzed transformation of Fh at 25 °C and circumneutral pH. The transformation of ferrihydrite to possible secondary Fe(III) mineralization products was quantified using Fourier transform infrared (FTIR) spectroscopy, with supporting data obtained using X-ray absorbance spectroscopy (XAS) and X-ray diffraction (XRD). Whilst the amount of Fe(II) formed in the presence of ascorbate has resulted in Fh transformation in previous studies, no transformation of Fh to more crystalline Fe(III) (oxyhydr)oxides was observed in this study. Further experiments indicated this was due to the ability of ascorbate to inhibit the formation of goethite, lepidocrocite and magnetite. The manner in which ascorbate associated with Fh was investigated using FTIR and total organic carbon (TOC) analysis. The majority of ascorbate was found to adsorb to the Fh surface under anoxic conditions but, under oxic conditions, ascorbate was initially adsorbed then became incorporated within the Fe(III) (oxyhydr)oxide structure (i.e., co-precipitated) over time. Copyright © 2018 Elsevier B.V. All rights reserved.

  14. Acidic Microenvironments in Waste Rock Characterized by Neutral Drainage: Bacteria–Mineral Interactions at Sulfide Surfaces

    Directory of Open Access Journals (Sweden)

    John W. Dockrey

    2014-03-01

    Full Text Available Microbial populations and microbe-mineral interactions were examined in waste rock characterized by neutral rock drainage (NRD. Samples of three primary sulfide-bearing waste rock types (i.e., marble-hornfels, intrusive, exoskarn were collected from field-scale experiments at the Antamina Cu–Zn–Mo mine, Peru. Microbial communities within all samples were dominated by neutrophilic thiosulfate oxidizing bacteria. However, acidophilic iron and sulfur oxidizers were present within intrusive waste rock characterized by bulk circumneutral pH drainage. The extensive development of microbially colonized porous Fe(III (oxyhydroxide and Fe(III (oxyhydroxysulfate precipitates was observed at sulfide-mineral surfaces during examination by field emission-scanning electron microscopy-energy dispersive X-ray spectroscopy (FE-SEM-EDS. Linear combination fitting of bulk extended X-ray absorption fine structure (EXAFS spectra for these precipitates indicated they were composed of schwertmannite [Fe8O8(OH6–4.5(SO41–1.75], lepidocrocite [γ-FeO(OH] and K-jarosite [KFe3(OH6(SO42]. The presence of schwertmannite and K-jarosite is indicative of the development of localized acidic microenvironments at sulfide-mineral surfaces. Extensive bacterial colonization of this porous layer and pitting of underlying sulfide-mineral surfaces suggests that acidic microenvironments can play an important role in sulfide-mineral oxidation under bulk circumneutral pH conditions. These findings have important implications for water quality management in NRD settings.

  15. Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

    Science.gov (United States)

    Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

    2018-06-14

    To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

  16. Microbial reduction of ferric iron oxyhydroxides as a way for remediation of grey forest soils heavily polluted with toxic metals by infiltration of acid mine drainage

    Science.gov (United States)

    Georgiev, Plamen; Groudev, Stoyan; Spasova, Irena; Nicolova, Marina

    2015-04-01

    The abandoned uranium mine Curilo is a permanent source of acid mine drainage (AMD) which steadily contaminated grey forest soils in the area. As a result, the soil pH was highly acidic and the concentration of copper, lead, arsenic, and uranium in the topsoil was higher than the relevant Maximum Admissible Concentration (MAC) for soils. The leaching test revealed that approximately half of each pollutant was presented as a reducible fraction as well as the ferric iron in horizon A was presented mainly as minerals with amorphous structure. So, the approach for remediation of the AMD-affected soils was based on the process of redoxolysis carried out by iron-reducing bacteria. Ferric iron hydroxides reduction and the heavy metals released into soil solutions was studied in the dependence on the source of organic (fresh or silage hay) which was used for growth and activity of soil microflora, initial soil pH (3.65; 4.2; and 5.1), and the ion content of irrigation solutions. The combination of limestone (2.0 g/ kg soil), silage addition (at rate of 45 g dry weight/ kg soil) in the beginning and reiterated at 6 month since the start of soil remediation, and periodical soil irrigation with slightly acidic solutions containing CaCl2 was sufficient the content of lead and arsenic in horizon A to be decreased to concentrations similar to the relevant MAC. The reducible, exchangeable, and carbonate mobile fractions were phases from which the pollutants was leached during the applied soil remediation. It determined the higher reduction of the pollutants bioavailability also as well as the process of ferric iron reduction was combined with neutralization of the soil acidity to pH (H2O) 6.2.

  17. Hydrolysis of bis(dimethylamido)tin to tin (II) oxyhydroxide and its selective transformation into tin (II) or tin (IV) oxide

    KAUST Repository

    Khanderi, Jayaprakash; Shi, Lei; Rothenberger, Alexander

    2015-01-01

    Sn6O4(OH)4, a hydrolysis product of Sn(NMe2)2, is transformed to tin (II) or tin (IV) oxide by solid and solution phase processing. Tin (II) oxide is formed by heating Sn6O4(OH)4 at ≤200 °C in air or under inert atmosphere. Tin (IV) oxide

  18. Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Paik, Younkee; Julmis, Keinia

    2005-01-01

    High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, th...... on the goethite surface. Even larger Li hyperfine shifts (289 ppm) were observed for Li+-exchanged goethite, which contains lithium ions in the tunnels of the goethite structure, confirming the Li assignment of the 145 ppm Li resonance to the surface sites. Udgivelsesdato: 2005-Oct-6...

  19. Hydrolysis of bis(dimethylamido)tin to tin (II) oxyhydroxide and its selective transformation into tin (II) or tin (IV) oxide

    KAUST Repository

    Khanderi, Jayaprakash

    2015-03-01

    Sn6O4(OH)4, a hydrolysis product of Sn(NMe2)2, is transformed to tin (II) or tin (IV) oxide by solid and solution phase processing. Tin (II) oxide is formed by heating Sn6O4(OH)4 at ≤200 °C in air or under inert atmosphere. Tin (IV) oxide nanoparticles are formed in the presence of a carboxylic acid and base in air at room temperature. IR spectroscopy, Raman spectroscopy, thermogravimetry (coupled with infrared spectroscopy), powder X-ray diffraction, high temperature X-ray diffraction, scanning electron and transmission electron microscopy are used for the characterization of Sn6O4(OH)4 and the investigation of its selective decomposition into SnO or SnO2. Spectroscopic and X-ray diffraction results indicate that SnO is formed by the removal of water from crystalline Sn6O4(OH)4. SEM shows octahedral morphology of the Sn6O4(OH)4, SnO and SnO2 with particle size from 400 nm-2 μm during solid state conversion. Solution phase transformation of Sn6O4(OH)4 to SnO2 occurs in the presence of potassium glutarate and oxygen. SnO2 particles are 15-20 nm in size.

  20. Contribution to the study of sorption mechanisms at solid-liquid interfaces: application to the cases of apatites and oxy-hydroxides

    International Nuclear Information System (INIS)

    Duc, M.

    2002-11-01

    Sorption-desorption phenomena play an important role in the transport of toxic and radioactive elements in surface and underground water in contact with solid matter. Selenium, which is one of the long-lived radionuclides present in radioactive waste, is characterized by several oxidation states and by anionic species in aqueous solutions. In order to predict its transport, we need a good knowledge of its sorption processes. We have studied the sorption of Se(IV) and Se(VI) on two types of solids present in natural media or which have been proposed as additives to active barriers: hydroxy-apatites, fluoro-apatite and iron oxi-hydroxides (goethite and hematite). Sorption mechanisms have been studied through an approach including several different and complementary methods: titrimetry, zeta-metry, scanning and transmission electron microscopy, infrared spectroscopy, X-ray diffraction, X-ray photo electron spectroscopy, etc... Results showed that Se(VI) is much less sorbed than Se(VI) on both types of solids. For Se(IV) the sorption mechanisms are different for iron oxides and apatites. On oxides, sorption increases when pH decreases. It can be interpreted by a surface complexation model, essentially through an inner sphere complex (monodentate or bidentate). Modelling of Se sorption curves was performed after the determination of acido-basic properties of oxides. However, the determination of the intrinsic properties of oxides is disturbed by several parameters identified as impurities, evolution of the solid in solution, kinetic and solubility of the solid. For apatites, selenium sorption proceeds by exchange with superficial groups, with a maximum of fixation at approximately pH 8. Thanks to XPS measurements and the elaboration of a mathematical model, we could determine the depth of penetration of both selenium and cadmium on apatites. (author)

  1. Iron geochemistry and organic carbon preservation by iron (oxyhydr)oxides in surface sediments of the East China Sea and the south Yellow Sea

    Science.gov (United States)

    Ma, Wei-Wei; Zhu, Mao-Xu; Yang, Gui-Peng; Li, Tie

    2018-02-01

    In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (FeAVS + carb) and magnetite (Femag) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fecarb and Femag, a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (FeHR) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of FeHR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions (fFe-OC) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the fFe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO2 release to the atmosphere. In the SYS, consistently less 13C-depleted Fe-OC relative to 13C of non-Fe-bound OC (13Cnon-Fe-OC) suggests selective sequestration of labile marine OC in the marine OC-dominated sediments of the central SYS. In the ECS, however, efficient oxidation of OC and frequent redox cycling of Fe in the unsteady depositional regimes may complicate the isotopic compositions of Fe-OC. A combination of our results and literature data demonstrates that Fe-OC contents are strongly dependent on the availability of TOC and reactive Fe, but the fFe-OC is primarily controlled by the processes of Fe redox cycling in the sediments.

  2. Preliminary characterization and biological reduction of putative biogenic iron oxides (BIOS) from the Tonga-Kermadec Arc, southwest Pacific Ocean.

    Science.gov (United States)

    Langley, S; Igric, P; Takahashi, Y; Sakai, Y; Fortin, D; Hannington, M D; Schwarz-Schampera, U

    2009-01-01

    Sediment samples were obtained from areas of diffuse hydrothermal venting along the seabed in the Tonga sector of the Tonga-Kermadec Arc, southwest Pacific Ocean. Sediments from Volcano 1 and Volcano 19 were analyzed by X-ray diffraction (XRD) and found to be composed primarily of the iron oxyhydroxide mineral, two-line ferrihydrite. XRD also suggested the possible presence of minor amounts of more ordered iron (hydr)oxides (including six-line ferrihydrite, goethite/lepidocrocite and magnetite) in the biogenic iron oxides (BIOS) from Volcano 1; however, Mössbauer spectroscopy failed to detect any mineral phases more crystalline than two-line ferrihydrite. The minerals were precipitated on the surfaces of abundant filamentous microbial structures. Morphologically, some of these structures were similar in appearance to the known iron-oxidizing genus Mariprofundus spp., suggesting that the sediments are composed of biogenic iron oxides. At Volcano 19, an areally extensive, active vent field, the microbial cells appeared to be responsible for the formation of cohesive chimney-like structures of iron oxyhydroxide, 2-3 m in height, whereas at Volcano 1, an older vent field, no chimney-like structures were apparent. Iron reduction of the sediment material (i.e. BIOS) by Shewanella putrefaciens CN32 was measured, in vitro, as the ratio of [total Fe(II)]:[total Fe]. From this parameter, reduction rates were calculated for Volcano 1 BIOS (0.0521 day(-1)), Volcano 19 BIOS (0.0473 day(-1)), and hydrous ferric oxide, a synthetic two-line ferrihydrite (0.0224 day(-1)). Sediments from both BIOS sites were more easily reduced than synthetic ferrihydrite, which suggests that the decrease in effective surface area of the minerals within the sediments (due to the presence of the organic component) does not inhibit subsequent microbial reduction. These results indicate that natural, marine BIOS are easily reduced in the presence of dissimilatory iron-reducing bacteria, and that the

  3. Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination Processes

    International Nuclear Information System (INIS)

    Satish C. B. Myneni

    2005-01-01

    Siderophores are biological macromolecules (400-2000 Da) released by bacteria in iron limiting situations to sequester Fe from iron oxyhydroxides and silicates in the natural environment. These molecules contain hydroxamate and phenolate functional groups, and exhibit very high affinity for Fe 3+ . While several studies were conducted to understand the behavior of siderophores and their application to the metal sequestration and mineral dissolution, only a few of them have examined the molecular structure of siderophores and their interactions with metals and mineral surfaces in aqueous solutions. Improved understanding of the chemical state of different functional moieties in siderophores can assist in the application of these biological molecules in actinide separation, sequestration and decontamination processes. The focus of our research group is to evaluate the (a) functional group chemistry of selected siderophores and their metal complexes in aqueous solutions, and (b) the nature of siderophore interactions at the mineral-water interfaces. We selected desferrioxamine B (desB), a hydroxamate siderophore, and its small structural analogue, acetohydroxamic acid (aHa), for this investigation. We examined the functional group chemistry of these molecules as a function of pH, and their complexation with aqueous and solid phase Fe(III). For solid phase Fe, we synthesized all naturally occurring Fe(III)-oxyhydroxides (goethite, lepidocrocite, akaganeite, feroxyhite) and hematite. We also synthesized Fe-oxides (goethite and hematite) of different sizes to evaluate the influence of particle size on mineral dissolution kinetics. We used a series of molecular techniques to explore the functional group chemistry of these molecules and their complexes. Infrared spectroscopy is used to specifically identify the variations in oxime group as a function of pH and Fe(III) complexation. Resonance Raman spectroscopy was used to evaluate the nature of hydroxamate binding in the

  4. Internal features, mineralogy and geochemistry of ferromanganese nodules from the Gulf of Cadiz: The role of the Mediterranean Outflow Water undercurrent

    Science.gov (United States)

    González, F. J.; Somoza, L.; Lunar, R.; Martínez-Frías, J.; Rubí, J. A. Martín; Torres, T.; Ortiz, J. E.; Díaz-del-Río, V.

    2010-03-01

    A large suite of Fe-Mn nodules (561 samples) were recovered during the Anastasya2001 cruise (TASYO project) along the continental margin of the Gulf of Cadiz (Eastern Central Atlantic), at the confluence of the Mediterranean Sea with the Atlantic Ocean, where extensive nodule fields were discovered. Based on wide previous studies that included swath bathymetry, multi-channel and very high-resolution seismic reflection, gravimetry, magnetism, heat flow probes and underwater photography surveys, nodules were collected at water depths ranging from 850 to 1000 m, associated with hydrocarbon-derived Mg-calcite, ankerite and dolomite chimneys and crusts. Forty-six selected samples among the various morphological types were used for the laboratory analysis of physical properties (morphology, color, surface texture, sphericity, weight and size), mineralogy (XRD, optical and electronic microscopy), geochemistry (XRF, AAS, ICP-MS, ICP-AES, EPMA, and GC-MS) and stable isotopes. The nodules show a wide range of sizes, densities, weights and morphologies. They are formed by multiple millimeter-thick layers of Fe and Mn oxyhydroxides surrounding the nucleus composed of Early-Middle Miocene plastic marl and sediment, which were derived from underlying units by fluid venting. Massive, laminated, detrital and mottled to dendritic textural features were developed by the Fe and Mn oxyhydroxide layers. The main components are Goethite, lepidocrocite, Mn oxides (7 Å manganates and 10 Å manganates), quartz, and phyllosilicates. Accessory minerals are calcite, dolomite, siderite, rhodochrosite, kutnahorite, pyrite, chalcopyrite, potassium feldspar, zircon, rutile, ilmenite and chlorite. Fe-Mn carbonates from the siderite-rhodochrosite continuous series are the principal constituent of the nuclei. Framboidal, filamentous and globular textures are observed in Fe-Mn oxides and pyrite, suggesting biogenic origin. The nodules show a high mean abundance of Fe (38.6%), moderate Mn (6.0%) and

  5. Lithotrophic iron-oxidizing bacteria produce organic stalks to control mineral growth: implications for biosignature formation

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Clara S; Fakra, Sirine C; Emerson, David; Fleming, Emily J; Edwards, Katrina J

    2011-07-01

    Neutrophilic Fe-oxidizing bacteria (FeOB) are often identified by their distinctive morphologies, such as the extracellular twisted ribbon-like stalks formed by Gallionella ferruginea or Mariprofundus ferrooxydans. Similar filaments preserved in silica are often identified as FeOB fossils in rocks. Although it is assumed that twisted iron stalks are indicative of FeOB, the stalk's metabolic role has not been established. To this end, we studied the marine FeOB M. ferrooxydans by light, X-ray and electron microscopy. Using time-lapse light microscopy, we observed cells excreting stalks during growth (averaging 2.2 {micro}m h(-1)). Scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy show that stalks are Fe(III)-rich, whereas cells are low in Fe. Transmission electron microscopy reveals that stalks are composed of several fibrils, which contain few-nanometer-sized iron oxyhydroxide crystals. Lepidocrocite crystals that nucleated on the fibril surface are much larger ({approx}100 nm), suggesting that mineral growth within fibrils is retarded, relative to sites surrounding fibrils. C and N 1s NEXAFS spectroscopy and fluorescence probing show that stalks primarily contain carboxyl-rich polysaccharides. On the basis of these results, we suggest a physiological model for Fe oxidation in which cells excrete oxidized Fe bound to organic polymers. These organic molecules retard mineral growth, preventing cell encrustation. This model describes an essential role for stalk formation in FeOB growth. We suggest that stalk-like morphologies observed in modern and ancient samples may be correlated confidently with the Fe-oxidizing metabolism as a robust biosignature.

  6. Influence of lactate ions on the formation of rust

    International Nuclear Information System (INIS)

    Sabot, R.; Jeannin, M.; Gadouleau, M.; Guo, Q.; Sicre, E.; Refait, Ph.

    2007-01-01

    The formation of rust can be simulated by oxidation of aqueous suspensions of Fe(OH) 2 obtained by mixing solutions of NaOH and a Fe(II) salt. The aim of this study was to investigate the influence of organic species associated with microbially influenced corrosion. The lactate anion, often used as a carbon and electrons source for the development of microorganisms, was chosen as an example. Then, in the first part of the study, Fe(OH) 2 was precipitated using iron(II) lactate and NaOH. Its oxidation process involved two stages, as usually observed. The first stage led to a Fe(II-III) intermediate compound, the lactate green rust, GR(C 3 H 5 O 3 - ). This compound has never been reported yet. Its existence demonstrates that the GR structure is able to incorporate a very wide range of anions, whatever the size and geometry. The second stage corresponded to the oxidation of GR(C 3 H 5 O 3 - ). It led to ferrihydrite, the most poorly ordered form of iron(III) oxides and oxyhydroxides. In the second part of the study, the formation of rust in seawater was simulated by oxidation of Fe(OH) 2 in an aqueous media containing both Cl - and SO 4 2- anions. The first stage led to the sulphate green rust, GR(SO 4 2- ), the second stage to lepidocrocite γ-FeOOH. Small amounts of iron(II) lactate were added to the reactants. Lactate ions did not modify the first stage but drastically perturbed the second stage, as ferrihydrite was obtained instead of γ-FeOOH

  7. Weathering of post-impact hydrothermal deposits from the Haughton impact structure: implications for microbial colonization and biosignature preservation.

    Science.gov (United States)

    Izawa, M R M; Banerjee, Neil R; Osinski, G R; Flemming, R L; Parnell, J; Cockell, C S

    2011-01-01

    Meteorite impacts are among the very few processes common to all planetary bodies with solid surfaces. Among the effects of impact on water-bearing targets is the formation of post-impact hydrothermal systems and associated mineral deposits. The Haughton impact structure (Devon Island, Nunavut, Canada, 75.2 °N, 89.5 °W) hosts a variety of hydrothermal mineral deposits that preserve assemblages of primary hydrothermal minerals commonly associated with secondary oxidative/hydrous weathering products. Hydrothermal mineral deposits at Haughton include intra-breccia calcite-marcasite vugs, small intra-breccia calcite or quartz vugs, intra-breccia gypsum megacryst vugs, hydrothermal pipe structures and associated surface "gossans," banded Fe-oxyhydroxide deposits, and calcite and quartz veins and coatings in shattered target rocks. Of particular importance are sulfide-rich deposits and their associated assemblage of weathering products. Hydrothermal mineral assemblages were characterized structurally, texturally, and geochemically with X-ray diffraction, micro X-ray diffraction, optical and electron microscopy, and inductively coupled plasma atomic emission spectroscopy. Primary sulfides (marcasite and pyrite) are commonly associated with alteration minerals, including jarosite (K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6), rozenite FeSO(4)·4(H(2)O), copiapite (Fe,Mg)Fe(4)(SO(4))(6)(OH)(2)·20(H(2)O), fibroferrite Fe(SO(4))(OH)·5(H(2)O), melanterite FeSO(4)·7(H(2)O), szomolnokite FeSO(4)·H(2)O, goethite α-FeO(OH), lepidocrocite γ-FeO(OH) and ferrihydrite Fe(2)O(3)·0.5(H(2)O). These alteration assemblages are consistent with geochemical conditions that were locally very different from the predominantly circumneutral, carbonate-buffered environment at Haughton. Mineral assemblages associated with primary hydrothermal activity, and the weathering products of such deposits, provide constraints on possible microbial activity in the post-impact environment. The initial period of

  8. Grand Challenges for Environmental Magnetism

    Science.gov (United States)

    Verosub, K. L.

    2009-05-01

    The development of new, inexpensive, and rapid geochemical methods for determining the ages of geologic materials, their elemental composition, and their isotopic ratios over a broad array of elements puts into sharp focus the question: What information can environmental magnetic methods provide that can't be obtained using these other methods? Because iron is ubiquitous in the Earth's crust and because it exists in so many different forms, a discipline that looks in detail at iron-bearing minerals does have the potential to make significant contributions to the study of surficial processes. However, to reach that potential requires the development of new environmental magnetic methods. I would like to put forward three Grand Challenges for environmental magnetism that have the potential to move the field forward to a new level of scientific sophistication and that will allow environmental magnetists to compete successfully in a world increasingly dominated by geochemists. The first Grand Challenge is the development of new techniques that lead to the direct and unambiguous identification of the full suite of magnetic minerals. For many environmental magnetic applications, the key magnetic minerals are not just magnetite and hematite but also iron oxy-hydroxides (goethite, lepidocrocite, akaganeite, ferrihydrite), carbonates (siderite) and sulfides (pyrrhotite and greigite) as well as compounds involving iron and other transition metals (cobalt and nickel). The second Grand Challenge is the development of new analytical methods that provide specific quantitative values for the amount of each magnetic mineral present in a sample. One promising approach to this problem is the application of two- or three-component multivariate analysis to arrays of downcore environmental magnetic parameters. The third Grand Challenge is the development of new ways of determining, not just the average values, but the actual distributions of grain sizes and coercivities of each mineral

  9. In situ evidence of mineral physical protection and carbon stabilization revealed by nanoscale 3-D tomography

    Science.gov (United States)

    Weng, Yi-Tse; Wang, Chun-Chieh; Chiang, Cheng-Cheng; Tsai, Heng; Song, Yen-Fang; Huang, Shiuh-Tsuen; Liang, Biqing

    2018-05-01

    An approach for nanoscale 3-D tomography of organic carbon (OC) and associated mineral nanoparticles was developed to illustrate their spatial distribution and boundary interplay, using synchrotron-based transmission X-ray microscopy (TXM). The proposed 3-D tomography technique was first applied to in situ observation of a laboratory-made consortium of black carbon (BC) and nanomineral (TiO2, 15 nm), and its performance was evaluated using dual-scan (absorption contrast and phase contrast) modes. This novel tool was then successfully applied to a natural OC-mineral consortium from mountain soil at a spatial resolution of 60 nm, showing the fine structure and boundary of OC, the distribution of abundant nano-sized minerals, and the 3-D organo-mineral association in situ. The stabilization of 3500-year-old natural OC was mainly attributed to the physical protection of nano-sized iron (Fe)-containing minerals (Fe oxyhydroxides including ferrihydrite, goethite, and lepidocrocite), and the strong organo-mineral complexation. In situ evidence revealed an abundance of mineral nanoparticles, in dense thin layers or nano-aggregates/clusters, instead of crystalline clay-sized minerals on or near OC surfaces. The key working minerals for C stabilization were reactive short-range-order (SRO) mineral nanoparticles and poorly crystalline submicron-sized clay minerals. Spectroscopic analyses demonstrated that the studied OC was not merely in crisscross co-localization with reactive SRO minerals; there could be a significant degree of binding between OC and the minerals. The ubiquity and abundance of mineral nanoparticles on the OC surface, and their heterogeneity in the natural environment may have been severely underestimated by traditional research approaches. Our in situ description of organo-mineral interplay at the nanoscale provides direct evidence to substantiate the importance of mineral physical protection for the long-term stabilization of OC. This high-resolution 3-D

  10. Fe-C-S systematics in Bengal Fan sediments

    Science.gov (United States)

    Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.

    2017-12-01

    Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide

  11. Corrosion products study of alcohol by Mossbauer spectroscopy

    International Nuclear Information System (INIS)

    Velazquez, R.; Gil de Larre, M.

    1995-01-01

    Simulated corrosion essays in alcohol is presented and corrosion products of storage tanks (CAPASA) were analyzed. The analysis by Mossbauer absortion and transmission spectroscopy shows the formation of hematite substratum in the rust of the storage tanks of carburetant and burning alcohol. In the sample of corrosion with strong rum shows the formation of lepidocrocite and with destilled water besides of lepidocrocite, magnetite (Fe3 O4) is detected

  12. Influence of silicon species on the transformation of green rust I(Cl-) in aqueous solution by oxidation

    International Nuclear Information System (INIS)

    Sahoo, Gadadhar; Fujieda, Shun; Shinoda, Kozo; Yamaguchi, Shinichi; Korosaki, Masao; Suzuki, Shigeru

    2011-01-01

    Highlights: → Addition of silicate species and silica to GRI(Cl - ) increased oxidation time. → The lepidocrocite particle size in silicate added case has been reduced significantly. → The influence of silicate was attributed to its adsorption on lepidocrocite. → Silicate also influenced GRI(Cl - ) transformation due to adsorption on it. - Abstract: X-ray diffraction (XRD) and solution analysis were used for characterizing the influence of different silicon species on oxidation of green rust (GRI(Cl - )) suspension. While addition of silicon to metallic iron enhanced the formation of β-FeOOH, GRI(Cl - ) in aqueous solution oxidized into lepidocrocite and oxidation was delayed in presence of silica and silicate species as noticed from potential, pH, and dissolved oxygen (DO) measurements. Transmission electron micrographs showed that the particle size of lepidocrocite was reduced due to silicate addition. The influence of silicate was attributed to its adsorption on GRI(Cl - ) and lepidocrocite particles as confirmed from ICP-AES analysis of supernatant solution.

  13. Contribution to the study of sorption mechanisms at solid-liquid interfaces: application to the cases of apatites and oxy-hydroxides; Contribution a l'etude des mecanismes de sorption aux interfaces solide-liquide: application aux cas des apatites et des oxy-hydroxydes

    Energy Technology Data Exchange (ETDEWEB)

    Duc, M

    2002-11-15

    Sorption-desorption phenomena play an important role in the transport of toxic and radioactive elements in surface and underground water in contact with solid matter. Selenium, which is one of the long-lived radionuclides present in radioactive waste, is characterized by several oxidation states and by anionic species in aqueous solutions. In order to predict its transport, we need a good knowledge of its sorption processes. We have studied the sorption of Se(IV) and Se(VI) on two types of solids present in natural media or which have been proposed as additives to active barriers: hydroxy-apatites, fluoro-apatite and iron oxi-hydroxides (goethite and hematite). Sorption mechanisms have been studied through an approach including several different and complementary methods: titrimetry, zeta-metry, scanning and transmission electron microscopy, infrared spectroscopy, X-ray diffraction, X-ray photo electron spectroscopy, etc... Results showed that Se(VI) is much less sorbed than Se(VI) on both types of solids. For Se(IV) the sorption mechanisms are different for iron oxides and apatites. On oxides, sorption increases when pH decreases. It can be interpreted by a surface complexation model, essentially through an inner sphere complex (monodentate or bidentate). Modelling of Se sorption curves was performed after the determination of acido-basic properties of oxides. However, the determination of the intrinsic properties of oxides is disturbed by several parameters identified as impurities, evolution of the solid in solution, kinetic and solubility of the solid. For apatites, selenium sorption proceeds by exchange with superficial groups, with a maximum of fixation at approximately pH 8. Thanks to XPS measurements and the elaboration of a mathematical model, we could determine the depth of penetration of both selenium and cadmium on apatites. (author)

  14. A comparative study of nitrite reduction by synthetic and biogenic Fe(II-III) hydroxysalts green rusts: Evidence for hydroxyl-nitrite green rust formation as an intermediate reaction product.

    Science.gov (United States)

    Ona-Nguema, G.; Guerbois, D.; Morin, G.; Zhang, Y.; Noel, V.; Brest, J.

    2013-12-01

    The occurrence of high nitrite concentrations as a result of anthropogenic activities is an important water quality concern as it is highly toxic to human and fauna, and it is used as a nitrogen source for the assimilation process. The toxicity of nitrite is related to its transformation into carcinogenic N-nitroso compounds, which are suspected to be responsible for some gastric cancers, and to its ability to convert the hemoglobin to methaemoglobin what is then unable to fix oxygen and to transport it to the tissues, involving hypoxia and the blue-baby syndrome [1]. To reduce the adverse effect of nitrite on human health and on macroalgal blooms, any process enhancing the transformation of nitrite ions to nitrogen gas is of interest for the remediation of natural environments. To achieve this purpose the use of processes involving Fe(II)-containing minerals could be considered as one of the best options. Green-rusts are mixed Fe(II-III) layered double hydroxides commonly found in anoxic zones of natural environments such as sediments and hydromorphic soils. In such anoxic environments, green rust minerals play an important role in the biogeochemical redox cycling of iron and nitrogen, and can affect the speciation and mobility of many organic and inorganic contaminants. The present study investigates the reduction of nitrite by two synthetic and two biogenic green rusts. On the one hand, Fe(II-III) hydroxychloride and Fe(II-III) hydroxycarbonate green rusts were used as synthetic interlayer forms of GR, which are referred to as ';syn-GR(CO3)' and ';syn-GR(Cl)', respectively. On the other hand, the study was performed with biogenic Fe(II-III) hydroxycarbonate green rusts obtained from the bioreduction of two ferric precursors, either Fe(III)-oxyhydroxycarbonate or lepidocrocite; these biogenic green rusts are referred to as ';bio-GR(CO3)F' and ';bio-GR(CO3)L', respectively. For synthetic green rusts, results showed that the oxidation of both syn-GR(CO3) and syn

  15. Structure of Fe(III) precipitates generated by Fe(0) electrocoagulation in the presence of groundwater ions

    Science.gov (United States)

    van Genuchten, C. M.; Pena, J.; Addy, S. E.; Gadgil, A. J.

    2012-12-01

    Electrocoagulation (EC) using Fe(0) electrodes is an inexpensive and efficient technology capable of removing a variety of contaminants from water supplies. Because of its ease of use and modest electricity and Fe(0) requirements, EC has potential as an arsenic-removal technology for rural South Asia, where millions drink groundwater contaminated by arsenic. In EC, a small external voltage applied to a sacrificial Fe(0) anode in contact with an electrolyte (e.g. pumped groundwater containing arsenic) promotes the oxidative dissolution of Fe ions, which polymerize and create reactive hydrous ferric oxides (HFO) in-situ with a high affinity for binding contaminants. The chemical composition of the electrolyte influences EC performance. For example, major inorganic ions present in groundwater (e.g. Ca, Mg, P, As(V), Si) alter the pathway by which FeO6 oligomers polymerize to form crystalline Fe (oxyhydr)oxide minerals. Because the precipitate structure largely determines properties that govern the efficiency of EC systems (e.g. precipitate reactivity and colloidal stability), it is essential to understand the individual and interdependent structural effects of common groundwater ions. In this work, we integrate Fe K-edge EXAFS spectroscopy with the Pair Distribution Function (PDF) technique to create a detailed description of EC precipitate structure as a function of electrolyte chemistry. EC precipitate samples were generated in a range of individual and combined concentrations of Ca, Mg, P, As(V), and Si, encompassing most of the typical levels found in natural groundwater. Combining complementary EXAFS and PDF techniques with batch uptake experiments and general chemical reasoning, we obtain structural representations of EC precipitates that are inaccessible with any single characterization technique. Our results indicate that the presence of As(V), P, and Si oxyanions promote the formation of nanoscale material bearing similar, but not identical, intermediate

  16. Bacterial and iron oxide aggregates mediate secondary iron mineral formation: green rust versus magnetite.

    Science.gov (United States)

    Zegeye, A; Mustin, C; Jorand, F

    2010-06-01

    In the presence of methanoate as electron donor, Shewanella putrefaciens, a Gram-negative, facultative anaerobe, is able to transform lepidocrocite (gamma-FeOOH) to secondary Fe (II-III) minerals such as carbonated green rust (GR1) and magnetite. When bacterial cells were added to a gamma-FeOOH suspension, aggregates were produced consisting of both bacteria and gamma-FeOOH particles. Recently, we showed that the production of secondary minerals (GR1 vs. magnetite) was dependent on bacterial cell density and not only on iron reduction rates. Thus, gamma-FeOOH and S. putrefaciens aggregation pattern was suggested as the main mechanism driving mineralization. In this study, lepidocrocite bioreduction experiments, in the presence of anthraquinone disulfonate, were conducted by varying the [cell]/[lepidocrocite] ratio in order to determine whether different types of aggregate are formed, which may facilitate precipitation of GR1 as opposed to magnetite. Confocal laser scanning microscopy was used to analyze the relative cell surface area and lepidocrocite concentration within the aggregates and captured images were characterized by statistical methods for spatial data (i.e. variograms). These results suggest that the [cell]/[lepidocrocite] ratio influenced both the aggregate structure and the nature of the secondary iron mineral formed. Subsequently, a [cell]/[lepidocrocite] ratio above 1 x 10(7) cells mmol(-1) leads to densely packed aggregates and to the formation of GR1. Below this ratio, looser aggregates are formed and magnetite was systematically produced. The data presented in this study bring us closer to a more comprehensive understanding of the parameters governing the formation of minerals in dense bacterial suspensions and suggest that screening mineral-bacteria aggregate structure is critical to understanding (bio)mineralization pathways.

  17. Moessbauer spectroscopy study of a mineral sample from Oshno Hill, District of Chavin de Pariarca, Huanuco Region, Peru

    International Nuclear Information System (INIS)

    Bustamante, A.; Lovera, D.; Quille, R.; Arias, A. V.; Quinones, J.

    2010-01-01

    The analysis by X-ray diffraction of a mining sample collected from Oshno hill, which is located in the District of Chavin de Pariarca, Huamalies Province, Huanuco, Peru, indicates the presence of lepidocrocite (γ-FeOOH) and goethite (α-FeOOH). The room temperature Moessbauer spectrum (MS) doublet with broad lines displays hyperfine parameters corresponding to the presence of particles of iron hydroxides smaller than 100 A in a superparamagnetic regime. The measurement of a MS at 4.2 K allowed confirming the presence of goethite and lepidocrocite (with average magnetic fields of 49.21 T and 44.59 T, respectively).

  18. Biogenic Fe(III) minerals lower the efficiency of iron-mineral based commercial filter systems for arsenic removal

    DEFF Research Database (Denmark)

    Kleinert, Susanne; Muehe, Eva M.; Posth, Nicole

    2011-01-01

    Millions of people worldwide are affected by As (arsenic) contaminated groundwater. Fe(III) (oxy)hydroxides sorb As efficiently and are therefore used in water purification filters. Commercial filters containing abiogenic Fe(III) (oxy)hydroxides (GEH) showed varying As removal, and it was unclear...

  19. Hybrid n-Alkylamine Intercalated Layered Titanates for Solid Lubrication

    NARCIS (Netherlands)

    Gonzalez Rodriguez, P.; Yuan, H.; van den Nieuwenhuijzen, Karin Jacqueline Huberta; Lette, W.; Schipper, Dirk J.; ten Elshof, Johan E.

    2016-01-01

    The intercalation of different primary n-alkylamines in the structure of a layered titanate of the lepidocrocite type (H1.07Ti1.73O4) for application in high-temperature solid lubrication is reported. The intercalation process of the amines was explored by means of in situ small-angle X-ray

  20. The reduction of 4-chloronitrobenzene by Fe(II)-Fe(III) oxide systems - correlations with reduction potential and inhibition by silicate

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Adele M., E-mail: adele.jones1@unsw.edu.au; Kinsela, Andrew S.; Collins, Richard N.; Waite, T. David, E-mail: d.waite@unsw.edu.au

    2016-12-15

    Recent studies have demonstrated that the rate at which Fe(II)-Fe(III) oxyhydroxide systems catalyze the reduction of reducible contaminants, such as 4-chloronitrobenzene, is well correlated to their thermodynamic reduction potential. Here we confirm this effect in the presence of Fe(III) oxyhydroxide phases not previously assessed, namely ferrihydrite and nano-goethite, as well as Fe(III) oxyhydroxide phases previously examined. In addition, silicate is found to decrease the extent of Fe(II) sorption to the Fe(III) oxyhydroxide surface, increasing the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspension and, accordingly, decreasing the rate of 4-chloronitrobenzene reduction. A linear relationship between the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspensions and the reduction rate of 4-chloronitrobenzene (normalized to surface area and concentration of sorbed Fe(II)) was obtained in the presence and absence of silicate. However, when ferrihydrite was doped with Si (through co-precipitation) the reduction of 4-chloronitrobenzene was much slower than predicted from its reduction potential. The results obtained have significant implications to the likely effectiveness of naturally occurring contaminant degradation processes involving Fe(II) and Fe(III) oxyhydroxides in groundwater environments containing high concentrations of silicate, or other species which compete with Fe(II) for sorption sites.

  1. Abdus-Salam and Ikudayisi (10)

    African Journals Online (AJOL)

    DELL

    Instrumental characterization such as Fourier Transform Infrared (FTIR) for ... The nano-sizer also revealed a near nano-size for the synthesized goethite ... Keywords: Iron oxy-hydroxide, Goethite, Date-palm seeds, Particle nano-sizer, BET.

  2. Controls on ferromanganese crust composition and reconnaissance resource potential, Ninetyeast Ridge, Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Hein, J.R.; Conrad, T.; Mizell, K.; Banakar, V.K.; Frey, F.A.; Sager, W.W.

    adsorbed on the Fe oxyhydroxide. The enrichment of Ni, Zn, and Cu in the phosphatized crust reflects preferential adsorption into the tunnel structure of todorokite. The rare earth element plus yttrium (REY) patterns indicate a lower oxidation potential...

  3. Early diagenetic processes affecting nutrients in the pore waters of Central Indian Ocean cores

    Digital Repository Service at National Institute of Oceanography (India)

    Nath, B.N.; Mudholkar, A.V.

    and unoxidized organic carbon are observed in the Arabian Sea core, while nitrification with intermediate low nitrate and high organic carbon are found in the mottled zones of the pelagic cores. Mobilization of iron-host oxyhydroxides and peaked profiles...

  4. Structural transformation of nickel hydroxide films during anodic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Crocker, Robert W. [Univ. of California, Berkeley, CA (United States); Muller, Rolf H. [Univ. of California, Berkeley, CA (United States)

    1992-05-01

    The transformation of anodically formed nickel hydroxide/oxy-hydroxide electrodes has been investigated. A mechanism is proposed for the anodic oxidation reaction, in which the reaction interface between the reduced and oxidized phases of the electrode evolves in a nodular topography that leads to inefficient utilization of the active electrode material. In the proposed nodular transformation model for the anodic oxidation reaction, nickel hydroxide is oxidized to nickel oxy-hydroxide in the region near the metal substrate. Since the nickel oxy-hydroxide is considerably more conductive than the surrounding nickel hydroxide, as further oxidation occurs, nodular features grow rapidly to the film/electrolyte interface. Upon emerging at the electrolyte interface, the reaction boundary between the nickel hydroxide and oxy-hydroxide phases spreads laterally across the film/electrolyte interface, creating an overlayer of nickel oxy-hydroxide and trapping uncharged regions of nickel hydroxide within the film. The nickel oxy-hydroxide overlayer surface facilitates the oxygen evolution side reaction. Scanning tunneling microscopy of the electrode in its charged state revealed evidence of 80 - 100 Angstrom nickel oxy-hydroxide nodules in the nickel hydroxide film. In situ spectroscopic ellipsometer measurements of films held at various constant potentials agree quantitatively with optical models appropriate to the nodular growth and subsequent overgrowth of the nickel oxy-hydroxide phase. A two-dimensional, numerical finite difference model was developed to simulate the current distribution along the phase boundary between the charged and uncharged material. The model was used to explore the effects of the physical parameters that govern the electrode behavior. The ratio of the conductivities of the nickel hydroxide and oxy-hydroxide phases was found to be the dominant parameter in the system.

  5. Structural transformation of nickel hydroxide films during anodic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Crocker, R.W.; Muller, R.H.

    1992-05-01

    The transformation of anodically formed nickel hydroxide/oxy-hydroxide electrodes has been investigated. A mechanism is proposed for the anodic oxidation reaction, in which the reaction interface between the reduced and oxidized phases of the electrode evolves in a nodular topography that leads to inefficient utilization of the active electrode material. In the proposed nodular transformation model for the anodic oxidation reaction, nickel hydroxide is oxidized to nickel oxy-hydroxide in the region near the metal substrate. Since the nickel oxy-hydroxide is considerably more conductive than the surrounding nickel hydroxide, as further oxidation occurs, nodular features grow rapidly to the film/electrolyte interface. Upon emerging at the electrolyte interface, the reaction boundary between the nickel hydroxide and oxy-hydroxide phases spreads laterally across the film/electrolyte interface, creating an overlayer of nickel oxy-hydroxide and trapping uncharged regions of nickel hydroxide within the film. The nickel oxy-hydroxide overlayer surface facilitates the oxygen evolution side reaction. Scanning tunneling microscopy of the electrode in its charged state revealed evidence of 80 {endash} 100 Angstrom nickel oxy-hydroxide nodules in the nickel hydroxide film. In situ spectroscopic ellipsometer measurements of films held at various constant potentials agree quantitatively with optical models appropriate to the nodular growth and subsequent overgrowth of the nickel oxy-hydroxide phase. A two-dimensional, numerical finite difference model was developed to simulate the current distribution along the phase boundary between the charged and uncharged material. The model was used to explore the effects of the physical parameters that govern the electrode behavior. The ratio of the conductivities of the nickel hydroxide and oxy-hydroxide phases was found to be the dominant parameter in the system.

  6. Use of Infrared spectroscopy for the akaganeite identification 3. NACE Latin American Corrosion Congress and the 6. Ibero-American Congress of Corrosion and Protection; Uso de la espectroscopia IR para la identificacion de la kaganeita

    Energy Technology Data Exchange (ETDEWEB)

    Parra, A.; Martinez, L. [Instituto de Fisica, UNAM, A.P. 48-3, C.P. 62251, Cuernavaca, Morelos, Mexico (Mexico); Mondragon, M.A.; Castano, V. [Instituto de Fisica, UNAM, Mexico D.F. (Mexico)

    1998-12-31

    It is now knew that 1020 and 750 bands belong to lepidocrocite phase; 890 and 790 are goethite bands. The akaganeite is identified in the 840 band; but when it is in a small quantity, its spectra is opaque by the goethite. It is considered that this type of IR analysis, is ideal to identify the lepidocrocite and goethite not so for the akaganeite. In order to identify and to quantify the akaganeite it is used the X-ray spectroscopy and Moessbauer, moreover to identify the akaganeite with Moessbauer analysis, which is realized at low temperature. However, if the quantity of akaganeite is significant the infrared spectra will be very clear for the 840 band that is characteristic of the akaganeite. (Author)

  7. Use of Infrared spectroscopy for the akaganeite identification 3. NACE Latin American Corrosion Congress and the 6. Ibero-American Congress of Corrosion and Protection

    International Nuclear Information System (INIS)

    Parra, A.; Martinez, L.; Mondragon, M.A.; Castano, V.

    1998-01-01

    It is now knew that 1020 and 750 bands belong to lepidocrocite phase; 890 and 790 are goethite bands. The akaganeite is identified in the 840 band; but when it is in a small quantity, its spectra is opaque by the goethite. It is considered that this type of IR analysis, is ideal to identify the lepidocrocite and goethite not so for the akaganeite. In order to identify and to quantify the akaganeite it is used the X-ray spectroscopy and Moessbauer, moreover to identify the akaganeite with Moessbauer analysis, which is realized at low temperature. However, if the quantity of akaganeite is significant the infrared spectra will be very clear for the 840 band that is characteristic of the akaganeite. (Author)

  8. Iron oxide and hydroxide precipitation from ferrous solutions and its relevance to Martian surface mineralogy

    Science.gov (United States)

    Posey-Dowty, J.; Moskowitz, B.; Crerar, D.; Hargraves, R.; Tanenbaum, L.

    1986-01-01

    Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished.

  9. Iron oxide and hydroxide precipitation from ferrous solutions and its relevance to Martian surface mineralogy

    International Nuclear Information System (INIS)

    Posey-Dowty, J.; Moskowitz, B.; Crerar, D.; Hargraves, R.; Tanenbaum, L.

    1986-01-01

    Experiments were performed to examine if the ubiquitousness of a weak magnetic component in all Martian surface fines tested with the Viking Landers can be attributed to ferric iron precipitation in aqueous solution under oxidizing conditions at neutral pH. Ferrous solutions were mixed in deionized water and various minerals were added to separate liquid samples. The iron-bearing additives included hematite, goethite, magnetite, maghemite, lepidocrocite and potassium bromide blank at varying concentrations. IR spectroscopic scans were made to identify any precipitates resulting from bubbling oxygen throughout the solutions; the magnetic properties of the precipitates were also examined. The data indicated that the lepidocrocite may have been preferentially precipitated, then aged to maghemite. The process would account for the presumed thin residue of maghemite on the present Martian surface, long after abundant liquid water on the Martian surface vanished. 40 references

  10. Influence of Oxygen and Nitrate on Fe (Hydr)oxide Mineral Transformation and Soil Microbial Communities during Redox Cycling.

    Science.gov (United States)

    Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew

    2016-04-05

    Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments.

  11. Moessbauer spectroscopy characterization and electrochemical study of the kinetics of oxidation of iron in chlorinated aqueous media: structure and equilibrium diagram of green rust one

    International Nuclear Information System (INIS)

    Genin, J.M.R.; Rezel, D.; Bauer, Ph.; Olowe, A.; Beral, A.

    1986-01-01

    Moessbauer spectroscopy allows to precise the structure of akaganeite, lepidocrocite, green rust I and initial hydroxide of a simulated corrosion process of iron in chlorinated aqueous media. The characterization of the compounds during the process is coupled with E - pH recordings, yielding the kinetics of the various reactions (order and activation energy) as well as the Pourbaix diagram of Green Rust I by scanning the [Cl - ]/[OH - ] ratio. (author) 16 refs., 15 figs

  12. A modelling of the mechanisms occurring during the atmospheric corrosion of iron

    International Nuclear Information System (INIS)

    Marechal, L.; Perrin, S.; Hoerle, S.; Mazaudier, F.; Dillmann, P.

    2004-01-01

    In order to predict the long-term corrosion of metallic containers in storage conditions, a modelling of atmospheric corrosion of iron is proposed. This modelling takes into account the mechanisms which occur during the three stages of a wet-dry cycle. During the wetting stage, the reduction of lepidocrocite (g-FeOOH), a constituent of the rust layer, is considered to be the rate-limiting step of the corrosion. During the second stage of the cycle, the wet period, the reduction of dissolved oxygen on the lepidocrocite, previously reduced, is controlling the mechanism. The amount of oxidized metal depends on the quantity of reduced lepidocrocite and also on the oxygen diffusion in the electrolyte and the rust layer. At the end of the cycle, the blocking of the anodic sites is considered to describe the extinction of electrochemical corrosion during the drying. It appears that each stage of the cycle depends mainly on the chemical and morphological properties of the rust layer. (authors)

  13. Origin and Reactivity of the Martian Soil: A 2003 Micromission

    Science.gov (United States)

    Yen, Albert S.; Kim, S. Sam; Marshall, John; Murray, Bruce C.

    1999-01-01

    The role of water in the development of the martian surface remains a fundamental scientific question. Did Mars have one or more "warm and wet" climatic episodes where liquid water was stable at the surface? If so, the mineral phases present in the soils should be consistent with a history of aqueous weathering. More generally, the formation of hydrated mineral phases on Mars is a strong indicator of past habitable surface environments. The primary purpose of this investigation is to help resolve the question of whether such aqueous indicators are present on Mars by probing the upper meter for diagnostic mineral species. According to Burns [1993], the formation of the ferric oxides responsible for the visible color of Mars are the result of dissolution of Fe (+2) phases from basalts followed by aqueous oxidation and precipitation of Fe" mineral assemblages. These precipitates likely included iron oxyhydroxides such as goethite (a-FeOOH) and lepidocrocite (g-FeOOH), but convincing evidence for these phases at the surface is still absent. The stability of these minerals is enhanced beneath the surface, and thus we propose a subsurface search for hydroxylated iron species as a test for a large-scale chemical weathering process based on interactions with liquid water. It is also possible that the ferric minerals on Mars are not aqueous alteration products of the rocks. A chemical study of the Pathfinder landing site concluded that the soils are not directly derived from the surrounding rocks and are enhanced in Mg and Fe. The additional source of these elements might be from other regions of Mars and transported by winds, or alternatively, from exogenic sources. Gibson [1970] proposed that the spectral reflectivity of Mars is consistent with oxidized meteoritic material. Yen and Murray [1998] further extend Gibson's idea and show, in the laboratory, that metallic iron can be readily oxidized to maghemite and hematite under present-day martian surface conditions (in the

  14. Mineralogy and geochemistry of uranium mill tailings

    International Nuclear Information System (INIS)

    Pagel, M.; Somot, S.

    2002-01-01

    We have investigated three main types of uranium mill tailings: (1) acid mill tailings (Mounana, Gabon), (2) neutralized acid mill tailings (Ecarpiere and Jouac, France) and (3) alkaline mill tailings (Lodeve, France). We have focused especially on radium behaviour which is of major environmental concern in these tailings, but other metals were also studied. It is shown that in type 1 , trapping of 226 Ra by anglesite and barite is dominant whereas in types 2 and 3, 226 Ra is mainly or significantly scavenged by Fe- Mn oxyhydroxides. This study points out the importance of keeping conditions in which these oxyhydroxides will be stable for the long-term. Uranium would be also released during acidification of the tailings. This shows the importance to know more about the behavior of Ra during the crystallization of oxyhydroxides and during tailings diagenesis. Therefore, it is very important to study the sorption of Ra by clay minerals or late authigeneous minerals such as barite. (author)

  15. Iron oxide nanoparticles for plant nutrition? A preliminary Mössbauer study

    Energy Technology Data Exchange (ETDEWEB)

    Homonnay, Z., E-mail: homonnay@caesar.elte.hu [EötvösLoránd University, Institute of Chemistry (Hungary); Tolnai, Gy. [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry (Hungary); Fodor, F.; Solti, Á. [EötvösLoránd University, Institute of Biology (Hungary); Kovács, K.; Kuzmann, E.; Ábrahám, A. [EötvösLoránd University, Institute of Chemistry (Hungary); Szabó, E. Gy.; Németh, P.; Szabó, L.; Klencsár, Z. [Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry (Hungary)

    2016-12-15

    One of the most important micronutrients for plants is iron. We have prepared iron(III) oxyhydroxide and magnetite nanoparticles with the aim to use them as possible nutrition source for plants. The iron(III)-oxide/oxyhydroxide nanoparticles prepared under our experimental conditions as colloidal suspensions proved to be 6-line ferrihydrite nanoparticles as verified by XRD, TEM/SAED and Mössbauer spectroscopy measurements. {sup 57}Fe Mössbauer spectra of magnetite nanoparticles prepared under different preparation conditions could be analyzed on the basis of a common model based on the superposition of four sextet components displaying Gaussian-shaped hyperfine magnetic field distributions.

  16. Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

    Science.gov (United States)

    ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben

    2016-04-05

    Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

  17. Mössbauer spectroscopy and X-ray fluorescence studies on sediments from the methanic zone of the Helgoland mud area, North Sea

    Energy Technology Data Exchange (ETDEWEB)

    Costa, B. F. O. [University of Coimbra, CFisUC, Physics Department (Portugal); Blumers, M.; Shylin, S. I.; Ksenofontov, V. [Johannes Gutenberg University, Institute for Inorganic and Analytical Chemistry (Germany); Oni, O. [University of Bremen, Microbial Ecophysiology group, Faculty of Biology/Chemistry (Germany); Kasten, S.; Fischer, D. [University of Bremen, MARUM, Center for Marine Environmental Sciences (Germany); Wagenknecht, L. [Alfred Wegener Institute Helmholtz Center for Polar and Marine Research (Germany); Kulkarni, A.; Friedrich, M. W. [University of Bremen, Microbial Ecophysiology group, Faculty of Biology/Chemistry (Germany); Klingelhöfer, G., E-mail: klingel@mail.uni-mainz.de [Johannes Gutenberg University, Institute for Inorganic and Analytical Chemistry (Germany)

    2016-12-15

    {sup 57}Fe Mössbauer spectroscopy (MS) and X-ray fluorescence spectroscopy (XRF) were used to determine the identity of iron(III) oxides in surface (top 30 cm ) and subsurface (> 30 cm – 500 cm)sediments from the Helgoland mud area in the German Bight of the North Sea. A 500 cm-long sediment core was cut in 25 cm sections while only the top 10 cm of a 30 cm-long sediment core was sampled. Using a MIMOS spectrometer, MS spectra were recorded at 293 K (RT) in backscattering geometry. At 80 K and 5.5 K, MS analysis was carried out in transmission geometry. At RT and 80 K only illite was observed, but at 5.5 K lepidocrocite was revealed in the MS spectra. The relation between Fe(III) and Fe(II) doublets of illite did not significantly vary with depth, but the relative amount of lepidocrocite increased with depth reaching about 24 % of iron phases, as revealed by MS. XRF measurements showed that the amount of Fe in the sediments varied with depth but was always less than 4 % of total elemental composition. The main component of the sediment was silica and its depth profile alternated with those of other elements, especially aluminium and iron. It was observed that elevated concentrations of dissolved iron in the subsurface sediment of the Helgoland mud area correlated with the depth-wise distribution of distinct microbial populations presumably due to microbial reduction of excess bioavailable iron minerals such as lepidocrocite. These results are thus, important in the context of microbe-mineral interactions in marine sediments as iron oxides are an electron acceptor for microbial anaerobic respiration.

  18. The Mineralogic Transformation of Ferrihydrite Induced by Heterogeneous Reaction with Bioreduced Anthraquinone Disulfonate (AQDS) and the Role of Phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Zachara, John M.; Kukkadapu, Ravi K.; Peretyazhko, Tetyana; Bowden, Mark E.; Wang, Chong M.; Kennedy, David W.; Moore, Dean A.; Arey, Bruce W.

    2011-10-12

    Anthraquinone-2-6-disulfonate (AQDS) enhances electron donor utilization and mineral product crystallization in studies of Fe(III) oxide reductive mineralization by metal reducing bacteria (MRB) through heterogeneous redox reaction. In spite of the strong effect of AQDS in these systems, little information exits on its direct role in reductive mineralization. To provide such insights, bioreduced AQDS (AH2DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH2DS oxidation coupled with Fe(III) reduction occurred within 0.13-1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. P inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)]=0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)aq system, while AQDS was more effective than Fe(II)aq in promoting magnetite formation. The direct AH2DS-driven reductive reaction pathway produced mineral products that were different from AH2DS-ferrihydite-MRB systems, particularly in presence of P.

  19. Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

    Science.gov (United States)

    Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

    2015-08-30

    Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Sorption of pesticides to aquifer minerals

    DEFF Research Database (Denmark)

    Clausen, Liselotte; Fabricius, Ida Lykke

    2000-01-01

    This paper summarizes results from a work were the sorption of five pesticides on seven minerals were studied in order to quantify the adsorption to different mineral surfaces. Investigated mineral phases are: quartz, calcite, kaolinite, a-alumina, and three iron oxides (2-line ferrihydrite......, goethite, lepidocrocite). Selected pesticides are: atrazine, isoproturon, mecoprop, 2,4-D, and bentazone. The results demonstrate that pesticides adsorb to pure mineral surfaces. However, the size of the adsorption depends on the type of pesticide and the type of mineral....

  1. Influence of silicon on local structure and morphology of γ-FeOOH and α-FeOOH particles

    International Nuclear Information System (INIS)

    Kwon, Sang-Koo; Shinoda, Kozo; Suzuki, Shigeru; Waseda, Yoshio

    2007-01-01

    The extended X-ray absorption fine structure (EXAFS) method was used for investigating the local structures of lepidocrocite and goethite with and without silicon. The structure and morphology of these particles were investigated using X-ray diffraction and transmission electron microscopy, respectively. The bonding structure was examined by Fourier transform infrared spectroscopy (FT-IR). When silicon species was added, the structure and morphology changed while the linkage of FeO 6 octahedral units was distorted. The FT-IR spectra revealed the formation of the Fe-O-Si bond in particles containing silicate ions, and the characteristic bond affects the local structure and morphology of the particles

  2. A contribution to the modelling of atmospheric corrosion of iron

    International Nuclear Information System (INIS)

    Hoerle, S.; Mazaudier, F.

    2003-01-01

    With the aim of predicting the long term atmospheric corrosion behaviour of iron, the characteristics of the rust layer formed during this process and the mechanisms occurring inside the rust layer during a wet-dry cycle are considered. A first step in modelling the behaviour is proposed, based on the description of the cathodic reactions associated with iron oxidation: reduction of a part of the rust layer (lepidocrocite) and reduction of dissolved oxygen on the rust layer. The modelling, by including some composition and morphological data of the rust layer as parameters, is able to account for the metal damage after one Wet-Dry cycle. (authors)

  3. A Moessbauer and Electrochemical Characterization of the Corrosion Products Formed from Marine and Marine-Antartic Environments

    Energy Technology Data Exchange (ETDEWEB)

    Ohanian, M.; Caraballo, R.; Dalchiele, E. A.; Quagliata, E. [Instituto de Ingenieria Quimica, Facultad de Ingenieria (Uruguay)

    2003-06-15

    Corrosion products formed on low alloy steel under two marine environments are characterised. Both environments are classified as C4 according to the ISO 9223 Standard. The corrosion products are identified and their relative proportion is determined by Moessbauer spectroscopy (transmission geometry). Free potentials of corrosion are measured to evaluate the activity of their surfaces. Structural characterisation by XRD were performed on selected samples. It is concluded that the principal phases are goethite, lepidocrocite, ferrihidrite and maghemite. The relative amount of each of them changes with time and with the atmospheric dynamics of each environment.

  4. A Moessbauer and Electrochemical Characterization of the Corrosion Products Formed from Marine and Marine-Antartic Environments

    International Nuclear Information System (INIS)

    Ohanian, M.; Caraballo, R.; Dalchiele, E. A.; Quagliata, E.

    2003-01-01

    Corrosion products formed on low alloy steel under two marine environments are characterised. Both environments are classified as C4 according to the ISO 9223 Standard. The corrosion products are identified and their relative proportion is determined by Moessbauer spectroscopy (transmission geometry). Free potentials of corrosion are measured to evaluate the activity of their surfaces. Structural characterisation by XRD were performed on selected samples. It is concluded that the principal phases are goethite, lepidocrocite, ferrihidrite and maghemite. The relative amount of each of them changes with time and with the atmospheric dynamics of each environment.

  5. Evaluation of sorption capacity of adjusted woody biomass for pentavalent arsenic

    International Nuclear Information System (INIS)

    Littera, P.

    2009-01-01

    Aim of the present experiment was to evaluate the sorption capacity of wood biomass modified by iron oxyhydroxide. Capacity was assessed in tank experiments. Model solutions of pentavalent arsenic in concentration range of 20 mg L -1 -500 mg L -1 were used. Binder dosing 10 g L -1 was selected, contact time of the binder with solution was 2 hours. (author)

  6. Precipitation pathways for ferrihydrite formation in acidic solutions

    DEFF Research Database (Denmark)

    Zhu, Mengqiang; Frandsen, Cathrine; Wallace, Adam F.

    2016-01-01

    to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 ... occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process....

  7. Interactions of silica with iron oxides: Effects on oxide transformations and sorption properties

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, P

    1995-08-01

    This report is a review of the literature on the adsorption of silica species on iron oxides and oxyhydroxides, and its effects on the adsorption of other species and on oxide interconversion reactions. The information is discussed briefly in the contexts of nuclear waste disposal and boiler-water chemistry. (author). 76 refs.

  8. Phosphate fixation and the response of maize to fertilizer phosphate in Kenyan soils

    NARCIS (Netherlands)

    Eijk, van der D.

    1997-01-01

    In tropical soils, plant growth is often limited by a low P availability. In addition, these soils often have high P-fixation capacities due to high amounts of iron and aluminum oxyhydroxides. Furthermore, small-scale farming systems in which subsistence crops are produced for local markets are

  9. Primary sink and source of geogenic arsenic in sedimentary aquifers in the southern Choushui River alluvial fan, Taiwan

    International Nuclear Information System (INIS)

    Lu, Kuang-Liang; Liu, Chen-Wuing; Wang, Sheng-Wei; Jang, Cheng-Shin; Lin, Kao-Hung; Liao, Vivian Hsiu-Chuan; Liao, Chung-Min; Chang, Fi-John

    2010-01-01

    This work characterized the sink and source/mobility of As in the As-affected sedimentary aquifers of the southern Choushui River alluvial fan, central Taiwan. Major mineral phases and chemical components were determined by XRD and X-ray photoelectron spectroscopy (XPS). The partitioning of As and Fe among cores were determined by sequential extraction. Based on XPS results, the primary forms of Fe were hematite, goethite and magnetite. Sequential extraction data and the XRF analysis indicated that Fe oxyhydroxides and sulfides were likely to be the major sinks of As, particularly in the distal-fan. Furthermore, Fe oxyhydroxides retained higher As contents than As-bearing sulfides. The reductive dissolution of Fe oxyhydroxides, which accompanied high levels of HCO 3 - and NH 4 + concentrations, was likely the principal release mechanism of As into groundwater in this area. The dual roles of Fe oxyhydroxides which are governed by the local redox condition act as a sink and source in the aquifer. Ionic replacement by PO 4 3- and HCO 3 - along with seasonal water table fluctuation, caused by monsoons and excessive pumping, contributed specific parts of As in the groundwater. The findings can be used to account for the inconsistency between Fe and As concentrations observed in groundwater.

  10. Rare earth element studies of surficial sediments from the southwestern Carlsberg Ridge, Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Pattan, J.N.; Higgs, N.C.

    content. REEs show a strong positive correlation with Al+Fe+K+Mg+Na (r sup(2)=0.98) and Mn+Fe+Cu+Ni (r sup(2)=0.86) suggesting that the REE is associated with a combined phase of clays (mainly illite) and Mn-Fe oxyhydroxides. The aeolian input...

  11. Geochemical fractionation of Ni, Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment

    Digital Repository Service at National Institute of Oceanography (India)

    Sensarma, S.; Chakraborty, P.; Banerjee, R.; Mukhopadhyay, S.

    speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase...

  12. Journal of Earth System Science | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    ... extracellular polymeric substance (EPS). Mineralization took place on these organotemplates by the process of permineralization as well as replacement in an early diagenetic pore-water environment with reduction of higher manganese oxy-hydroxides by organic matter and consequent increase in dissolved carbonate.

  13. Ecological aspects of Moessbauer study of iron-containing atmospheric aerosols

    International Nuclear Information System (INIS)

    Kopcewicz, B.; Kopcewicz, M.

    2000-01-01

    Moessbauer spectroscopy was applied to analyze the iron compounds in atmospheric aerosol. Seasonal variations of iron concentration in atmospheric air measured over twenty years in Poland are discussed. It was observed that the concentration of iron sulfides (FeS, FeS 2 ) related to coal combustion dropped significantly, however, concentration of iron oxides and iron oxyhydroxides related to fuel combustion increased

  14. Ferrite grade iron oxides from ore rejects

    Indian Academy of Sciences (India)

    Iron oxyhydroxides and hydroxides were synthesized from chemically beneficiated high SiO2/Al2O3 low-grade iron ore (57.49% Fe2O3) rejects and heated to get iron oxides of 96–99.73% purity. The infrared band positions, isothermal weight loss and thermogravimetric and chemical analysis established the chemical ...

  15. Multifunctional Silver Coated E-33/Iron Oxide Water Filters: Inhibition of Biofilm Growth and Arsenic Removal

    Science.gov (United States)

    Bayoxide® E33 (E-33, Goethite) is a widely used commercial material for arsenic adsorption. It is a mixture of iron oxyhydroxide and oxides. E-33 is primarily used to remove arsenic from water and to a lesser extent, other anions, but generally lacks multifunctuality. It is a non...

  16. Effect Of Imposed Anaerobic Conditions On Metals Release From Acid-Mine Drainage Contaminated Streambed Sediments

    Science.gov (United States)

    Remediation of streams influenced by mine-drainage may require removal and burial of metal-containing bed sediments. Burial of aerobic sediments into an anaerobic environment may release metals, such as through reductive dissolution of metal oxyhydroxides. Mining-impacted aerob...

  17. Kinetics of microbial Fe(III) oxyhydroxidereduction: The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, Steeve

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  18. Interactions of silica with iron oxides: Effects on oxide transformations and sorption properties

    International Nuclear Information System (INIS)

    Taylor, P.

    1995-08-01

    This report is a review of the literature on the adsorption of silica species on iron oxides and oxyhydroxides, and its effects on the adsorption of other species and on oxide interconversion reactions. The information is discussed briefly in the contexts of nuclear waste disposal and boiler-water chemistry. (author). 76 refs

  19. The Role of Chloride Ions during the Formation of Akaganéite Revisited

    Directory of Open Access Journals (Sweden)

    Johanna Scheck

    2015-11-01

    Full Text Available Iron(III hydrolysis in the presence of chloride ions yields akaganéite, an iron oxyhydroxide mineral with a tunnel structure stabilized by the inclusion of chloride. Yet, the interactions of this anion with the iron oxyhydroxide precursors occurring during the hydrolysis process, as well as its mechanistic role during the formation of a solid phase are debated. Using a potentiometric titration assay in combination with a chloride ion-selective electrode, we have monitored the binding of chloride ions to nascent iron oxyhydroxides. Our results are consistent with earlier studies reporting that chloride ions bind to early occurring iron complexes. In addition, the data suggests that they are displaced with the onset of oxolation. Chloride ions in the akaganéite structure must be considered as remnants from the early stages of precipitation, as they do not influence the basic mechanism, or the kinetics of the hydrolysis reactions. The structure-directing role of chloride is based upon the early stages of the reaction. The presence of chloride in the tunnel-structure of akagenéite is due to a relatively strong binding to the earliest iron oxyhydroxide precursors, whereas it plays a rather passive role during the later stages of precipitation.

  20. Untitled

    Indian Academy of Sciences (India)

    attributed to their incorporation in the CaCO lattice or adsorption of Fe-Mn oxyhydroxide coatings (Palmer 1985; Shaw and Wasserberg 1985; Wang et al 1986). REE distribution patterns and their association with a limited number of calcareous sediments from the Indian Ocean (Central Indian Basin and Wharton Basin) ...

  1. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    Van Der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; Van Der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  2. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water.

    NARCIS (Netherlands)

    Grift, van der B.; Rozemeijer, J.C.; Griffioen, J.; Velde, van der Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and 5 P immobilization along the flow-path

  3. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  4. Corrosion of steel in carbonated media: The oxidation processes of chukanovite (Fe2(OH)2CO3)

    International Nuclear Information System (INIS)

    Azoulay, I.; Rémazeilles, C.; Refait, Ph.

    2014-01-01

    Highlights: • Oxidation of chukanovite does not lead to carbonated green rust. • Both lepidocrocite and goethite can result from the oxidation of chukanovite. • Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate. • Chukanovite crystal structure withstands a partial oxidation of Fe(II) to Fe(III). - Abstract: The oxidation of aqueous suspensions of chukanovite (Fe 2 (OH) 2 CO 3 ) obtained by mixing NaOH, FeCl 2 and Na 2 CO 3 solutions was studied. The reaction was monitored by recording the pH and the redox potential of a platinum electrode immersed in the suspension. The precipitate was analyzed at various oxidation stages by infrared spectroscopy. The end products were also characterized by X-ray diffraction. The oxidation by air of the suspensions leads to lepidocrocite and goethite without formation of an intermediate green rust compound. Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate with a crystal structure closely related to that of chukanovite

  5. The formation of green rust induced by tropical river biofilm components

    International Nuclear Information System (INIS)

    Jorand, F.; Zegeye, A.; Ghanbaja, J.; Abdelmoula, M.

    2011-01-01

    In the Sinnamary Estuary (French Guiana), a dense red biofilm grows on flooded surfaces. In order to characterize the iron oxides in this biofilm and to establish the nature of secondary minerals formed after anaerobic incubation, we conducted solid analysis and performed batch incubations. Elemental analysis indicated a major amount of iron as inorganic compartment along with organic matter. Solid analysis showed the presence of two ferric oxides ferrihydrite and lepidocrocite. Bacteria were abundant and represented more than 10 11 cells g -1 of dry weight among which iron reducers were revealed. Optical and electronic microscopy analysis revealed than the bacteria were in close vicinity of the iron oxides. After anaerobic incubations with exogenous electron donors, the biofilm's ferric material was reduced into green rust, a Fe II -Fe III layered double hydroxide. This green rust remained stable for several years. From this study and previous reports, we suggest that ferruginous biofilms should be considered as a favorable location for GR biomineralization when redox conditions and electron donors availability are gathered. - Research highlights: → Characterization of ferruginous biofilm components by solid analysis methods. → Lepidocrocite and ferrihydrite were the main iron oxides. → Anaerobic incubation of biofilm with electron donors produced green rust. → Biofilm components promote the formation of the green rust. → Ferruginous biofilm could contribute to the natural mercury attenuation.

  6. The formation of green rust induced by tropical river biofilm components

    Energy Technology Data Exchange (ETDEWEB)

    Jorand, F., E-mail: jorand@pharma.uhp-nancy.fr [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME) UMR 7564, CNRS-Nancy-Universite, Institut Jean Barriol, 405 rue de Vandoeuvre, F-54600 Villers-les Nancy (France); Zegeye, A. [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME) UMR 7564, CNRS-Nancy-Universite, Institut Jean Barriol, 405 rue de Vandoeuvre, F-54600 Villers-les Nancy (France); Ghanbaja, J. [Service Commun de Microscopies Electroniques et Microanalyses X (SCMEM), Nancy-Universite, Bvd des Aiguillettes, BP 239, 54506, Vandoeuvre-les-Nancy (France); Abdelmoula, M. [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME) UMR 7564, CNRS-Nancy-Universite, Institut Jean Barriol, 405 rue de Vandoeuvre, F-54600 Villers-les Nancy (France)

    2011-06-01

    In the Sinnamary Estuary (French Guiana), a dense red biofilm grows on flooded surfaces. In order to characterize the iron oxides in this biofilm and to establish the nature of secondary minerals formed after anaerobic incubation, we conducted solid analysis and performed batch incubations. Elemental analysis indicated a major amount of iron as inorganic compartment along with organic matter. Solid analysis showed the presence of two ferric oxides ferrihydrite and lepidocrocite. Bacteria were abundant and represented more than 10{sup 11} cells g{sup -1} of dry weight among which iron reducers were revealed. Optical and electronic microscopy analysis revealed than the bacteria were in close vicinity of the iron oxides. After anaerobic incubations with exogenous electron donors, the biofilm's ferric material was reduced into green rust, a Fe{sup II}-Fe{sup III} layered double hydroxide. This green rust remained stable for several years. From this study and previous reports, we suggest that ferruginous biofilms should be considered as a favorable location for GR biomineralization when redox conditions and electron donors availability are gathered. - Research highlights: {yields} Characterization of ferruginous biofilm components by solid analysis methods. {yields} Lepidocrocite and ferrihydrite were the main iron oxides. {yields} Anaerobic incubation of biofilm with electron donors produced green rust. {yields} Biofilm components promote the formation of the green rust. {yields} Ferruginous biofilm could contribute to the natural mercury attenuation.

  7. On the Rust Products Formed on Weathering and Carbon Steels Exposed to Chloride in Dry-Wet Cyclical Processes

    International Nuclear Information System (INIS)

    Garcia, K. E.; Morales, A. L.; Barrero, C. A.; Greneche, J. M.

    2005-01-01

    The rust products formed on weathering and carbon steels exposed to dry-wet cyclical processes in different chloride-rich solutions are carefully examined by means of different techniques. Special emphasis is given to the methodology of analysis of the data using 300 K and 77 K Moessbauer spectrometry and X-ray diffraction. The rust that is loosely bound to the metal surface and that it is lost during the corrosion process, for both types of steel, was found to be composed of lepidocrocite, superparamagnetic goethite, hematite, and traces of akaganeite. On the other hand, the adherent rust, which is differentiated as scraped and hit according to the way it is obtained, from both steels was found to be composed of akaganeite, spinel phase, goethite exhibiting broad distribution of particle sizes and lepidocrocite. The relative abundances of rust components for both steels were very similar, suggesting similar corrosion processes. Mass loss measurements show that the corrosion rates increases with increasing the chloride concentration. The presence of large quantities of spinel phase and akaganeite are a consequence of a corrosion process under the influence of very high chloride concentrations. Our results are useful for assessing the behavior of weathering steels where the levels of chlorides are high or in contact with sea water.

  8. Characterisation of rust surfaces formed on mild steel exposed to marine atmospheres using XRD and SEM/Micro-Raman techniques

    International Nuclear Information System (INIS)

    Fuente, D. de la; Alcántara, J.; Chico, B.; Díaz, I.; Jiménez, J.A.; Morcillo, M.

    2016-01-01

    Highlights: • SEM/Micro-Raman is very useful for characterizing rust phases morphologies. • SEM/Micro-Raman enables unequivocal rust phases identification. • γ-FeOOH basically presents two types of morphologies: globular and laminar. • Fe 3 O 4 presents two morphologies: flat patches and black doughnut-type formations. • β-FeOOH presents highly porous morphologies comprised by fine prismatic crystals. - Abstract: The exposure of mild steel to marine atmospheres gives rise to the formation of various corrosion products, mainly lepidocrocite, goethite, magnetite and akaganeite. In this study, Grazing Incidence X-Ray Diffraction, Micro-X-Ray Diffraction and Scanning Electron Microscopy/Micro-Raman are used to characterise rust layer surfaces and to identify the principal component rust phases and their morphology. The main conclusion reached is that lepidocrocite is preferentially located on the outermost surface while magnetite and akaganeite form mostly close to base steel. The Scanning Electron Microscopy/Micro-Raman technique has been very useful for characterising (identifying) the wide variety of morphologies presented by the rust phases.

  9. Subsurface injection of dissolved ferric chloride to form a chemical barrier: Laboratory investigations

    International Nuclear Information System (INIS)

    Morrison, S.J.; Spangler, R.R.; Morris, S.A.

    1996-01-01

    A chemical barrier is a permeable zone of reactive materials emplaced in the subsurface to remove ground-water contaminants while allowing clean ground water to pass through. Because dissolved ferric chloride hydrolyzes to amorphous ferric oxyhydroxide when it contacts calcite (CaCO 3 ), it may be viable to emplace a zone of amorphous ferric oxyhydroxide (an absorbent for U, Mo, and other inorganic contaminants) into calcite-bearing geologic units by injecting ferric chloride through wells. For a chemical barrier to be successful, it must remain permeable and must be immobile. This investigation monitored chemical compositions, hydraulic conductivity, and iron mobility in laboratory columns and in a two-dimensional tank to determine the viability of injecting ferric chloride to form an amorphous ferric oxyhydroxide chemical barrier. The authors introduced a ferric chloride solution (1,345 mg/1[0.024 m] Fe) to calcite-bearing alluvial gravel to form a chemical barrier of amorphous ferric oxyhydroxide, followed by solutions contaminated with U and Mo. The simulated chemical barriers decreased U and Mo concentrations to less than 0.05 mg/l (2.1 x 10 -7 m) and 0.01 (1.0 x 10 -7 m), respectively; however, the breakthrough front is spread out with concentrations increasing to more than regulatory guideline values sooner than predicted. The hydraulic conductivity of calcite-bearing alluvial gravel decreased substantially during ferric chloride introduction because of the formation of carbon dioxide but increased to within factors of 1 to 5 of the original value as synthetic ground water flowed through the system. Amorphous ferric oxyhydroxide that formed in these experiments remained immobile at flow rates exceeding those typical of ground water. These laboratory results, in conjunction with site-specific characterization data, can be used to design chemical barriers emplaced by injection of ferric chloride

  10. Surface analytical techniques applied to minerals processing

    International Nuclear Information System (INIS)

    Smart, R.St.C.

    1991-01-01

    An understanding of the chemical and physical forms of the chemically altered layers on the surfaces of base metal sulphides, particularly in the form of hydroxides, oxyhydroxides and oxides, and the changes that occur in them during minerals processing lies at the core of a complete description of flotation chemistry. This paper reviews the application of a variety of surface-sensitive techniques and methodologies applied to the study of surface layers on single minerals, mixed minerals, synthetic ores and real ores. Evidence from combined XPS/SAM/SEM studies have provided images and analyses of three forms of oxide, oxyhydroxide and hydroxide products on the surfaces of single sulphide minerals, mineral mixtures and complex sulphide ores. 4 refs., 2 tabs., 4 figs

  11. Arsenic-Microbe-Mineral Interactions in Mining-Affected Environments

    Directory of Open Access Journals (Sweden)

    Karen A. Hudson-Edwards

    2013-10-01

    Full Text Available The toxic element arsenic (As occurs widely in solid and liquid mine wastes. Aqueous forms of arsenic are taken up in As-bearing sulfides, arsenides, sulfosalts, oxides, oxyhydroxides, Fe-oxides, -hydroxides, -oxyhydroxides and -sulfates, and Fe-, Ca-Fe- and other arsenates. Although a considerable body of research has demonstrated that microbes play a significant role in the precipitation and dissolution of these As-bearing minerals, and in the alteration of the redox state of As, in natural and simulated mining environments, the molecular-scale mechanisms of these interactions are still not well understood. Further research is required using traditional and novel mineralogical, spectroscopic and microbiological techniques to further advance this field, and to help design remediation schemes.

  12. Municipal compost-based mixture for acid mine drainage bioremediation: Metal retention mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Oriol Gibert; Joan de Pablo; Jose Luis Cortina; Carlos Ayora [Universitat Politecnica de Catalunya, Barcelona (Spain). Departament d' Enginyeria Qumica

    2005-09-15

    An upflow packed column was operated to evaluate the potential of a mixture of municipal compost and calcite to promote sulphidogenesis in the remediation of a simulated mine water at high flows (>0.1 m d{sup -1}). Results showed that the pH was neutralised and metals (Fe, Al, Zn, Cu) were significantly removed. Metal removal was attributed to the combined result of precipitation as metal (oxy)hydroxides and carbonates, co-precipitation with these (oxy)hydroxides and sorption onto the compost surface rather than to precipitation as metal sulphides. The two last mechanisms are especially significant for Zn, whose hydroxide is not expected to precipitate at pH 6-7. Before the saturation of compost sorption sites, 60% of the influent Zn was estimated to have been removed by co-precipitation with Fe- and Al-(oxy)hydroxide and 40% by sorption onto the municipal compost.

  13. 57Fe Moessbauer spectroscopic characterisation of a ferromanganese nodule from the Central Indian Ocean

    International Nuclear Information System (INIS)

    Dutta, R.K.; Chakravortty, V.

    1997-01-01

    The iron bearing phases present in a ferromanganese nodule from the Central Indian Ocean have been determined using 57 Fe Moessbauer spectroscopy. The Moessbauer results have been corroborated by XRD, IR and TG-DTA studies. The Moessbauer spectrum of a ferromanganese nodule shows a broad line width which indicates the presence of more than one iron bearing paramagnetic oxide or oxyhydroxide phases where iron is present as Fe 3+ . γ-FeOOH has been distinctly characterised as one of the iron bearing phases in the nodule. Other oxyhydroxide and oxide phases of iron in the nodule have been ruled out. A typical paramagnetic doublet persists even at very high temperature which has been proposed to be due to iron(III)phosphate. Formation of solid solution of Mn 2 O 3 -Fe 2 O 3 has been observed in the heat treated nodule at 1073 K, which has been characterised by the Moessbauer technique. (author)

  14. Evolution of the local structure of ferric gels and polymers during the crystallisation of iron oxides. Application to uranium trapping

    International Nuclear Information System (INIS)

    Combes, Jean-Marie

    1988-01-01

    A first part of this research thesis reports the study of the structure of the main iron oxides and oxy-hydroxides, and of the protocols for the synthesis of ferric gels. The second part reports a topological approach by EXAFS (Extended X-Ray Absorption Fine Structure) of the structure of Mn and Fe oxides and oxy-hydroxides. The third part reports the study of the formation of ferric oxides from aqueous solutions by using a polyhedral approach by X-ray absorption spectroscopy in the case of hydrolysis and formation of ferric gels, and in the case of haematite formation from ferric gels. The next parts respectively report the study of the local structure of gels synthesised from iron(II), and the study of the local structure of natural ferric gels. Then, the author reports the study of sites of uranium bonding on ferric gels [fr

  15. Enhancement of particle aggregation in the presence of organic matter during neutralization of acid drainage in a stream confluence and its effect on arsenic immobilization.

    Science.gov (United States)

    Arce, Guillermo; Montecinos, Mauricio; Guerra, Paula; Escauriaza, Cristian; Coquery, Marina; Pastén, Pablo

    2017-08-01

    Acid drainage (AD) is an important environmental concern that impacts water quality. The formation of reactive Fe and Al oxyhydroxides during the neutralization of AD at river confluences is a natural attenuation process. Although it is known that organic matter (OM) can affect the aggregation of Fe and Al oxyhydroxides and the sorption of As onto their surfaces, the role of OM during the neutralization of AD at river confluences has not been studied. Field and experimental approaches were used to understand this role, using the Azufre River (pH 2) - Caracarani River (pH 8.6) confluence (northern Chile) as model system. Field measurements of organic carbon revealed a 10-15% loss of OM downstream the confluence, which was attributed to associations with Fe and Al oxyhydroxides that settle in the river bed. Laboratory mixtures of AD water with synthetic Caracarani waters under varying conditions of pH, concentration and type of OM revealed that OM promoted the aggregation of Fe oxyhydroxides without reducing As sorption, enhancing the removal of As at slightly acidic conditions (pH ∼4.5). At acidic conditions (pH ∼3), aggregation of OM - metal complexes at high OM concentrations could become the main removal mechanism. One type of OM promoted bimodal particle size distributions with larger mean sizes, possibly increasing the settling velocity of aggregates. This work contributes to a better understanding of the role of OM in AD affected basins, showing that the presence of OM during processes of neutralization of AD can enhance the removal of toxic elements. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Spatial evolution of phosphorus fractionation in the sediments of Rhumel River in the northeast Algeria

    OpenAIRE

    Azzouz , Sarah; Chellat , Smaine; Boukhalfa , Chahrazed; Amrane , Abdeltif

    2014-01-01

    International audience; The objective of the present study is the characterization of the spatial evolution of phosphorus forms in sediments of Rhumel River located in northeast Algeria during winter conditions. Sediments samples were collected along the river in Constantine city during the year 2012. The samples were subjected to physicochemical characterization and metals analysis. Phosphorus was fractionated by sequential extractions procedure in exchangeable, oxyhydroxides bound; calcium ...

  17. Natural nanomaterials : reappraising the elusive structure of the nano-sized mineral ferrihydrite through X-Ray absorption spectroscopy at the iron K-edge

    OpenAIRE

    Figueiredo, M. Ondina; Silva, Teresa Pereira; Veiga, João Pedro

    2013-01-01

    Ferrihydrite is natural ferric oxyhydroxide occurring exclusively nanocrystalline. With ideal formula 5 Fe2 O3 . 9 H2 O, ferrihydrite is quite abundant in sediments, weathering crusts and mine wastes, being characteristic of red pre-soils formed by loose weathered rock plus mineral debris (regoliths) and commonly designated as “2-line” or “6-line” on the basis of the broadened maxima observed in the X-ray diffraction pattern. Synthetic nanocrystalline “6-line” ferrihydrite was...

  18. Synthesis and characterization of boehmite γ-AIOOH and goethite α-FeOOH

    International Nuclear Information System (INIS)

    Corral C, N. G.; Granados C, F.

    2009-01-01

    The aluminum oxy-hydroxides (boehmite) and of iron (goethite) were synthesized by means of the Sol-Gel and oxidative hydrolysis methods, to be employees as adsorbent materials of the present Cd 2+ in aqueous solution. The synthesized materials were characterized by means of X-ray diffraction, infrared analysis and scanning electron microscopy, to identify their purity, elementary chemical composition and morphology. (Author)

  19. EMP and SIMS studies on Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ: a contribution to the identification of potential redox proxies and the impact of cleaning protocols

    OpenAIRE

    Glock, N.; Eisenhauer, A.; Liebetrau, V.; Wiedenbeck, M.; Hensen, C.; Nehrke, G.

    2012-01-01

    In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that...

  20. Study of a low alloy steel rust using Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Maier, I.A.; Saragovi-Badler, C.; Labenski, F.

    1978-01-01

    Moessbauer spectroscopy has been used to analyze the internal and external rust layers of a weathering steel exposed for ten months to an urban-industrial atmosphere. Superparamagnetic α-FeOOH and γ-FeOOH were found in both layers. The external one also contained small sized delta-FeOOH and/or amorphous iron oxyhydroxide. These compounds were not present in the internal layer at this stage of the patina formation. (author)

  1. Anaerobic carbon mineralisation through sulphate reduction in the inner shelf sediments of eastern Arabian sea

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, R.; Naqvi, S.W.A.; Araujo, J.

    ,G.-J. .Reichart and S. W. Poulton. 2012. Sedimentary phosphorus and iron cycling in and below the oxygen minimum zone of the northern Arabian Sea.Biogeosciences Discussion. 9, 3829–3880. Pratihary A.K, S. W. A. Naqvi, H. Naik,B.R. Thorat, G. Narvenkar...). Other factors such as sedimentation rate and the presence of anaerobic electron acceptors asnitrate, Fe and Mn oxyhydroxides also affect sedimentary Corg mineralization rates.Under anoxic conditions, reductive dissolution of Fe oxyhyroxides produces...

  2. Active slag filters-simple and sustainable phosphorus removal from wastewater using steel industry byproduct.

    Science.gov (United States)

    Pratt, C; Shilton, A

    2010-01-01

    Active filtration, where effluent is passed through a reactive substrate such as steel slag, offers a simple and cost-effective option for removing phosphorus (P) from effluent. This work summarises a series of studies that focused on the world's only full-scale active slag filter operated through to exhaustion. The filter achieved 75% P-removal during its first 5 years, reaching a retention capacity of 1.23 g P/kg slag but then its performance sharply declined. Scanning electron microscopy, X-ray diffraction, X-ray fluorescence, and chemical extractions revealed that P sequestration was primarily achieved via adsorption onto iron (Fe) oxyhydroxides on the slag's surface. It was concluded that batch equilibrium tests, whose use has been repeatedly proposed in the literature, cannot be used as an accurate predictor of filter adsorption capacity because Fe oxyhydroxides form via chemical weathering in the field, and laboratory tests don't account for this. Research into how chemical conditions affect slag's P retention capacity demonstrated that near-neutral pH and high redox are optimal for Fe oxyhydroxide stability and overall filter performance. However, as Fe oxyhydroxide sites fill up, removal capacity becomes exhausted. Attempts to regenerate P removal efficiency using physical techniques proved ineffective contrary to dogma in the literature. Based on the newly-developed understanding of the mechanisms of P removal, chemical regeneration techniques were investigated and were shown to strip large quantities of P from filter adsorption sites leading to a regenerated P removal efficiency. This raises the prospect of developing a breakthrough technology that can repeatedly remove and recover P from effluent.

  3. Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

    Science.gov (United States)

    Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

    2018-05-01

    Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

  4. Nanoparticles modified with multiple organic acids

    Science.gov (United States)

    Cook, Ronald Lee (Inventor); Luebben, Silvia DeVito (Inventor); Myers, Andrew William (Inventor); Smith, Bryan Matthew (Inventor); Elliott, Brian John (Inventor); Kreutzer, Cory (Inventor); Wilson, Carolina (Inventor); Meiser, Manfred (Inventor)

    2007-01-01

    Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

  5. Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Rustad, James R.; Zarzycki, Piotr

    2008-07-29

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

  6. Arsenic partitioning among particle-size fractions of mine wastes and stream sediments from cinnabar mining districts.

    Science.gov (United States)

    Silva, Veronica; Loredo, Jorge; Fernández-Martínez, Rodolfo; Larios, Raquel; Ordóñez, Almudena; Gómez, Belén; Rucandio, Isabel

    2014-10-01

    Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80% of total As.

  7. Electrochemical preparation of hematite nanostructured films for solar hydrogen production

    Directory of Open Access Journals (Sweden)

    Ebadzadeh T.

    2012-10-01

    Full Text Available Photoelectrochemical water splitting is a clean and promising technique for using a renewable source of energy, i.e., solar energy, to produce hydrogen. In this work electrochemical formation of iron oxyhydroxide and its conversion to hematite (α- Fe2O3 through thermal treatment have been studied. Oxyhydroxide iron compounds have been prepared onto SnO2/F covered glass substrate by potential cycling with two different potential sweep rate values; then calcined at 520 °C in air to obtain α-Fe2O3 nanostrutured films for their implementation as photoanode in a photoelectrochemical cell. X-ray diffraction analysis allowed finding that iron oxides films have nanocrystalline character. Scanning electron microscopy revealed that films have nanostructured morphology. The obtained results are discussed considering the influence of potential sweep rate employed during the preparation of iron oxyhydroxide film on optical, structural and morphological properties of hematite nanostructured films. Results show that films have acceptable characteristics as photoanode in a photoelectrochemical cell for hydrogen generation from water.

  8. Fungal Iron Biomineralization in Río Tinto

    Directory of Open Access Journals (Sweden)

    Monike Oggerin

    2016-04-01

    Full Text Available Although there are many studies on biomineralization processes, most of them focus on the role of prokaryotes. As fungi play an important role in different geological and biogeochemical processes, it was considered of interest to evaluate their role in a natural extreme acidic environment, Río Tinto, which has a high level of fungal diversity and a high concentration of metals. In this work we report, for the first time, the generation of iron oxyhydroxide minerals by the fungal community in a specific location of the Tinto basin. Using Transmission Electron Microscopy (TEM and High Angle Angular Dark Field coupled with Scanning Transmission Electron Microscopy (HAADF-STEM and Energy-Dispersive X-ray Spectroscopy (EDX, we observed fungal structures involved in the formation of iron oxyhydroxide minerals in mineralized sediment samples from the Río Tinto basin. Although Río Tinto waters are supersaturated in these minerals, they do not precipitate due to their slow precipitation kinetics. The presence of fungi, which simply provide charged surfaces for metal binding, favors the precipitation of Fe oxyhydroxides by overcoming these kinetic barriers. These results prove that the fungal community of Río Tinto participates very actively in the geochemical processes that take place there.

  9. Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Feitosa-Felizzola, Juliana [Laboratoire Chimie Provence, Aix-Marseille Universites-CNRS (UMR 6264), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France); Hanna, Khalil [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement, CNRS-Universite Henri Poincare-Nancy 1 (UMR 7564), 405 rue de Vandoeuvre, 54600 Villers-les-Nancy (France); Chiron, Serge [Laboratoire Chimie Provence, Aix-Marseille Universites-CNRS (UMR 6264), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)], E-mail: serge.chiron@univ-provence.fr

    2009-04-15

    The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity. - Iron(III) and manganese(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of macrolide antibacterial agents.

  10. Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

    International Nuclear Information System (INIS)

    Feitosa-Felizzola, Juliana; Hanna, Khalil; Chiron, Serge

    2009-01-01

    The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity. - Iron(III) and manganese(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of macrolide antibacterial agents

  11. Fissure fillings from the Klipperaas study site

    International Nuclear Information System (INIS)

    Tullborg, E.L.

    1986-07-01

    The Klipperaas study site is located within the Smaaland-Vaermland granitoid belt in southern Sweden. The area investigated can be subdivided into blocks with different hydraulic character and fracture frequency of the rocks. A fissure filling, study has been carried out within the area. This includes identification of the minerals, mineral frequency, textures within the fissures and isotope analyses of calcites. Four generation of fissure fillings, within the time space c. 1600 M.a. to present, has been distinguished. These are 1) quartz; 2) epidote + muscovite and adularia + hematite; 3) calcite + chlorite +/hematite; 4) calcite, clay minerals and Fe-oxyhydroxide. It is observed that the surface water affect the uppermost part of the bedrock resulting in calcite dissolution, break down of pyrite and precipitation of Fe-oxyhydroxide. It is also obvious from the fracture calcite frequency that calcite dissolution is more intensive close to and within the fracture zones. There, Fe-oxyhydroxide can be found down to at least 400 m depth. This gives valuable information about the physic-chemical character of the groundwater within the bedrock. Several fracture zones have been reactivated. It is also suspected that relatively late movements have taken place causing crushing of the rock and only a slight cementation of the crushed material is visible. Some of the fracture zones correspond to mafic dikes. These zones exhibit lower hydraulic conductivity than other zones due to fracture sealing by clay minerals but also by chlorite and calcite. (author)

  12. Nanoparticles modified with multiple organic acids

    Science.gov (United States)

    Cook, Ronald Lee; Luebben, Silvia DeVito; Myers, Andrew William; Smith, Bryan Matthew; Elliott, Brian John; Kreutzer, Cory; Wilson, Carolina; Meiser, Manfred

    2007-07-17

    Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

  13. Green superlubricity of Nitinol 60 alloy against steel in presence of castor oil

    Science.gov (United States)

    Zeng, Qunfeng; Dong, Guangneng; Martin, Jean Michel

    2016-07-01

    In the present work, first, we show that sliding Nitinol 60 alloy against steel under castor oil lubrication exhibits a new case of superlubricity (coefficient of friction CoF ≪ 0.01). So far, CoF below 0.01 have never been achieved under boundary lubrication at high contact pressure and in presence of vegetable oil as a green lubricant. Next, it is demonstrated that superlubricity is controlled by tribochemical reactions, involving chemical degradation of castor oil and the formation of metal oxy-hydroxides. Finally, to explain these findings, we propose a novel superlubricity mechanism consisting of hexanoic acid molecules intercalated between nickel and iron oxy-hydroxide lamellar layers, a structure very similar to the one found in Fe-Ni batteries. We propose that superlubricity is achieved due to repulsive electrostatic forces acting between the intercalated metal oxy-hydroxide lamellar compounds. This system would be suitable for practical engineering applications in many fields including biotechnologies.

  14. Nanophase Iron Oxides as an Ultraviolet Sunscreen for Ancient Photosynthetic Microbes: A Possible Link Between Early Organisms, Banded-Iron Formations, and the Oxygenation of the Atmosphere

    Science.gov (United States)

    Bishop, Janice L.; Rothschild, Lynn J.; Rothschild, Lynn J.; Rogoff, Dana A.

    2006-01-01

    We propose that nanophase iron oxide-bearing materials provided important niches for ancient photosynthetic microbes on the early Earth that ultimately led to the oxygenation of the Earth s atmosphere and the formation of iron oxide deposits. Atmospheric oxygen and ozone attenuate UV radiation on the Earth today providing substantial protection for photosynthetic organisms. With ultraviolet radiation fluxes likely to have been even higher on the early Earth than today, accessing solar radiation was particularly risky for early organisms. Yet, we know that photosynthesis arose then and played a critical role in subsequent evolution. Of primary importance was protection at approx.250-290 nm, where peak nucleic acid (approx.260 nm) and protein (approx.280 nm) absorptions occur. Nanophase ferric oxide/oxyhydroxide minerals absorb, and thus block, the lethal UV radiation, while transmitting light through much of the visible and near-infrared regions of interest to photosynthesis (400 to 1100 nm). Further, they were available in early environments, and are synthesized by many organisms. Based on ferric oxide/oxyhydroxide spectral properties, likely geologic processes, and the results of experiments with the photosynthetic organisms, Euglena sp. and Chlumydomonus reinhardtii, we propose a scenario where photosynthesis, and ultimately the oxygenation of the atmosphere, depended on the protection of early microbes by nanophase ferric oxides/oxyhydroxides. The results of this study are also applicable to other potentially habitable iron-bearing planetary bodies because of the evolutionary pressure to utilize solar radiation when available as an energy source.

  15. Thermodynamic studies of chromium adsorption on iron species generated by electrocoagulation

    Energy Technology Data Exchange (ETDEWEB)

    Parga, J.R.; Vazquez, V.; Gonzalez, G.; Cisneros, M.M. [Metallurgy and Materials Science Department, Institute Technology of Saltillo (Mexico)

    2010-10-15

    The protection of the global environment and in particular, the provision of a sustainable source of clean water is a necessity for human survival. Specifically, large quantities of chromium containing compounds are being discharged into the environment. This study has been carried out to determine the feasibility of chromium adsorption on iron species by an Electrocoagulation (EC) process using the Langmuir Isotherm. The full potential of EC with air injection as an alternative wastewater treatment technique to remove chromium from well water shows more than 99 % removal without the addition of any chemical reagents. In this study, X-Ray Diffraction, Scanning Electron Microscopy, Moessbauer Spectroscopy and Fourier Transform Infrared Spectroscopy are used to characterize the solid products that reveal the expected crystalline iron oxides, i.e., lepidocrocite, magnetite, gohetite, and iron oxide. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  16. Moessbauer Spectroscopy at the University of Dar Es Salaam

    International Nuclear Information System (INIS)

    Kiwanga, C.A.

    1989-01-01

    A recently acquired facility for Moessbauer spectroscopy is described. Test results on samples of an iron ore and a steel corrosion product are given. It is deduced that the iron ore contained hematite (alpha-Fe203) constituting 41.5%, magnetite (Fe 304) constituting of 39.5% and two doublet phases: a paramagnetic Fe 3+ phase constituting 4.8% and a paramagnetic Fe 2+ phase constituting 14.2%. The steel corrosion product seems to be entirely composed of lepidocrocite (gamma-FeOOH). The results obtained are in excellent agreement with the literature data with regard to the identified iron compounds. It is concluded that the facility including the data processing computer programs which are essentially home-made is capable of producing very high quality research findings. (author)

  17. BET measurements: Outgassing of minerals

    DEFF Research Database (Denmark)

    Clausen, Liselotte; Fabricius, Ida Lykke

    2000-01-01

    Outgassing minerals at elevated temperatures prior to BET measurements can lead to phase changes, especially in the case of amorphous and poorly crystalline materials. In order to evaluate the applicability of the BET method when low outgassing temperatures are required, selected aquifer minerals...... were outgassed at different temperatures and for different times. The studied minerals are 2-line ferrihydrite, goethite, lepidocrocite, quartz, calcite, ®-alumina, and kaolinite. The results demonstrate that measured specific surface areas of iron oxides are strongly dependent on outgassing conditions...... because the surface area increased by 170% with increasing temperature. In the poorly crystalline minerals, phase changes caused by heating were observed at temperatures lower than 100±C. Therefore low outgassing temperatures are preferable for minimizing phase changes. As demonstrated in this study...

  18. Monitoring structural transformation of hydroxy-sulphate green rust in the presence of sulphate reducing bacteria

    International Nuclear Information System (INIS)

    Abdelmoula, M.; Zegeye, A.; Jorand, F.; Carteret, C.

    2006-01-01

    The activities of bacterial consortia enable organisms to maximize their metabolic capabilities. This article assesses the synergetic relationship between iron reducing bacteria (IRB), Shewanella putrefaciens and sulphate reducing bacteria (SRB) Desulfovibrio alaskensis. Thus, the aim of this study was first to form a biogenic hydroxy-sulpahte green rust GR2(SO 4 -2 ) through the bioreduction of lepidocrocite by S. putrefaciens and secondly to investigate if sulfate anions intercalated in the biogenic GR2(SO 4 -2 ) could serve as final electron acceptor for a sulfate reducing bacterium, D. alaskensis. The results indicate that the IRB lead to the formation of GR2(SO 4 -2 ) and this mineral serve as an electron acceptor for SRB. GR2(SO 4 -2 ) precipitation and its transformation was demonstrated by using X-ray diffraction (DRX), Moessbauer spectroscopy (TMS) and transmission electron spectroscopy (TEM). These observations point out the possible acceleration of steel corrosion in marine environment in presence of IRB/SRB consortia.

  19. Insight into the product film formed on Ni-advanced weathering steel in a tropical marine atmosphere

    Science.gov (United States)

    Wu, Wei; Cheng, Xuequn; Hou, Huaxing; Liu, Bo; Li, Xiaogang

    2018-04-01

    The product film formed on Ni-advanced weathering steel in a tropical marine environment was investigated in detail through outdoor exposure by using diverse surface analysis techniques combined with electrochemical impedance spectroscopy and scanning kelvin probe measurements. The results showed that the product film was mainly composed of nanophasic goethite in the inner layer and maghemite, akaganeite, and hematite in the outer layer. Moreover, the resistance to atmospheric corrosion gradually increased from the outermost product film to the innermost film. Ni was significantly enriched in the inner layer in the form of the spinel phase NiFe2O4, which transformed lepidocrocite to fine-grained goethite, withstood the invasion of chloridion, and improved the corrosion potential of the product film in a tropical marine atmosphere.

  20. Sedimentary uranium deposit of the Ipora/Amorinopolis region, state of Goias, Brazil

    International Nuclear Information System (INIS)

    Fernandes, S.M.; Leonardos, O.H.

    1984-01-01

    The uranium mineralization is chiefly found within arkosic sandstones at the base of the Devonian Ponta Grossa Formation. The ore is tabular and concordant with the bedding, the controls being simultaneously litho-stratigraphical and biochemical. Narrow permeable horizons of arkosic sandstone lie between impermeable shale and siltstone layers. Within the permeable horizon, the fossil remains (probably brachiopods) are replaced by uranium minerals. The oxidized iron minerals may have acted as to insulate and preserve the secondary soluble uranium minerals. The mineral paragenesis is represented by renardite, meta - autunite I, fourmarierite, Koninckite, ranquilite, meta-uranocircite II, barite, apatite, calophane, wavelite, varscite, an unnamed uranium mineral, quartz, calcedony, goethite, lepidocrocite and hematite. (Author) [pt

  1. An X-ray diffraction study of corrosion products from low carbon steel

    International Nuclear Information System (INIS)

    Morales, A. L.

    2003-01-01

    It was found in earlier work a decrease in the corrosion rate from low carbon steel when it was subjected to the action of a combined pollutant concentration (SO 4 ''2-=10''-4 M+Cl=1.5x 10''-3 M). It was also found that large magnetic content of the rust was related to higher corrosion rates. In the present study corrosion products are further analyzed by means of X-ray diffraction to account for composition changes during the corrosion process. it is found that lepidocrocite and goethite are the dominant components for the short-term corrosion in all batches considered while for log-term corrosion lepidocrite and goethite dominates if the corrosion rates is low and magnetite dominates if the corrosion rate is high. The mechanism for decreasing the corrosion rate is related to the inhibition of magnetite production at this particular concentration. (Author) 15 refs

  2. Characterization of Corrosion Products on Carbon Steel Exposed to Natural Weathering and to Accelerated Corrosion Tests

    Directory of Open Access Journals (Sweden)

    Renato Altobelli Antunes

    2014-01-01

    Full Text Available The aim of this work was to compare the corrosion products formed on carbon steel plates submitted to atmospheric corrosion in urban and industrial atmospheres with those formed after accelerated corrosion tests. The corrosion products were characterized by X-ray diffraction, Mössbauer spectroscopy, and Raman spectroscopy. The specimens were exposed to natural weathering in both atmospheres for nine months. The morphologies of the corrosion products were evaluated using scanning electron microscopy. The main product found was lepidocrocite. Goethite and magnetite were also found on the corroded specimens but in lower concentrations. The results showed that the accelerated test based on the ASTM B117 procedure presented poor correlation with the atmospheric corrosion tests whereas an alternated fog/dry cycle combined with UV radiation exposure provided better correlation.

  3. New Insights in the Long-Term Atmospheric Corrosion Mechanisms of Low Alloy Steel Reinforcements of Cultural Heritage Buildings

    Directory of Open Access Journals (Sweden)

    Marie Bouchar

    2017-06-01

    Full Text Available Reinforcing clamps made of low alloy steel from the Metz cathedral and corroded outdoors during 500 years were studied by OM, FESEM/EDS, and micro-Raman spectroscopy. The corrosion product layer is constituted of a dual structure. The outer layer is mainly constituted of goethite and lepidocrocite embedding exogenous elements such as Ca and P. The inner layer is mainly constituted of ferrihydrite. The behaviour of the inner layer under conditions simulating the wetting stage of the RH wet/dry atmospheric corrosion cycle was observed by in situ micro-Raman spectroscopy. The disappearance of ferrihydrite near the metal/oxide interface strongly suggests a mechanism of reductive dissolution caused by the oxidation of the metallic substrate and was observed for the first time in situ on an archaeological system.

  4. Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

    Science.gov (United States)

    Bassez, Marie-Paule

    2017-12-01

    In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as

  5. The correlation between accelerated and field corrosion tests performed in carbon steel and weathering steel coupons, coated and non-coated

    International Nuclear Information System (INIS)

    Antunes, Renato Altobelli

    2002-01-01

    The performance of four different organic coating systems applied to carbon and weathering steel coupons has been assessed in this investigation. applied on the surface of carbon steel and weathering steel coupons. The coupons have been evaluated using five different tests, three field tests and two accelerated tests. The field tests were carried out at three atmospheric stations, located at COSIPA in Cubatao-SP, at Alto da Serra in Cubatao-SP and at Paula Souza in Sao Paulo city. The accelerated tests consisted of (a) exposure to alternate cycles of ultraviolet radiation/condensation combined with salt spray cycles (UVCON combined with Salt Spray) and of (b) exposure to alternate cycles of ultraviolet radiation/condensation combined with the Prohesion test. The performance of the coatings was assessed by visual observation and photographs, using a method based on ASTM D-610, ASTM D-714 and ASTM-1654 standards to rank them. The oxide phases formed on the surfaces of the non-coated specimens of carbon and weathering steels, exposed to the same tests performed with the coated specimens, were identified using three different techniques: X-ray diffraction, Raman microscopy and Moessbauer spectroscopy. In the field tests, the specimens have been exposed for 1, 2, 3, 6 and 9 months. In the accelerated ones, the results were obtained after 1340 hours (4 cycles) test. The main component identified in all the specimens collected from the field tests and from the UVCON combined with the Prohesion test was lepidocrocite (γ-FeOOH). Goethite (α-FeOOH ) and magnetite (Fe 3 O 4 ) were identified as the other two main phases present in ali the specimens. In the UVCON combined with Salt Spray test, the dominant phase was magnetite, followed by goethite and lepidocrocite. The morphology of the rust formed on the specimens was examined by scanning electron microscopy (SEM). Structures corresponding to goethite and lepidocrocited were recognized on ali specimens, except those

  6. Mineralogical aspects of the laterites of Maicuru

    International Nuclear Information System (INIS)

    Lemos, V.P.; Costa, M.C. da

    1989-01-01

    This paper presents the prelimary mineralogical data of the weathering materials derived from the alkaline-ultramafic-carbonatitic Maicuru complex, State of Para. These material include several minerals species: iron, titanium and aluminium oxides/hydroxides as aluminous goethite, geothite, hematite, maghemite, lepidocrocite, anatase; and gibbsite; clay minerals of the smectite, chlorite, vermiculite and kaolinite groups and interstratified chlorite-smectite, mica-vermiculite, vermiculite-chlorite and Kaolinite-smectite; and aluminous phosphates of the crandalite group, wardite, augelite, senegalite, wavelite and variscite. The principal characteristics of these minerals were obtained by X-ray diffraction, optical methods, electron probe microanalysis, energy dispersive scanning electron microscope, X-ray fluorescence, atomic absorption, inductively coupled plasma-ICP source spectrometry and colorimetric methods. (author) [pt

  7. The Moessbauer spectroscopy in the characterization of atmospheric corrosion products

    International Nuclear Information System (INIS)

    Hernandez Torres, D.; Leiva Ronda, P.; Gomez, J.; Ronda, M.

    1996-01-01

    A study of corrosion products on mild steel formed after 1 and 5 years exposure in two industrial coastal weathering stations in the Bay from Matanzas City, Cuba, has been carried out. Structural analysis was conducted using mainly transmission Moessbauer Spectroscopy and the X-ray diffraction as complementary technique. The main phases found in the specimen exposed to high chloride containing environment were: lepidocrocite (γ- FeOOH), goethite (α- FeOOH) and magnetite concentration was the lowest, the phases found were γ- FeOOH and α- FeOOH, and the phase transformation proposed was γ- FeOOh -> α- Fe-OOH. In this station were found also amorphous corrosion products. There amorphous phases could be responsible for the lowest levels of corrosion on steel in this station

  8. The Moessbauer spectroscopy in the characterization of atmospheric corrosion products; La espectroscopia Moessbauer en la caracterizacion de productos de corrosion atmosferica

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez Torres, D; Leiva Ronda, P [Centro de Estudios Aplicados al Desarrollo Nuclear (CEADEN), La Habana (Cuba); Gomez, J; Ronda, M [Centro de Investigaciones del Petroleo, La Habana (Cuba)

    1996-07-01

    A study of corrosion products on mild steel formed after 1 and 5 years exposure in two industrial coastal weathering stations in the Bay from Matanzas City, Cuba, has been carried out. Structural analysis was conducted using mainly transmission Moessbauer Spectroscopy and the X-ray diffraction as complementary technique. The main phases found in the specimen exposed to high chloride containing environment were: lepidocrocite ({gamma}- FeOOH), goethite ({alpha}- FeOOH) and magnetite concentration was the lowest, the phases found were {gamma}- FeOOH and {alpha}- FeOOH, and the phase transformation proposed was {gamma}- FeOOh -> {alpha}- Fe-OOH. In this station were found also amorphous corrosion products. There amorphous phases could be responsible for the lowest levels of corrosion on steel in this station.

  9. The correlation between accelerated and field corrosion tests performed in carbon steel and weathering steel coupons, coated and non-coated; Correlacao entre ensaios acelerados e ensaios de campo em corpos-de-provas de aco carbono e aco patinavel, sem e com revestimento

    Energy Technology Data Exchange (ETDEWEB)

    Antunes, Renato Altobelli

    2002-07-01

    The performance of four different organic coating systems applied to carbon and weathering steel coupons has been assessed in this investigation. applied on the surface of carbon steel and weathering steel coupons. The coupons have been evaluated using five different tests, three field tests and two accelerated tests. The field tests were carried out at three atmospheric stations, located at COSIPA in Cubatao-SP, at Alto da Serra in Cubatao-SP and at Paula Souza in Sao Paulo city. The accelerated tests consisted of (a) exposure to alternate cycles of ultraviolet radiation/condensation combined with salt spray cycles (UVCON combined with Salt Spray) and of (b) exposure to alternate cycles of ultraviolet radiation/condensation combined with the Prohesion test. The performance of the coatings was assessed by visual observation and photographs, using a method based on ASTM D-610, ASTM D-714 and ASTM-1654 standards to rank them. The oxide phases formed on the surfaces of the non-coated specimens of carbon and weathering steels, exposed to the same tests performed with the coated specimens, were identified using three different techniques: X-ray diffraction, Raman microscopy and Moessbauer spectroscopy. In the field tests, the specimens have been exposed for 1, 2, 3, 6 and 9 months. In the accelerated ones, the results were obtained after 1340 hours (4 cycles) test. The main component identified in all the specimens collected from the field tests and from the UVCON combined with the Prohesion test was lepidocrocite ({gamma}-FeOOH). Goethite ({alpha}-FeOOH ) and magnetite (Fe{sub 3}O{sub 4}) were identified as the other two main phases present in ali the specimens. In the UVCON combined with Salt Spray test, the dominant phase was magnetite, followed by goethite and lepidocrocite. The morphology of the rust formed on the specimens was examined by scanning electron microscopy (SEM). Structures corresponding to goethite and lepidocrocited were recognized on ali specimens

  10. Service life prediction for 50-year-old buildings in marine environments

    Directory of Open Access Journals (Sweden)

    Agustín Sánchez-Deza

    2018-03-01

    Full Text Available Steel reinforcing bars are often coated with rusts formed during service in reinforced concrete (RC structures. Rust layers growing on steel rebars induce expansive stresses and cause cracking on cover concrete. This study uses steel corrosion rate results measured on reinforced concrete buildings of more than 50 years of age located in marine environments and considers the pressure generated by the volume expansion of corrosion product layers to calculate the service life of the RC structures using a numerical simulation, estimating the time to corrosion cracking of the concrete cover. Akaganeite, goethite, lepidocrocite, hematite, magnetite and maghemite were identified by X-ray diffraction as crystalline phase constituents of the rust layers.

  11. The Electrochemical Properties of Low-crystallinity TiO2(B)-Carbon Composite as an Anode Material in Lithium Ion Battery

    International Nuclear Information System (INIS)

    Furuya, Yasuyuki; Zhao, Wenwen; Unno, Masashi; Noguchi, Hideyuki

    2014-01-01

    Highlights: • TiO 2 (B)-carbon composites was synthesized from Lepidocrocite-type compounds. • Tight adhesion between TiO 2 (B) and CNT in the composite is confirmed. • TiO 2 (B)-carbon composite delivers higher capacity than that of bare TiO 2 (B). • TiO 2 (B)-carbon composite exhibits improved rate performance. - Abstract: We have prepared two types TiO 2 (B)-carbon composites from Lepidocrocite-type compounds (K 0.86 Li 0.26 T i1.72 O 4 ) heated at 700 and 900 °C under presence of carbon nanotube (CNT) and glucose as carbon sources. The XRD data shows that it contains a single phase of TiO 2 (B) and the existence of carbon was confirmed by Raman spectra. TEM image confirms that TiO 2 (B) primary particles and carbon nanotube are scattered randomly and contact tightly in the composite. Carbon content in the composite was found to be 5 - 8% and CNT is the major carbonaceous material. The charge and discharge curves of TiO 2 (B)-carbon composite prepared from precursor heated at 700 °C resemble with that of amorphous TiO 2 . The calculated discharge capacity of the composite is 323 mAh g −1 at a cut off voltage of 0.9 V, which is higher than that of bare TiO 2 (B). It is suggested that the electrochemical performance of this material is strongly influenced by both the operating temperature and cut off voltage. The discharge capacity can reach 198 mAh g −1 at 4.5 C rate at a cut off voltage 1.3 V and the coulombic efficiency is over 99.8% after 10 th cycles

  12. An alkali-metal ion extracted layered compound as a template for a metastable phase synthesis in a low-temperature solid-state reaction: preparation of brookite from K0.8Ti1.73Li0.27O4.

    Science.gov (United States)

    Ozawa, Tadashi C; Sasaki, Takayoshi

    2010-03-15

    We have designed a new approach to synthesize brookite, i.e., to extract alkali-metal ions from K(0.8)Ti(1.73)Li(0.27)O(4) (KTLO) and to apply simultaneous heat treatment to the remaining lepidocrocite-type layers of TiO(6) octahedra. For the alkali-metal ion extraction and the simultaneous heat treatment, KTLO was heated at 400 degrees C with polytetrafluoroethylene (PTFE) in flowing Ar. PTFE has been found to be an effective agent to extract strongly electropositive alkali-metal ions from KTLO because of the strong electronegativity of F as its component. The product of this reaction consists of a mixture of brookite, K(2)CO(3), LiF, and PTFE derivatives, indicating the complete extraction of K(+) and Li(+) from KTLO and formation of brookite from the lepidocrocite-type layer of TiO(6) octahedra as a template. This brookite has a partial replacement of O(2-) with F(-) and/or slight oxygen deficiency; thus, its color is light-bluish gray. Fully oxidized brookite formation and complete decomposition of PTFE derivatives have been achieved by further heating in flowing air, and coproduced alkali-metal salts have been removed by washing in water. Powder X-ray diffraction, Raman spectroscopy, and chemical analysis results have confirmed that the final brookite product treated at 600 degrees C is single phase, and it is white. The method to extract alkali-metal ions from a crystalline material using PTFE is drastically different from the common methods such as soft-chemical and electrochemical reactions. It is likely that this new synthetic approach is applicable to other layered systems to prepare a diverse family of compounds, including novel metastable ones.

  13. Aging study on carboxymethyl cellulose-coated zero-valent iron nanoparticles in water: Chemical transformation and structural evolution

    International Nuclear Information System (INIS)

    Dong, Haoran; Zhao, Feng; Zeng, Guangming; Tang, Lin; Fan, Changzheng; Zhang, Lihua; Zeng, Yalan; He, Qi; Xie, Yankai; Wu, Yanan

    2016-01-01

    Highlights: • The chemical transformation and structural evolution of CMC-nZVI were investigated. • CMC could slow down the aging rate of nZVI and alter the species transformation. • Fe_3O_4 and/or γ-Fe_2O_3 are the dominant corrosion products of bare nZVI after aging. • γ-FeOOH is the primary corrosion product of CMC-nZVI after aging. - Abstract: To assess the long-term fate and the associated risks of nanoscale zero-valent iron (nZVI) used in the water remediation, it is essential to understand the chemical transformations during aging of nZVI in water. This study investigated the compositional and structural evolution of bare nZVI and carboxymethyl cellulose (CMC) coated nZVI in static water over a period of 90 days. Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the corrosion products of nZVI and CMC-nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging, but the coating of CMC could slow down the aging rate of nZVI (as indicated by the slower drop in Fe"0 intensity in XRD pattern). For the bare nZVI, magnetite (Fe_3O_4) and/or maghemite (γ-Fe_2O_3) are the dominant corrosion products after 90 days of aging. However, for the CMC-nZVI, the core-shell spheres collapses to acicular-shaped structures after aging with crystalline lepidocrocite (γ-FeOOH) as the primary end product. Moreover, more lepidocrocite present in the corrosion products of CMC-nZVI with higher loading of CMC, which reveals that the CMC coating could influence the transformation of iron oxides.

  14. Evolution of nanoscale zero-valent iron (nZVI) in water: Microscopic and spectroscopic evidence on the formation of nano- and micro-structured iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Airong, E-mail: liuairong@tongji.edu.cn; Liu, Jing; Han, Jinhao; Zhang, Wei-xian, E-mail: zhangwx@tongji.edu.cn

    2017-01-15

    Highlights: • A comprehensive study of corrosion products for nZVI under both oxic and anoxic conditions is performed. • Under anoxic conditions, the oxidation products contain a mixture of wustite (FeO), goethite (α-FeOOH) and akaganeite (β-FeOOH). • Under oxic conditions, the final products are mainly crystalline lepidocrocite (γ-FeOOH) with acicular-shaped structures. • Morphological and structural evolution of nZVI under both oxic and anoxic conditions are substantially different. - Abstract: Knowledge on the transformation of nanoscale zero-valent iron (nZVI) in water is essential to predict its surface chemistry including surface charge, colloidal stability and aggregation, reduction and sorption of organic contaminants, heavy metal ions and other pollutants in the environment. In this work, transmission electronic microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy are applied to study the compositional and structural evolution of nZVI under oxic and anoxic conditions. Under anoxic conditions, the core–shell structure of nZVI is well maintained even after 72 h, and the corrosion products usually contain a mixture of wustite (FeO), goethite (α-FeOOH) and akaganeite (β-FeOOH). Under oxic conditions, the core–shell structure quickly collapses to flakes or acicular-shaped structures with crystalline lepidocrocite (γ-FeOOH) as the primary end product. This work provides detailed information and fills an important knowledge gap on the physicochemical characteristics and structural evolution of engineered nanomaterials in the environment.

  15. Effects of water chemistry on arsenic removal from drinking water by electrocoagulation.

    Science.gov (United States)

    Wan, Wei; Pepping, Troy J; Banerji, Tuhin; Chaudhari, Sanjeev; Giammar, Daniel E

    2011-01-01

    Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations. Copyright © 2010 Elsevier Ltd. All rights reserved.

  16. Reductive Dissolution of Goethite and Hematite by Reduced Flavins

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhi; Zachara, John M.; Wang, Zheming; Shi, Liang; Fredrickson, Jim K.

    2013-10-02

    The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive than hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.

  17. Antimony sinks in the weathering crust of bullets from Swiss shooting ranges

    International Nuclear Information System (INIS)

    Ackermann, Sonia; Giere, Reto; Newville, Matthew; Majzlan, Juraj

    2009-01-01

    Shooting ranges represent sites heavily polluted by Pb, Sb, Cu, Ni, and Zn, which are released during the weathering of bullets. The pristine bullets are made of a Pb-Sb core, Fe mantle, and minor amounts of Cu, Ni, and Zn in an interlayer between the core and mantle. At two selected sampling sites (Losone and Lucerne, both in Switzerland), corroding bullets were collected to determine the sinks of Sb within the weathering crust of the bullets. Bulk Sb concentrations in the crust were found to be as high as 1.3 wt.%. The oxalate-extractable fraction of Fe showed that the amorphous Fe oxides (e.g., ferrihydrite) prevail over goethite and lepidocrocite, which were identified by bulk X-ray diffraction experiments. Crystalline Pb phases are litharge (only found by X-ray diffraction) and cerussite, which result from weathering of the Pb core. No distinct Sb minerals were identified by X-ray diffraction. Investigations with electron microprobe (EMP) showed that Sb is mostly accumulated in those regions in the weathering crust where there is also a high concentration of Fe. In the weathering crust from Losone, such Fe-rich regions with Sb are represented by material that cements or rims silicate mineral grains. The cement was identified as lepidocrocite by micro-Raman analysis. At Lucerne, Sb is found in Fe-oxide aggregates, in sawdust particles where it may be bound to organic matter, or in aggregates enriched in Pb and depleted in Fe. Bulk EXAFS experiments suggested that the Fe oxides are the most important sink for Sb. Our modelling of Sb next-nearest neighbours suggests two types of inner-sphere complexes on the surfaces of Fe oxides. These are edge- and corner-sharing adsorption complexes. Hence, the predominant sink of Sb in the weathering crust of the bullets at the selected shooting ranges is Fe oxides, amorphous or crystalline

  18. The Corrosion of High Performance Steel in Adverse Environments

    International Nuclear Information System (INIS)

    Cook, Desmond C.

    2005-01-01

    The corrosion products that have formed on weathering steel bridges exposed to different weather conditions in the United States have been evaluated. They have been analyzed by spectroscopic techniques to determine the relationship between protective and non-protective rust coatings, and their relationship to the exposure conditions. Bridges constructed recently using High Performance Steel, as well as older bridges built with Type A588B weathering steel, were evaluated for corrosion performance of the rust coatings. In locations where the steel is subjected to regular wet-dry cycling, where the surface is wet for less than about 20% of the time, a protective patina starts to form after a few months exposure, and continues to an adherent, impervious coating after a decade. The protective patina is characterized by the formation of only goethite and lepidocrocite. The goethite makes up about 80% of the rust, and itself consists of a nanophase component, 40%, or infrequent drying cycles (regions close to waterways, fog or having high humidity), the weathering steel forms a rust coating that consists of a large amount of maghemite, and goethite that contains very little of the nanophase component. The rust coating ex-foliates from the steel and is not protective. Under exposure conditions in which chlorides are deposited onto the weathering steel surface (marine or de-icing salt locations), the protective patina also does not form. Instead, the rust coating consists of a large fraction of akaganeite that forms at the expense of the lepidocrocite and nanophase goethite. The bridges exposed to high chloride concentrations, 1.5 wt%, and therefore having no protective patina, have corrosion rates measured to be 6 times larger than expected for weathering steel with the protective patina

  19. Suppression of exchange bias effect in maghemite nanoparticles functionalized with H{sub 2}Y

    Energy Technology Data Exchange (ETDEWEB)

    Guivar, Juan A. Ramos, E-mail: juan.ramos5@unmsm.edu.pe [Faculty of Physical Sciences, National University of San Marcos, P. O. Box 14-0149, Lima, 14 Peru (Peru); Morales, M.A. [Departamento de Física Teórica e Experimental, UFRN, Natal, RN, 59078-970 Brazil (Brazil); Litterst, F. Jochen [Institut für Physik der Kondensierten Materie, Technische Universität Braunschweig, Braunschweig, 38110 Germany (Germany)

    2016-12-15

    The structural, vibrational, morphological and magnetic properties of maghemite (γ-Fe{sub 2}O{sub 3}) nanoparticles functionalized with polar molecules EDTA(or H{sub 4}Y) and H{sub 2}Y are reported. The samples were functionalized before and after total synthesis of γ-Fe{sub 2}O{sub 3} nanoparticles. The molecules are anchored on the monodentate mode on the nanoparticles surface. Transmission electron microscopy (TEM) revealed the formation of maghemite nanoparticles with small diameter of 4 nm for the sample functionalized upon synthesis and 7.6 and 6.9 nm for the samples functionalized with EDTA and H{sub 2}Y after the formation of nanoparticles. Exchange bias phenomena were observed in some of the samples functionalized with EDTA at temperatures below 70 K. The presence of the bias effect was discussed in terms of the formation of a thin layer of a secondary phase like lepidocrocite, and the absence of this effect was explained in terms of the chemisorption of carboxylic groups from EDTA which suppressed the canting. Studies of Mössbauer spectroscopy as a function of temperature showed slow relaxation effects and allowed discussion of the secondary phase. In the M–T curves a maximum around 116 K was associated with this secondary phase also in agreement with the Mössbauer studies. The dynamic properties were studied by AC susceptibility, the out of phase signal revealed a spin glass like regime below 36.5 K. - Highlights: • Coprecipitation in alkaline medium was used for the synthesis of EDTA functionalized small maghemite nanoparticles. • Exchange bias effect was observed due to a thin layer of lepidocrocite like second phase. • The sample coprecipitated in a weak base did not show exchange bias effect. • The bias effect is discussed in terms of suppression of canting due to chemisorption of carboxylic groups from EDTA.

  20. Long-term atmospheric corrosion of mild steel

    International Nuclear Information System (INIS)

    Fuente, D. de la; Diaz, I.; Simancas, J.; Chico, B.; Morcillo, M.

    2011-01-01

    Research highlights: → Atmospheric corrosion rate stabilises after the first 4-6 years of exposure. → Great compaction of the rust layers in rural and urban atmospheres. → Corrosion (in rural and urban) deviates from common behaviour of bilogarithmic law. → Typical structures of lepidocrocite, goethite and akaganeite are identified. → Formation of hematite (industrial atmosphere) and ferrihydrite (marine atmosphere). - Abstract: A great deal of information is available on the atmospheric corrosion of mild steel in the short, mid and even long term, but studies of the structure and morphology of corrosion layers are less abundant and generally deal with those formed in just a few years. The present study assesses the structure and morphology of corrosion product layers formed on mild steel after 13 years of exposure in five Spanish atmospheres of different types: rural, urban, industrial and marine (mild and severe). The corrosion layers have been characterised by X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). Long-term corrosion is seen to be more severe in the industrial and marine atmospheres, and less so in the rural and urban atmospheres. In all cases the corrosion rate is seen to decrease with exposure time, stabilising after the first 4-6 years of exposure. The most relevant aspects to be noted are (a) the great compaction of the rust layers formed in the rural and urban atmospheres, (b) the formation of hematite and ferrihydrite phases (not commonly found) in the industrial and marine atmospheres, respectively and (c) identification of the typical morphological structures of lepidocrocite (sandy crystals and flowery plates), goethite (cotton balls structures) and akaganeite (cotton balls structures and cigar-shaped crystals).

  1. The Redox Dynamics of Iron in a Seasonally Waterlogged Forest Soil (Chaux Forest, Eastern France) Traced with Rare Earth Element Distribution Patterns

    Science.gov (United States)

    Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.

    2014-12-01

    The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.

  2. Role of competing ions in the mobilization of arsenic in groundwater of Bengal Basin: insight from surface complexation modeling.

    Science.gov (United States)

    Biswas, Ashis; Gustafsson, Jon Petter; Neidhardt, Harald; Halder, Dipti; Kundu, Amit K; Chatterjee, Debashis; Berner, Zsolt; Bhattacharya, Prosun

    2014-05-15

    This study assesses the role of competing ions in the mobilization of arsenic (As) by surface complexation modeling of the temporal variability of As in groundwater. The potential use of two different surface complexation models (SCMs), developed for ferrihydrite and goethite, has been explored to account for the temporal variation of As(III) and As(V) concentration, monitored in shallow groundwater of Bengal Basin over a period of 20 months. The SCM for ferrihydrite appears as the better predictor of the observed variation in both As(III) and As(V) concentrations in the study sites. It is estimated that among the competing ions, PO4(3-) is the major competitor of As(III) and As(V) adsorption onto Fe oxyhydroxide, and the competition ability decreases in the order PO4(3-) ≫ Fe(II) > H4SiO4 = HCO3(-). It is further revealed that a small change in pH can also have a significant effect on the mobility of As(III) and As(V) in the aquifers. A decrease in pH increases the concentration of As(III), whereas it decreases the As(V) concentration and vice versa. The present study suggests that the reductive dissolution of Fe oxyhydroxide alone cannot explain the observed high As concentration in groundwater of the Bengal Basin. This study supports the view that the reductive dissolution of Fe oxyhydroxide followed by competitive sorption reactions with the aquifer sediment is the processes responsible for As enrichment in groundwater. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Precipitation and Deposition of Aluminum-Containing Phases in Tank Wastes

    Energy Technology Data Exchange (ETDEWEB)

    Dabbs, Daniel M.; Aksay, I.A.

    2005-12-01

    In the first phase of our study, we focused on the use of simple organics to raise the solubility of aluminum oxyhydroxides in high alkaline aqueous solvents. In a limited survey of common organic acids, we determined that citric acid had the highest potential to achieve our goal. However, our subsequent investigation revealed that the citric acid appeared to play two roles in the solutions: first, raising the concentration of aluminum in highly alkaline solutions by breaking up or inhibiting ''seed'' polycations and thereby delaying the nucleation and growth of particles; and second, stabilizing nanometer-sized particles in suspension when nucleation did occur. The results of this work were recently published in Langmuir: D.M. Dabbs, U. Ramachandran, S. Lu, J. Liu, L.-Q. Wang, I.A. Aksay, ''Inhibition of Aluminum Oxyhydroxide Precipitation with Citric Acid'' Langmuir, 21, 11690-11695 (2005). The second phase of our work involved the solvation of silicon, again in solutions of high alkalinity. Citric acid, due to its unfavorable pKa values, was not expected to be useful with silicon-containing solutions. Here, the use of polyols was determined to be effective in maintaining silicon-containing particles under high pH conditions but at smaller size with respect to standard suspensions of silicon-containing particles. There were a number of difficulties working with highly alkaline silicon-containing solutions, particularly in solutions at or near the saturation limit. Small deviations in pH resulted in particle formation or dissolution in the absence of the organic agents. One of the more significant observations was that the polyols appeared to stabilize small particles of silicon oxyhydroxides across a wider range of pH, albeit this was difficult to quantify due to the instability of the solutions.

  4. Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

    Science.gov (United States)

    Johannesson, Kevin H.; Zhou, Xiaoping

    1999-01-01

    -Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

  5. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  6. Mineralogy, geochemistry and petrophysics of red coloured granite adjacent to fractures

    International Nuclear Information System (INIS)

    Eliasson, T.

    1993-03-01

    Mineralogical, geochemical and petrophysical investigations were conducted of red-coloured alteration rims and of the neighbouring unaltered equivalents along fractures within granite from Aespoe. An investigation was made also of a weak to rather strong, red-coloured granite from the Stripa mine, as well as a weak brownish-red colouration, definitely no hydrothermal in origin, of weathered rinds at a glacial polished rock surface in the Bohus granite. When approaching the fracture planes in the Aespoe granite, the most diagnostic alteration features are * the saussuritisation and Fe-oxyhydroxide staining of plagioclase, * the crystallisation chlorite pseudomorphs after biotite and * the hematisation of magnetite. The porosity within the alteration zones increases generally 2 to 3 times compared with the protolith rock, whereas the densities decrease by some 5 to 10%. The oxidation of magnetite gives as much as a tenfold lowering of the magnetic susceptibility. The red colouration of the Stripa granite is caused by hematite ± Fe-oxyhydroxide formation along microfractures, grain boundaries and, subordinately, the main minerals. Oxidation and re-precipitation of iron liberated during a retrograde muscovitisation of principally chlorite is interpreted to be the cause of the formation of the ferric oxides. The rather homogeneous density and porosity values of the grey and of the red-coloured granites reflect the minor change in the mineralogy when going from fresh into altered granite. Weathering and whitening of plagioclase in the bleached, outer zone and precipitation of small quantities of Fe-oxyhydroxides/hydroxides in the brownish-red zone cause the macroscopic colouration of the weathering rind below the glacial polished rock surface of Bohus granite. There is a marked increase in porosity from the interior fresh (c. 0.4-0.5%) towards the exterior bleached zone (c.1.5-2%) of the subaerialy, weathered Bohus granite surface. The incipient decomposition of

  7. Trace metals of an acid mine drainage stream using a chemical model (WATEQ) and sediment analysis

    International Nuclear Information System (INIS)

    West, K.A.; Wilson, T.P.

    1992-01-01

    The high metal contents common to the discharge of acid-mine drainage (AMD) from mines and mine spoils is an environmental concern to both government and industry. This paper reports the results of investigation of the behavior of metals in an AMD system at a former surface coal mine in Tuscarawas County, Oh. AMD discharges from seeps travels, in respective order through a laminar flow stream; a Typha-dominated wetland; a turbulent flow stream; and a sediment retention pond. Dissolved metals (Fe, Mn, Zn, Cr, Cd, Cu, and Al) major and minor components, and other parameters (pH, dissolved oxygen and Eh) were measured in the AMD water at each sample location. A chemical mineral equilibrium model (WATEQ) was used to predict the minerals which should precipitate at each site. Results suggest that the seeps are supersaturated and should be precipitating hematite, goethite and magnetite (iron oxides), and siderite (iron carbonate), whereas water of the other downstream sites were at or below equilibrium conditions for these minerals. The hydrogeochemistry of the AMD was further studied using sequential chemical attacks on the precipitate sediment surface coatings, in order to determine metal concentrations in the exchangeable, carbonate, Fe-Mn oxyhydroxide, and oxidizable fractions. The carbonate and exchangeable fractions of the precipitate are dominated by Ca and Fe, as well as Mg in the carbonate fraction. The Fe-Mn oxyhydroxide fraction contained Fe, Al, Mn, Mg, and trace metals, and also contained the greatest concentration of total elements in the system. The Fe-Mn oxyhydroxide is therefore, the major sink for metals of this AMD system. The decrease in the concentration of metals in the sediment precipitates in the downstream locations, is consistent with WATEQ and water analysis results

  8. Attenuation of landfill leachate by UK Triassic sandstone aquifer materials. 1. Fate of inorganic pollutants in laboratory columns

    Science.gov (United States)

    Thornton, Steven F.; Tellam, John H.; Lerner, David N.

    2000-05-01

    The attenuation of inorganic contaminants in acetogenic and methanogenic landfill leachate by calcareous and carbonate-deficient, oxide-rich Triassic sandstone aquifer materials from the English Midlands was examined in laboratory columns. Aqueous equilibrium speciation modelling, simple transport modelling and chemical mass balance approaches are used to evaluate the key processes and aquifer geochemical properties controlling contaminant fate. The results indicate that leachate-rock interactions are dominated by ion-exchange processes, acid-base and redox reactions and sorption/precipitation of metal species. Leachate NH 4 is attenuated by cation exchange with the aquifer sediments; however, NH 4 migration could be described with a simple model using retardation factors. Organic acids in the acetogenic leachate buffered the system pH at low levels during flushing of the calcareous aquifer material. In contrast, equilibrium with Al oxyhydroxide phases initially buffered pH (˜4.5) during flushing of the carbonate-deficient sandstone with methanogenic leachate. This led to the mobilisation of sorbed and oxide-bound heavy metals from the aquifer sediment which migrated as a concentrated pulse at the leachate front. Abiotic reductive dissolution of Mn oxyhydroxides on each aquifer material by leachate Fe 2+ maintains high concentrations of dissolved Mn and buffers the leachate inorganic redox system. This feature is analogous to the Mn-reducing zones found in leachate plumes and in the experiments provides a sink for the leachate Fe load and other heavy metals. The availability of reactive solid phase Mn oxyhydroxides limits the duration of redox buffering and Fe attenuation by these aquifer sediments. Aquifer pH and redox buffering capacity exert a fundamental influence on leachate inorganic contaminant fate in these systems. The implications for the assessment of aquifer vulnerability at landfills are discussed and simple measurements of aquifer properties which

  9. Influence of iron redox cycling on organo-mineral associations in arctic tundra soils

    Science.gov (United States)

    Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.

    2016-12-01

    Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.

  10. Mineral Dissolution and Precipitation due to Carbon Dioxide-Water-Rock Interactions: The Significance of Accessory Minerals in Carbonate Reservoirs (Invited)

    Science.gov (United States)

    Kaszuba, J. P.; Marcon, V.; Chopping, C.

    2013-12-01

    Accessory minerals in carbonate reservoirs, and in the caprocks that seal these reservoirs, can provide insight into multiphase fluid (CO2 + H2O)-rock interactions and the behavior of CO2 that resides in these water-rock systems. Our program integrates field data, hydrothermal experiments, and geochemical modeling to evaluate CO2-water-rock reactions and processes in a variety of carbonate reservoirs in the Rocky Mountain region of the US. These studies provide insights into a wide range of geologic environments, including natural CO2 reservoirs, geologic carbon sequestration, engineered geothermal systems, enhanced oil and gas recovery, and unconventional hydrocarbon resources. One suite of experiments evaluates the Madison Limestone on the Moxa Arch, Southwest Wyoming, a sulfur-rich natural CO2 reservoir. Mineral textures and geochemical features developed in the experiments suggest that carbonate minerals which constitute the natural reservoir will initially dissolve in response to emplacement of CO2. Euhedral, bladed anhydrite concomitantly precipitates in response to injected CO2. Analogous anhydrite is observed in drill core, suggesting that secondary anhydrite in the natural reservoir may be related to emplacement of CO2 into the Madison Limestone. Carbonate minerals ultimately re-precipitate, and anhydrite dissolves, as the rock buffers the acidity and reasserts geochemical control. Another suite of experiments emulates injection of CO2 for enhanced oil recovery in the Desert Creek Limestone (Paradox Formation), Paradox Basin, Southeast Utah. Euhedral iron oxyhydroxides (hematite) precipitate at pH 4.5 to 5 and low Eh (approximately -0.1 V) as a consequence of water-rock reaction. Injection of CO2 decreases pH to approximately 3.5 and increases Eh by approximately 0.1 V, yielding secondary mineralization of euhedral pyrite instead of iron oxyhydroxides. Carbonate minerals also dissolve and ultimately re-precipitate, as determined by experiments in the

  11. Microbial community signature in Lake Coeur d’Alene: Association of environmental variables and toxic heavy metal phases

    International Nuclear Information System (INIS)

    Moberly, James; D'Imperio, Seth; Parker, Albert; Peyton, Brent

    2016-01-01

    The water and sediments of Lake Coeur d’Alene in northern Idaho (USA) have been impacted by decades of mining operations within the Coeur d’Alene mining district. Using a multivariate statistical approach, correlations were explored between the microbial community (via 16S rDNA microarray) in sediment cores and operationally defined heavy metal phases (via continuous sequential extractions). Candidate phyla NC10, OP8 and LD1PA were only detected in metal contaminated cores and diversity doubled among Natronoanaerobium in metal contaminated cores compared to the uncontaminated control site. This may suggest some increased fitness of these phyla in contaminated sediments. In contrast, diversity within the phyla Aquificae, Coprothermobacteria, and Synergistes was at least double in the uncontaminated control site. In linear models composed of two geochemical variables from the presumed sulfate reducing lineages detected in this study, orders Desulfobacterales, Desulfuromonadales, Desulfotomaculum, and Syntrophobacterales were highly correlated with Pb (positive influence) and Zn (negative influence) in the operationally defined residual fraction, and most taxa within orders from Desulfovibrionales. Bdellovibrionales highly correlated with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. Diversity within families from metal reducing bacterial lineages Shewanellaceae, Geobacteraceae, and Rhodocyclaceae showed high correlation with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. To our knowledge, this is the first time these techniques have been used in combination to describe a contaminated system. Resulting correlations suggest the diversity of the microbial community was influenced primarily by partitioning of heavy metals into exchangeable Pb over other Pb phases and, to a lesser extent, residual Pb to residual Zn phase partitioning. - Highlights: • Continuous

  12. Feed gas contaminant removal in ion transport membrane systems

    Science.gov (United States)

    Carolan, Michael Francis [Allentown, PA; Miller, Christopher Francis [Macungie, PA

    2008-09-16

    Method for gas purification comprising (a) obtaining a feed gas stream containing one or more contaminants selected from the group consisting of volatile metal oxy-hydroxides, volatile metal oxides, and volatile silicon hydroxide; (b) contacting the feed gas stream with a reactive solid material in a guard bed and reacting at least a portion of the contaminants with the reactive solid material to form a solid reaction product in the guard bed; and (c) withdrawing from the guard bed a purified gas stream.

  13. Gallic Acid, Ellagic Acid and Pyrogallol Reaction with Metallic Iron

    International Nuclear Information System (INIS)

    Jaen, J. A.; Gonzalez, L.; Vargas, A.; Olave, G.

    2003-01-01

    The reaction between gallic acid, ellagic acid and pyrogallol with metallic iron was studied using infrared and Moessbauer spectroscopy. Most hydrolysable tannins with interesting anticorrosive or inhibition properties are structurally related to these compounds, thus they may be used as models for the study of hydrolysable tannins and related polyphenols. The interaction was followed up to 3 months. Results indicated two different behaviors. At polyphenol concentrations higher than 1% iron converts to sparingly soluble and amorphous ferric (and ferrous) polyphenolate complexes. At lower concentrations (0.1%), the hydrolysis reactions are dominant, resulting in the formation of oxyhydroxides, which can be further reduced to compounds like magnetite by the polyphenols.

  14. Electron microscopy of Mg/TiO{sub 2} photocatalyst morphology for deep desulfurization of diesel

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Yee Cia, E-mail: gabrielle.ciayin@gmail.com [Department of Chemical Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak (Malaysia); Kait, Chong Fai, E-mail: chongfaikait@petronas.com.my; Fatimah, Hayyiratul, E-mail: hayyiratulfatimah@yahoo.com; Wilfred, Cecilia, E-mail: cecili@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak (Malaysia)

    2015-07-22

    A series of Mg/TiO{sub 2} photocatalysts were prepared and characterized using Field Emission Scanning Electron Microscopy (FESEM) and High-Resolution Transmission Electron Microscopy (HRTEM). The average particle sizes of the photocatalysts were ranging from 25.7 to 35.8 nm. Incorporation of Mg on TiO{sub 2} did not lead to any surface lattice distortion to TiO{sub 2}. HRTEM data indicated the presence of MgO and Mg(OH){sub 2} mixture at low Mg loading while at higher Mg loading, the presence of lamellar Mg-oxyhydroxide intermediates and Mg(OH){sub 2}.

  15. Electron microscopy of Mg/TiO2 photocatalyst morphology for deep desulfurization of diesel

    International Nuclear Information System (INIS)

    Yin, Yee Cia; Kait, Chong Fai; Fatimah, Hayyiratul; Wilfred, Cecilia

    2015-01-01

    A series of Mg/TiO 2 photocatalysts were prepared and characterized using Field Emission Scanning Electron Microscopy (FESEM) and High-Resolution Transmission Electron Microscopy (HRTEM). The average particle sizes of the photocatalysts were ranging from 25.7 to 35.8 nm. Incorporation of Mg on TiO 2 did not lead to any surface lattice distortion to TiO 2 . HRTEM data indicated the presence of MgO and Mg(OH) 2 mixture at low Mg loading while at higher Mg loading, the presence of lamellar Mg-oxyhydroxide intermediates and Mg(OH) 2

  16. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  17. Effects of manganese oxide on arsenic reduction and leaching from contaminated floodplain soil

    DEFF Research Database (Denmark)

    Ehlert, Katrin; Mikutta, Christian; Kretzschmar, Ruben

    2016-01-01

    Reductive release of the potentially toxic metalloid As from Fe(III) (oxyhydr)oxides has been identified as an important process leading to elevated As porewater concentrations in soils and sediments. Despite the ubiquitous presence of Mn oxides in soils and their oxidizing power toward As.......7) on As speciation and release from an As-contaminated floodplain soil (214 mg As/kg) under anoxic conditions. Our results show that birnessite additions significantly decreased As leaching. The reduction of both As and Fe was delayed, and As(III) accumulated in birnessite-rich column parts, indicating...

  18. HIGHER ORDER SPECIATION EFFECTS ON PLUTONIUM L3 X-RAY ABSORPTION NEAR EDGE SPECTRA.

    Energy Technology Data Exchange (ETDEWEB)

    Conradson, Steven D.; Abney, Kent D.; Begg, Bruce D.; Brady, Erik D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Lupinetti, Anthony J.; Neu, Mary P.; Palmer, Phillip D.; Paviet-Hartmann, Patricia; Reilly, Sean D.; Runde, Wolfgang H.; Tait, C. Drew; Veirs, D. Kirk

    2003-06-09

    Pu L{sub 3} X-ray Near Edge Absorption Spectra for Pu(0-VII) are reported for more than 50 chalcogenides, chlorides, hydrates, hydroxides, nitrates, carbonates, oxy-hydroxides, and other compounds both as solids and in solution, and substituted in zirconlite, perovksite, and borosilicate glass. This large data base extends the known correlations between the energy and shape of these spectra from the usual association of the XANES with valence and site symmetry to higher order chemical effects. Because of the large number of compounds of these different types a number of novel and unexpected behaviors are observed.

  19. Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

    International Nuclear Information System (INIS)

    Moncur, Michael C.; Paktunc, Dogan; Jean Birks, S.; Ptacek, Carol J.; Welsh, Brent; Thibault, Yves

    2015-01-01

    Highlights: • Widespread naturally occurring As in groundwater with concentrations up to 179 μg/L. • 50% of the 816 water wells sampled exceeded 10 μg/L of As. • As(III) was the dominant species in 74% of the groundwater samples. • Shallow groundwater As is derived from arsenian pyrite oxidation. • In deeper sediments, As release is associated with Fe(III) reduction. - Abstract: Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest

  20. Quantification of Multiple Components of Complex Aluminum-Based Adjuvant Mixtures by Using Fourier Transform Infrared Spectroscopy and Partial Least Squares Modeling.

    Science.gov (United States)

    Dowling, Quinton M; Kramer, Ryan M

    2017-01-01

    Fourier transform infrared (FTIR) spectroscopy is widely used in the pharmaceutical industry for process monitoring, compositional quantification, and characterization of critical quality attributes in complex mixtures. Advantages over other spectroscopic measurements include ease of sample preparation, quantification of multiple components from a single measurement, and the ability to quantify optically opaque samples. This method describes the use of a multivariate model for quantifying a TLR4 agonist (GLA) adsorbed onto aluminum oxyhydroxide (Alhydrogel ® ) using FTIR spectroscopy that may be adapted to quantify other complex aluminum based adjuvant mixtures.

  1. Gallic Acid, Ellagic Acid and Pyrogallol Reaction with Metallic Iron

    Energy Technology Data Exchange (ETDEWEB)

    Jaen, J. A., E-mail: jjaen@ancon.up.ac.p [Universidad de Panama, Departamento de Quimica Fisica, Facultad de Ciencias Naturales, Exactas y Tecnologia (Panama); Gonzalez, L.; Vargas, A.; Olave, G. [Universidad de Panama, Escuela de Quimica, Facultad de Ciencias Naturales, Exactas y Tecnologia (Panama)

    2003-06-15

    The reaction between gallic acid, ellagic acid and pyrogallol with metallic iron was studied using infrared and Moessbauer spectroscopy. Most hydrolysable tannins with interesting anticorrosive or inhibition properties are structurally related to these compounds, thus they may be used as models for the study of hydrolysable tannins and related polyphenols. The interaction was followed up to 3 months. Results indicated two different behaviors. At polyphenol concentrations higher than 1% iron converts to sparingly soluble and amorphous ferric (and ferrous) polyphenolate complexes. At lower concentrations (0.1%), the hydrolysis reactions are dominant, resulting in the formation of oxyhydroxides, which can be further reduced to compounds like magnetite by the polyphenols.

  2. Investigation of the interaction of Greek dolomitic marble with metal aqueous solutions using rutherford backscattering and X-ray photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Godelitsas, A.; Kokkoris, M.; Misaelides, P.

    2007-01-01

    The interaction of Greek dolomitic marble (from Thassos island, northern Greece) with Co 2+ , Cd 2+ , Pb 2+ and Cr 3+ containing aqueous solutions was studied by characterizing the surface of the solid experimental samples, using a combination of spectroscopic, microscopic, and diffraction techniques (RBS, XPS, SEM-EDS, FT-IR, powder-XRD). The obtained results indicated a considerable Cd 2+ and Co 2+ sorption on the dissolved surface of the carbonate substrate, whereas, under the same experimental conditions, the Pb 2+ and Cr 3+ interaction is more intense leading to extended overgrowth of crystalline Pb 2+ carbonates and massive surface precipitation of amorphous Cr 3+ hydroxide/oxyhydroxide. (author)

  3. Mixed waste treatment with a mediated electrochemical process

    International Nuclear Information System (INIS)

    Hickman, R.G.; Gray, L.W.; Chiba, Z.

    1991-01-01

    The process described in this paper is intended to convert mixed waste containing toxic organic compounds (not heavy metals) to ordinary radioactive waste, which is treatable. The process achieves its goal by oxidizing hydrocarbons to CO 2 and H 2 O. Other atoms that may be present in the toxic organic generally are converted to nonhazardous anions such as sulfate and phosphate. This electro chemical conversion is performed at conditions of temperature and pressure that are just moderately above ambient conditions. Gaseous hydroxides and oxyhydroxides that are formed by many radionuclides during incineration cannot form in this process. 1 ref., 3 figs

  4. Uranium distribution and fixation in main types of climatic and stational pedogenesis on crystalline rocks

    International Nuclear Information System (INIS)

    Gueniot, B.

    1983-11-01

    An experimental and analytical study of uranium behavior in soils and of its distribution was carried out for bioclimatic pedogenesis on crystalline rocks, generally granites. Uranium distribution, and sometimes thorium) is compared to the distribution of tracers of pedogenesis (C, Fe, Al, Si, alkalis, clays). Uranium and thorium behavior is dependent of pedogenesis and can be leached or concentrated. Various fractions of soil alteration complexes and associated uranium can be isolated by chemical and physical fractionation and fixation sites for U are evidenced, efficiency is tested in situ. Adsorption is low onclays, fixation is frequent on oxyhydroxides, organic compounds are active for uranium complexation [fr

  5. Natural analogue of redox front formation in near-field environment at post-closure phase of HLW geological disposal

    International Nuclear Information System (INIS)

    Yoshida, Hidekazu; Yamamoto, Koushi; Amano, Yuki

    2005-01-01

    Redox fronts are created in the near field of rocks, in a range of oxidation environments, by microbial activity in rock groundwater. Such fronts, and the associated oxide formation, are usually unavoidable around high level radioactive waste (HLW) repositories, whatever their design. The long term behaviour of these oxides after repositories have been closed is however little known. Here we introduce an analogue of redox front formation, such as 'iron oxide' deposits, known as takashikozo forming cylindrical nodules, and the long term behaviour of secondarily formed iron oxyhydroxide in subsequent geological environments. (author)

  6. The assessment of the long-term evolution of the spent nuclear fuel matrix by kinetic, thermodynamic and spectroscopic studies of uranium minerals

    International Nuclear Information System (INIS)

    Bruno, J.; Casas, I.; Cera, E.; Ewing, R.C.; Finch, R.J.

    1995-01-01

    The long term behavior of spent nuclear fuel is discussed in the light of recent thermodynamic and kinetic data on mineralogical analogues related to the key phases in the oxidative alteration of uraninite. The implications for the safety assessment of a repository of the established oxidative alteration sequence of the spent fuel matrix are illustrated with Pagoda calculations. The application to the kinetic and thermodynamic data to source term calculations indicates that the appearance and duration of the U(VI) oxyhydroxide transient is critical for the stability of the fuel matrix

  7. Conversion electron Moessbauer study of low carbon steel polarized in aqueous sulfate solution containing sulfite in low concentration

    International Nuclear Information System (INIS)

    Vertes, Cs.; Lakatos-Varsanyi, M.; Vertes, A.; Kuzmann, E.; Meisel, W.; Guetlich, P.

    1992-01-01

    The passivation of low carbon steel was studied in aqueous solution of 0.5 M Na 2 SO 4 +0.001 M NaHSO 3 at pH=3.5 and 6.5. The found major components at pH=3.5 were: γ-FeOOH and Fe 3 C, and also FeSO 4 .H 2 O could be identified on the surface of the low carbon steel as a minor component. At pH=6.5, the passive film contained only amorphous iron(III)-oxide or oxyhydroxide. (orig.)

  8. Lithium Hideout and Return in the CANDU Heat Transport System during Shutdown and Start-up

    International Nuclear Information System (INIS)

    Qiu, L.; Snaglewski, A.P.

    2012-09-01

    Lithium hydroxide is used to control the pH a (pH apparent) of the Heat Transport System (HTS) coolant in CANDU R reactors. The recommended range of the lithium concentration in the coolant is between 0.38 ppm (5.5x10 -5 m) and 0.60 ppm (8.7x10 -5 m) to minimize carbon steel corrosion in the HTS and magnetite deposition in the core during normal operation; this corresponds to pH a values between 10.2 and 10.4. Similar pH a and lithium concentrations should be maintained during shutdown and start-up. However, maintaining the pH a of the HTS coolant within specification during shutdown and start-up has been difficult for some CANDU stations, especially when the HTS is taken to a Low Level Drain State (LLDS), because of lithium hideout and return. This paper presents the results from lithium adsorption and desorption studies on iron oxides under relevant shutdown and start-up chemistry conditions performed to elucidate the mechanisms of the observed lithium hideout and return. The results show that lithium hideout and return are driven largely by changes in the solubility of magnetite as the HTS coolant chemistry changes during shutdown; changes in lithium concentration were inversely correlated with the solubility of magnetite. When the HTS system is de-pressurized and drained to a low coolant level, the ingress of air rapidly oxidizes the dissolved Fe (II) in the coolant, 2Fe +2 + 1 / 2 O 2 + 3 H 2 = 2FEOOH + 4 H + , resulting in the formation of lepidocrocite or maghemite, which have much lower solubilities but larger surface areas than does magnetite. The large surface area of the Fe (III) oxides can adsorb significant quantities of lithium from the coolant, leading to lithium hideout and a pH a decrease. During start-up, the chemistry of the coolant changes from oxidizing to reducing, and lepidocrocite and other Fe (III) oxides are reduced to Fe (II), gradually dissolving as their solubility increases with increasing temperature. The adsorbed lithium is released

  9. Aging study on carboxymethyl cellulose-coated zero-valent iron nanoparticles in water: Chemical transformation and structural evolution

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Haoran, E-mail: dongh@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha, Hunan 410082 (China); Zhao, Feng; Zeng, Guangming; Tang, Lin; Fan, Changzheng; Zhang, Lihua; Zeng, Yalan; He, Qi; Xie, Yankai; Wu, Yanan [College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha, Hunan 410082 (China)

    2016-07-15

    Highlights: • The chemical transformation and structural evolution of CMC-nZVI were investigated. • CMC could slow down the aging rate of nZVI and alter the species transformation. • Fe{sub 3}O{sub 4} and/or γ-Fe{sub 2}O{sub 3} are the dominant corrosion products of bare nZVI after aging. • γ-FeOOH is the primary corrosion product of CMC-nZVI after aging. - Abstract: To assess the long-term fate and the associated risks of nanoscale zero-valent iron (nZVI) used in the water remediation, it is essential to understand the chemical transformations during aging of nZVI in water. This study investigated the compositional and structural evolution of bare nZVI and carboxymethyl cellulose (CMC) coated nZVI in static water over a period of 90 days. Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the corrosion products of nZVI and CMC-nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging, but the coating of CMC could slow down the aging rate of nZVI (as indicated by the slower drop in Fe{sup 0} intensity in XRD pattern). For the bare nZVI, magnetite (Fe{sub 3}O{sub 4}) and/or maghemite (γ-Fe{sub 2}O{sub 3}) are the dominant corrosion products after 90 days of aging. However, for the CMC-nZVI, the core-shell spheres collapses to acicular-shaped structures after aging with crystalline lepidocrocite (γ-FeOOH) as the primary end product. Moreover, more lepidocrocite present in the corrosion products of CMC-nZVI with higher loading of CMC, which reveals that the CMC coating could influence the transformation of iron oxides.

  10. Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zheming; Shi, Zhi; Shi, Liang; White, Gaye F.; Richardson, David J.; Clarke, Thomas A.; Fredrickson, Jim K.; Zachara, John M.

    2015-08-25

    Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM) were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer

  11. Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

    Science.gov (United States)

    ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

    2017-06-20

    In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short

  12. Geochemical partitioning of Cu and Ni in mangrove sediments: Relationships with their bioavailability

    International Nuclear Information System (INIS)

    Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita

    2015-01-01

    Highlights: • Metal speciation controls bioavailability in mangrove ecosystem. • Bioavailability of Ni was controlled by Fe/Mn-oxyhydroxide and organic phases • Bioavailability of Cu in mangrove roots was controlled by organic phase in the sediments. • Cu interacts more strongly with organic phases than Ni in mangrove sediment. - Abstract: Sequential extraction study was performed to determine the concentrations of non-residual metal-complexes in the mangrove sediments from the Divar Island, (west coast of India). Accumulation of metal in the mangrove roots (from the same location) was determined and used as an indicator of bioavailability of metal. An attempt was made to establish a mechanistic linkage between the non-residual metal complexes and their bioavailability in the mangrove system. The non-residual fractions of Cu and Ni were mainly associated with Fe/Mn oxyhydroxide and organic phases in the sediments. A part of these metal fractions were bioavailable in the system. These two phases were the major controlling factors for Ni speciation and their bioavailability in the studied sediments. However, Cu was found to interact more strongly with the organic phases than Ni in the mangrove sediments. Organic phases in the mangrove sediments acted as buffer to control the speciation and bioavailability of Cu in the system

  13. Electron microscopy study of microbial mat in the North Fiji basin hydrothermal vent

    Science.gov (United States)

    Park, H.; Kim, J. W.; Lee, J. W.

    2017-12-01

    Hydrothermal vent systems consisting of hydrothermal vent, hydrothermal sediment and microbial mat are widely spread around the ocean, particularly spreading axis, continental margin and back-arc basin. Scientists have perceived that the hydrothermal systems, which reflect the primeval earth environment, are one of the best places to reveal the origin of life and extensive biogeochemical process of microbe-mineral interaction. In the present study multiline of analytical methods (X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM)) were utilized to investigate the mineralogy/chemistry of microbe-mineral interaction in hydrothermal microbial mat. Microbial mat samples were recovered by Canadian scientific submersible ROPOS on South Pacific North Fiji basin KIOST hydrothermal vent expedition 1602. XRD analysis showed that red-colored microbial mat contains Fe-oxides and Fe-oxyhydroxides. Various morphologies of minerals in the red-colored microbial mat observed by SEM are mainly showed sheath shaped, resembled with Leptothrix microbial structure, stalks shaped, similar with Marioprofundus microbial structure and globule shaped microbial structures. They are also detected with DNA analysis. The cross sectional observation of microbial structures encrusted with Fe-oxide and Fe-oxyhydroxide at a nano scale by Transmission Electron Microscopy (TEM) and Focused Ion Beam (FIB) technique was developed to verify the structural/biogeochemical properties in the microbe-mineral interaction. Systematic nano-scale measurements on the biomineralization in the microbial mat leads the understandings of biogeochemical environments around the hydrothermal vent.

  14. Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

    Science.gov (United States)

    Wang, Guohui; Um, Wooyong; Wang, Zheming; Reinoso-Maset, Estela; Washton, Nancy M; Mueller, Karl T; Perdrial, Nicolas; O'Day, Peggy A; Chorover, Jon

    2017-10-03

    The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO 2 )(PO 4 )·3H 2 O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10 -12 mol g -1 s -1 . In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10 -10 mol g -1 s -1 . The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

  15. Natural clinoptilolite exchanged with iron: characterization and catalytic activity in nitrogen monoxide reduction

    Directory of Open Access Journals (Sweden)

    Daria Tito-Ferro

    2016-12-01

    Full Text Available The aim of this work was to characterize the natural clinoptilolite from Tasajeras deposit, Cuba, modified by hydrothermal ion-exchange with solutions of iron (II sulfate and iron (III nitrate in acid medium. Besides this, its catalytic activity to reduce nitrogen monoxide with carbon monoxide/propene in the presence of oxygen was evaluated. The characterization was performed by Mössbauer and UV-Vis diffuse reflectance spectroscopies and adsorption measurements. The obtained results lead to conclude that in exchanged samples, incorporated divalent and trivalent irons are found in octahedral coordination. Both irons should be mainly in cationic extra-framework positions inside clinoptilolite channels as charge compensating cations, and also as iron oxy-hydroxides resulting from limited hydrolysis of these cations. The iron (III exchanged samples has a larger amount of iron oxy-hydroxides agglomerates. The iron (II exchanged samples have additionally iron (II sulfate adsorbed. The catalytic activity in the nitrogen monoxide reduction is higher in the exchanged zeolites than starting. Among all samples, those exchanged of iron (II has the higher catalytic activity. This lead to outline that, main catalytically active centers are associated with divalent iron.

  16. Change in catalyst properties during coal liquefaction; Kokoritsu sekitan ekika shokubai no kaihatsu (Hanno no shinko ni tomonau shokubai seijo no henka). 1

    Energy Technology Data Exchange (ETDEWEB)

    Koyama, T.; Sato, K.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

    1996-10-28

    The purpose of this study is to prevent the deactivation of catalysts recycled in the 0.1 t/d bench scale unit (BSU). Catalysts recovered during reactions in the BSU and after reactions in the 5-liter autoclave were analyzed, to investigate the influences of the reaction condition on the property and activity of catalysts. Were used {gamma}-iron oxyhydroxide ({gamma}-FeOOH), {alpha}-iron oxyhydroxide ({alpha}-FeOOH), and natural pyrite (FeS2) as catalysts. At the S/Fe atomic ration of 1.2 under the BSU reaction condition, troilite was more easily formed from {gamma}-FeOOH compared with pyrite and {alpha}-FeOOH. As the reaction proceeded through the first, second, and third reactors, the crystal size increased, the pyrrhotite content decreased, and the troilite content increased. Deactivation due to the formation of troilite was irreversible. At the S/Fe of 3.0, however, both the formation of troilite and the crystal growth of pyrrhotite were not observed. It was found that the deactivation of catalysts can be remarkably suppressed. 5 refs., 6 figs., 1 tab.

  17. A novel approach for arsenic adsorbents regeneration using MgO.

    Science.gov (United States)

    Tresintsi, Sofia; Simeonidis, Konstantinos; Katsikini, Maria; Paloura, Eleni C; Bantsis, Georgios; Mitrakas, Manassis

    2014-01-30

    An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Seasonal arsenic accumulation in stream sediments at a groundwater discharge zone.

    Science.gov (United States)

    MacKay, Allison A; Gan, Ping; Yu, Ran; Smets, Barth F

    2014-01-21

    Seasonal changes in arsenic and iron accumulation rates were examined in the sediments of a brook that receives groundwater discharges of arsenic and reduced iron. Clean glass bead columns were deployed in sediments for known periods over the annual hydrologic cycle to monitor changes in arsenic and iron concentrations in bead coatings. The highest accumulation rates occurred during the dry summer period (July-October) when groundwater discharges were likely greatest at the sample locations. The intermediate flow period (October-March), with higher surface water levels, was associated with losses of arsenic and iron from bead column coatings at depths below 2-6 cm. Batch incubations indicated iron releases from solids to be induced by biological reduction of iron (oxy)hydroxide solids. Congruent arsenic releases during incubation were limited by the high arsenic sorption capacity (0.536 mg(As)/mg(Fe)) of unreacted iron oxide solids. The flooded spring (March-June) with high surface water flows showed the lowest arsenic and iron accumulation rates in the sediments. Comparisons of accumulation rates across a shoreline transect were consistent with greater rates at regions exposed above surface water levels for longer times and greater losses at locations submerged below surface water. Iron (oxy)hydroxide solids in the shallowest sediments likely serve as a passive barrier to sorb arsenic released to pore water at depth by biological iron reduction.

  19. Mobilisation and Bioavailability of Arsenic Around Mesothermal Gold Deposits in a Semiarid Environment, Otago, New Zealand

    Directory of Open Access Journals (Sweden)

    D. Craw

    2002-01-01

    Full Text Available Arsenopyrite (FeAsS is the principal arsenic (As mineral in mineralised mesothermal veins (typically 5,000 mg/kg As in southeastern New Zealand. Groundwater in contact with arsenopyrite-bearing rocks has elevated As concentrations (up to 0.1 mg/l. The arsenopyrite decomposes slowly on oxidation in soils and historic mine workings in a cool semiarid climate. Dissolved As is predominantly As(III in association with arsenopyrite, but this is rapidly oxidised over days to weeks to As(V in the vadose zone. Oxidation is facilitated by particulate Fe and/or Mn oxyhydroxides, and by bacteria in surface waters. Evaporative concentration of dissolved As(V in the vadose zone causes precipitation of scorodite (Fe(IIIAs(VO4.2H2O. Adsorption of As(V to Fe oxyhydroxides in soils and groundwater pathways lowers dissolved As concentrations. Soils over mineralised veins typically have <200 mg/kg As, as most As is removed in solution on geological time scales. Most plants on the mineralised rocks and soils do not take up As, although some inedible species can fix up to 18 mg/kg As. Hence, bioavailability of As(V is low in this environment, despite the substantial As flux.

  20. Comparative study of biogenic and abiotic iron-containing materials

    Energy Technology Data Exchange (ETDEWEB)

    Cherkezova-Zheleva, Z., E-mail: zzhel@ic.bas.bg; Shopska, M., E-mail: shopska@ic.bas.bg; Paneva, D. [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria); Kovacheva, D. [Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry (Bulgaria); Kadinov, G.; Mitov, I. [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria)

    2016-12-15

    Series of iron-based biogenic materials prepared by cultivation of Leptothrix group of bacteria in different feeding media (Sphaerotilus-Leptothrix group of bacteria isolation medium, Adler, Lieske and silicon-iron-glucose-peptone) were studied. Control samples were obtained in the same conditions and procedures but the nutrition media were not infected with bacteria, i.e. they were sterile. Room and low temperature Mössbauer spectroscopy, powder X-ray diffraction (XRD), and infrared spectroscopy (IRS) were used to reveal the composition and physicochemical properties of biomass and respective control samples. Comparative analysis showed differences in their composition and dispersity of present phases. Sample composition included different ratio of nanodimensional iron oxyhydroxide and oxide phases. Relaxation phenomena such as superparamagnetism or collective magnetic excitation behaviour were registered for some of them. The experimental data showed that the biogenic materials were enriched in oxyhydroxides of high dispersion. Catalytic behaviour of a selected biomass and abiotic material were studied in the reaction of CO oxidation. In situ diffuse-reflectance (DR) IRS was used to monitor the phase transformations in the biomass and CO conversion.

  1. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    Energy Technology Data Exchange (ETDEWEB)

    Cole, T G [Imperial Coll. of Science and Technology, London (UK). Geology Dept.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO/sub 2/ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO/sub 3/ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.)

  2. Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

    Science.gov (United States)

    Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

    2018-05-01

    During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

  3. Preliminary delineation of natural geochemical reactions, Snake River Plain aquifer system, Idaho National Engineering Laboratory and vicinity, Idaho

    International Nuclear Information System (INIS)

    Knobel, L.L.; Bartholomay, R.C.; Orr, B.R.

    1997-05-01

    The U.S. Geological Survey, in cooperation with the U.S. Department of Energy, is conducting a study to determine the natural geochemistry of the Snake River Plain aquifer system at the Idaho National Engineering Laboratory (INEL), Idaho. As part of this study, a group of geochemical reactions that partially control the natural chemistry of ground water at the INEL were identified. Mineralogy of the aquifer matrix was determined using X-ray diffraction and thin-section analysis and theoretical stabilities of the minerals were used to identify potential solid-phase reactants and products of the reactions. The reactants and products that have an important contribution to the natural geochemistry include labradorite, olivine, pyroxene, smectite, calcite, ferric oxyhydroxide, and several silica phases. To further identify the reactions, analyses of 22 representative water samples from sites tapping the Snake River Plain aquifer system were used to determine the thermodynamic condition of the ground water relative to the minerals in the framework of the aquifer system. Principal reactions modifying the natural geochemical system include congruent dissolution of olivine, diopside, amorphous silica, and anhydrite; incongruent dissolution of labradorite with calcium montmorillonite as a residual product; precipitation of calcite and ferric oxyhydroxide; and oxidation of ferrous iron to ferric iron. Cation exchange reactions retard the downward movement of heavy, multivalent waste constituents where infiltration ponds are used for waste disposal

  4. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    International Nuclear Information System (INIS)

    Cole, T.G.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO 2 fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO 3 accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.) (author)

  5. The effect of aerobic corrosion on anaerobically-formed sulfide layers on carbon steel in dilute near-neutral pH saline solutions

    International Nuclear Information System (INIS)

    Sherar, B.W.A.; Keech, P.G.; Shoesmith, D.W.

    2013-01-01

    Highlights: •The corrosion rate is low when steel is exposed to anaerobic conditions (pH = 8.9). •An anaerobic corrosion with sulfide to aerobic switch increases the corrosion rate. •Aerobic conditions leads to corrosion and oxide deposition beneath FeS. •Continual air exposure leads to the blistering of the original FeS film. -- Abstract: The aerobic corrosion of pipeline steel was investigated in an aqueous sulfide solution by monitoring the corrosion potential and periodically measuring the polarization resistance. The properties and composition of the corrosion product deposits formed were determined using scanning electron microscopy, energy dispersive X-ray analysis, and Raman spectroscopy. The establishment of aerobic conditions leads to corrosion and (oxyhydr)oxide deposition beneath the anaerobically-formed mackinawite film originally present on the steel surface. This leads to blistering and spalling of the sulfide film. Chemical conversion of the mackinawite to Fe(III) (oxyhydr)oxides also occurs but is a relatively slow reaction

  6. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Yamamoto, K.; Murakami, Y.; Hoshii, D.; Kanekiyo, A.; Naganuma, T.; Hayashi, T.

    2008-01-01

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure

  7. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, H. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan)], E-mail: dora@num.nagoya-u.ac.jp; Metcalfe, R. [Quintessa Japan, Queen' s Tower A7-707, Minatomirai, Yokohama 220-6007 (Japan); Yamamoto, K. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan); Murakami, Y. [Japan Atomic Energy Agency (JAEA), Tono Geoscience Centre (Japan); Hoshii, D.; Kanekiyo, A.; Naganuma, T. [Hiroshima University, Higashi Hiroshima, Kagamiyama 1-4-4 (Japan); Hayashi, T. [Asahi University, Department of Dental Pharmacology, Hozumi, Gifu (Japan)

    2008-08-15

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure.

  8. Nuclear Energy Research Initiative (NERI) Program. Technical progress report

    International Nuclear Information System (INIS)

    Engelhardt, G.R.; MacDonald, D.D.

    2000-01-01

    During the past quartile the authors have explored the thermodynamics of various metal hydroxide and oxyhydroxide dehydration reactions of iron, nickel, and chromium with the objective of estimating the critical temperature, T(sub cr). This is the temperature at which the oxide is in equilibrium with the oxyhydroxide or hydroxide and water vapor under the expected repository conditions of temperature and pressure. Because localized corrosion requires the presence of an ionically conducting phase on the surface (to support oxygen reduction) T(sub cr) is also the temperature below which ''wet'' corrosion first becomes possible. Past analyses have assumed that wet corrosion requires the presence of a layer of bulk water on the surface and hence that corrosion is not possible at temperatures above the boiling temperature of bulk water under the prevailing atmospheric pressure. Furthermore, significant elevation of the boiling temperature may occur if the aqueous phase becomes concentrated in salts. Because of the hydration of hygroscopic corrosion products, which may occur at significantly higher temperatures than the boiling temperature of water, and because of boiling temperature elevation effects, the past assumption needs to be reevaluated. This is the primary goal of this work

  9. Photoemission study of metallic iron nanoparticles surface aging in biological fluids. Influence on biomolecules adsorption

    International Nuclear Information System (INIS)

    Canivet, L.; Denayer, F.O.; Champion, Y.; Cenedese, P.; Dubot, P.

    2014-01-01

    Iron nanoparticles (nFe) prepared by vaporization and cryogenic condensation process (10–100 nm) has been exposed to Hank's balanced salt solution (HBSS) and the B-Ali cell growth fluids. These media can be used for cellular growth to study nFe penetration through cell membrane and its induced cytotoxicity. Surface chemistry of nFe exposed to such complex fluids has been characterized as the nanoparticles surface can be strongly changed by adsorption or corrosion processes before reaching intracellular medium. Particle size and surface chemistry have been characterized by scanning electron microscopy (SEM) and high-resolution X-ray photoelectron spectroscopy (HR-XPS). Exposition of nFe particles to growth and differentiation media leads to the formation of an oxy-hydroxide layer containing chlorinated species. We found that the passivated Fe 2 O 3 layer of the bare nFe particles is rapidly transformed into a thicker oxy-hydroxide layer that has a greater ability to adsorb molecular ions or ionic biomolecules like proteins or DNA.

  10. Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

    Science.gov (United States)

    Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-07-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

  11. Characterisation of zinc in slags originated from a contaminated sediment by coupling μ-PIXE, μ-RBS, μ-EXAFS and powder EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Isaure, M.P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-01-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2 O 3 ·9H 2 O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation

  12. Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, A. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Duchesne, J., E-mail: josee.duchesne@ggl.ulaval.ca [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Fournier, B. [Centre de Recherche sur les Infrastructures en Beton (CRIB), Universite Laval, 1065 ave de la Medecine, Quebec, QC, Canada G1V 0A6 (Canada); Durand, B. [Institut de recherche d' Hydro-Quebec (IREQ), 1740 boul. Lionel-Boulet, Varennes, QC, Canada J3X 1S1 (Canada); Rivard, P. [Universite de Sherbrooke, Sherbrooke, QC, Canada J1K 2R1 (Canada); Shehata, M. [Ryerson University, 350 Victoria Street, Toronto, ON, Canada M5B 2K3 (Canada)

    2012-10-15

    Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damaged concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.

  13. The distribution of phosphorus in Popes Creek, VA, and in the Pocomoke River, MD: Two watersheds with different land management practices in the Chesapeake Bay Basin

    Science.gov (United States)

    Simon, N.S.; Bricker, O.P.; Newell, W.; McCoy, J.; Morawe, R.

    2005-01-01

    This paper compares phosphorus (P) concentrations in sediments from two watersheds, one with, and one without, intensive animal agriculture. The watersheds are in the coastal plain of the Chesapeake Bay and have similar physiographic characteristics. Agriculture in the Pocomoke River, MD, watershed supplied 2.7 percent of all broiler chickens produced in the USA in 1997. Poultry litter is an abundant, local source of manure for crops. Broiler chickens are not produced in the Popes Creek, VA, watershed and poultry manure is, therefore, not a major source of fertilizer. The largest concentrations of P in sediment samples are found in floodplain and main-stem bottom sediment in both watersheds. Concentrations of total P and P extracted with 1N HCl are significantly larger in main-stem bottom sediments from the Pocomoke River than in main-stem bottom sediments from Popes Creek. Larger concentrations of P are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Pocomoke River watershed than are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Popes Creek watershed. Data for P and iron (Fe) concentrations in sediments from the Popes Creek watershed provide a numerical framework (baseline) with which to compare P and Fe concentrations in sediment from the Pocomoke River watershed. ?? Springer 2005.

  14. Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

    Science.gov (United States)

    Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

    2009-01-01

    Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.

  15. Enhancing the natural removal of As in a reactive fluvial confluence receiving acid drainage

    Science.gov (United States)

    Abarca, M. I.; Arce, G.; Montecinos, M.; Guerra, P. A.; Pasten, P.

    2014-12-01

    Fluvial confluences are natural reactors that can determine the fate of contaminants in watersheds receiving acid drainage. Hydrological, hydrodynamic and chemical factors determine distinct conditions for the formation of suspended particles of iron and aluminum oxyhydroxides. The chemical and physical properties of these particle assemblages (e.g. particle size, chemical composition) can vary according to inflow mixing ratios, hydrodynamic velocity profiles, and chemical composition of the flows mixing at the confluence. Due to their capacity to sorb metals, it is important to identify the optimal conditions for removing metals from the aqueous phase, particularly arsenic, a contaminant frequently found in acid drainage. We studied a river confluence in the Lluta watershed, located in the arid Chilean Altiplano. We performed field measurements and laboratory studies to find optimal mixing ratio for arsenic sorption onto oxyhydroxide particles at the confluence between the Azufre (pH=2, As=2 mg/L) and the Caracarani river (pH=8, Ascontaminants. An analogy between confluences and coagulation-flocculation-sedimentation drinking water plants could be used to engineer such intervention.Acknowledgements: Proyecto Fondecyt 1130936 and Proyecto CONICYT FONDAP 15110020

  16. Enhanced As (V Removal from Aqueous Solution by Biochar Prepared from Iron-Impregnated Corn Straw

    Directory of Open Access Journals (Sweden)

    Jiaming Fan

    2018-01-01

    Full Text Available Fe-loaded adsorbents have received increasing attention for the removal of arsenic in contaminated water or soil. In this study, Fe-loaded biochar was prepared from iron-impregnated corn straw under a pyrolysis temperature of 600°C. The ratio of crystalline Fe oxides including magnetite and natrojarosite to amorphous iron oxyhydroxide in the composite was approximately 2 : 3. Consisting of 24.17% Fe and 27.76% O, the composite exhibited a high adsorption capacity of 14.77 mg g−1 despite low surface areas (4.81 m2 g−1. The pH range of 2.0–8.0 was optimal for arsenate removal and the adsorption process followed the Langmuir isotherms closely. In addition, pseudo-second-order kinetics best fit the As removal data. Fe oxide constituted a major As-adsorbing sink. Based on the X-ray diffraction spectra, saturation indices, and selective chemical extraction, the data suggested three main mechanisms for arsenate removal: sorption of arsenate, strong inner-sphere surface complexes with amorphous iron oxyhydroxide, and partial occlusion of arsenate into the crystalline Fe oxides or carbonized phase. The results indicated that the application of biochar prepared from iron-impregnated corn straw can be an efficient method for the remediation of arsenic contaminated water or soil.

  17. Synthesis, Structural Characterization, and Thermal Properties of the Poly(methylmethacrylate/δ-FeOOH Hybrid Material: An Experimental and Theoretical Study

    Directory of Open Access Journals (Sweden)

    Silviana Corrêa

    2016-01-01

    Full Text Available The δ-FeOOH/PMMA nanocomposites with 0.5 and 2.5 wt.% of δ-FeOOH were prepared by grafting 3-(trimethoxysilylpropyl methacrylate on the surface of the iron oxyhydroxide particles. The FTIR spectra of the δ-FeOOH/PMMA nanocomposites showed that the silane monomers were covalently attached to the δ-FeOOH particles. Because of the strong interaction between the PMMA and δ-FeOOH nanoparticles, the thermal stability of the δ-FeOOH/PMMA nanocomposites was improved compared to the pure PMMA. The SEM analysis conferred the size agglomerate of particles regarding the morphology of samples. The theoretical study enabled a better understanding of the interaction of the polymer with the iron oxyhydroxide. The DFT-based calculations reinforce the radical trapping mechanism of stabilization of nanocomposites; that is, Fe3+ species might be able to accept electrons coming from the organic phase that decomposes via radical unzipping. The radical scavenge effect delays the weight loss of polymer.

  18. Improved virus removal in ceramic depth filters modified with MgO.

    Science.gov (United States)

    Michen, Benjamin; Fritsch, Johannes; Aneziris, Christos; Graule, Thomas

    2013-02-05

    Ceramic filters, working on the depth filtration principle, are known to improve drinking water quality by removing human pathogenic microorganisms from contaminated water. However, these microfilters show no sufficient barrier for viruses having diameters down to 20 nm. Recently, it was shown that the addition of positively charged materials, for example, iron oxyhydroxide, can improve virus removal by adsorption mechanisms. In this work, we modified a common ceramic filter based on diatomaceous earth by introducing a novel virus adsorbent material, magnesium oxyhydroxide, into the filter matrix. Such filters showed an improved removal of about 4-log in regard to bacteriophages MS2 and PhiX174. This is explained with the electrostatic enhanced adsorption approach that is the favorable adsorption of negatively charged viruses onto positively charged patches in an otherwise negatively charged filter matrix. Furthermore, we provide theoretical evidence applying calculations according to Derjaguin-Landau-Verwey-Overbeek theory to strengthen our experimental results. However, modified filters showed a significant variance in virus removal efficiency over the course of long-term filtration experiments with virus removal increasing with filter operation time (or filter aging). This is explained by transformational changes of MgO in the filter upon contact with water. It also demonstrates that filter history is of great concern when filters working on the adsorption principles are evaluated in regard to their retention performance as their surface characteristics may alter with use.

  19. Evidence of synsedimentary microbial activity and iron deposition in ferruginous crusts of the Late Cenomanian Utrillas Formation (Iberian Basin, central Spain)

    Science.gov (United States)

    García-Hidalgo, José F.; Elorza, Javier; Gil-Gil, Javier; Herrero, José M.; Segura, Manuel

    2018-02-01

    Ferruginous sandstones and crusts are prominent sedimentary features throughout the continental (braided)-coastal siliciclastic (estuarine-tidal) wedges of the Late Cenomanian Utrillas Formation in the Iberian Basin. Crust types recognized are: Ferruginous sandy crusts (Fsc) with oxides-oxyhydroxides (hematite and goethite) concentrated on sandstone tops presenting a fibro-radial internal structure reminding organic structures that penetrate different mineral phases, suggesting the existence of bacterial activity in crust development; Ferruginous muddy crusts (Fmc) consisting of wavy, laminated, microbial mats, being composed mainly of hematite. On the other hand, a more dispersed and broader mineralization included as Ferruginous sandstones with iron oxides and oxyhydroxides (hematite and goethite) representing a limited cement phase on these sediments. The presence of microbial remains, ferruginous minerals, Microbially-induced sedimentary structures, microbial laminites and vertebrate tracks preserved due to the presence of biofilms suggest firstly a direct evidence of syn-depositional microbial activity in these sediments; and, secondly, that iron accumulation and ferruginous crusts development occurred immediately after deposition of the host, still soft sediments. Ferruginous crusts cap sedimentary cycles and they represent the gradual development of hard substrate conditions, and the development of a discontinuity surface at the top of the parasequence sets, related to very low sedimentary rates; the overlying sediments record subsequent flooding of underlying shallower environments; crusts are, consequently, interpreted as boundaries for these higher-order cycles in the Iberian Basin.

  20. Fate of Cd during microbial Fe(III) mineral reduction by a novel and Cd-tolerant Geobacter species.

    Science.gov (United States)

    Muehe, E Marie; Obst, Martin; Hitchcock, Adam; Tyliszczak, Tolek; Behrens, Sebastian; Schröder, Christian; Byrne, James M; Michel, F Marc; Krämer, Ute; Kappler, Andreas

    2013-12-17

    Fe(III) (oxyhydr)oxides affect the mobility of contaminants in the environment by providing reactive surfaces for sorption. This includes the toxic metal cadmium (Cd), which prevails in agricultural soils and is taken up by crops. Fe(III)-reducing bacteria can mobilize such contaminants by Fe(III) mineral dissolution or immobilize them by sorption to or coprecipitation with secondary Fe minerals. To date, not much is known about the fate of Fe(III) mineral-associated Cd during microbial Fe(III) reduction. Here, we describe the isolation of a new Geobacter sp. strain Cd1 from a Cd-contaminated field site, where the strain accounts for 10(4) cells g(-1) dry soil. Strain Cd1 reduces the poorly crystalline Fe(III) oxyhydroxide ferrihydrite in the presence of at least up to 112 mg Cd L(-1). During initial microbial reduction of Cd-loaded ferrihydrite, sorbed Cd was mobilized. However, during continuous microbial Fe(III) reduction, Cd was immobilized by sorption to and/or coprecipitation within newly formed secondary minerals that contained Ca, Fe, and carbonate, implying the formation of an otavite-siderite-calcite (CdCO3-FeCO3-CaCO3) mixed mineral phase. Our data shows that microbially mediated turnover of Fe minerals affects the mobility of Cd in soils, potentially altering the dynamics of Cd uptake into food or phyto-remediating plants.

  1. Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

    International Nuclear Information System (INIS)

    Rodrigues, A.; Duchesne, J.; Fournier, B.; Durand, B.; Rivard, P.; Shehata, M.

    2012-01-01

    Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivières area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damaged concrete include “rust” mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH 2 O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.

  2. Photoemission study of metallic iron nanoparticles surface aging in biological fluids. Influence on biomolecules adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Canivet, L.; Denayer, F.O. [Université de Lille 2, Droit et Santé, 42 rue P. Duez, 59000 Lille (France); Champion, Y.; Cenedese, P. [CNRS-ICMPE, 2 rue H. Dunant, 94320 Thiais (France); Dubot, P., E-mail: pdubot@icmpe.cnrs.fr [CNRS-ICMPE, 2 rue H. Dunant, 94320 Thiais (France)

    2014-07-01

    Iron nanoparticles (nFe) prepared by vaporization and cryogenic condensation process (10–100 nm) has been exposed to Hank's balanced salt solution (HBSS) and the B-Ali cell growth fluids. These media can be used for cellular growth to study nFe penetration through cell membrane and its induced cytotoxicity. Surface chemistry of nFe exposed to such complex fluids has been characterized as the nanoparticles surface can be strongly changed by adsorption or corrosion processes before reaching intracellular medium. Particle size and surface chemistry have been characterized by scanning electron microscopy (SEM) and high-resolution X-ray photoelectron spectroscopy (HR-XPS). Exposition of nFe particles to growth and differentiation media leads to the formation of an oxy-hydroxide layer containing chlorinated species. We found that the passivated Fe{sub 2}O{sub 3} layer of the bare nFe particles is rapidly transformed into a thicker oxy-hydroxide layer that has a greater ability to adsorb molecular ions or ionic biomolecules like proteins or DNA.

  3. Insight into the cellular fate and toxicity of aluminium adjuvants used in clinically approved human vaccinations.

    Science.gov (United States)

    Mold, Matthew; Shardlow, Emma; Exley, Christopher

    2016-08-12

    Aluminium adjuvants remain the most widely used and effective adjuvants in vaccination and immunotherapy. Herein, the particle size distribution (PSD) of aluminium oxyhydroxide and aluminium hydroxyphosphate adjuvants was elucidated in attempt to correlate these properties with the biological responses observed post vaccination. Heightened solubility and potentially the generation of Al(3+) in the lysosomal environment were positively correlated with an increase in cell mortality in vitro, potentially generating a greater inflammatory response at the site of simulated injection. The cellular uptake of aluminium based adjuvants (ABAs) used in clinically approved vaccinations are compared to a commonly used experimental ABA, in an in vitro THP-1 cell model. Using lumogallion as a direct-fluorescent molecular probe for aluminium, complemented with transmission electron microscopy provides further insight into the morphology of internalised particulates, driven by the physicochemical variations of the ABAs investigated. We demonstrate that not all aluminium adjuvants are equal neither in terms of their physical properties nor their biological reactivity and potential toxicities both at the injection site and beyond. High loading of aluminium oxyhydroxide in the cytoplasm of THP-1 cells without immediate cytotoxicity might predispose this form of aluminium adjuvant to its subsequent transport throughout the body including access to the brain.

  4. Thermodynamics of gas-metal-slag equilibria for applications in in situ and ex situ vitrification melts

    International Nuclear Information System (INIS)

    Miller, R.L.; Reimann, G.A.

    1993-05-01

    An equilibrium thermodynamic model for melting mixed waste was evaluated using the STEPSOL computer code. STEPSOL uses free energy minimization techniques to predict equilibrium composition from input species and user selected species in the output. The model assumes equilibrium between gas, slag, and metallic phases. Input for the model was developed using compositional data from Pit 9 of the Subsurface Disposal Area at the Idaho National Engineering Laboratory. Thermodynamic data were primarily from compilations published by the US Government. The results of model evaluation indicate that the amount of plutonium chloride or plutonium oxyhydroxide that would be evaporated into the vapor phase would be minor. Relatively more uranium chloride and uranium oxyhydroxide would be vaporized. However, a hazards analysis was not part of the present task. Minor amounts of plutonium and uranium would be reduced to the metallic state, but these amounts should alloy with the iron-chromium-nickel metallic phase. The vast majority of the plutonium and uranium are in the slag phase as oxides. Results of the calculations show that silica and silicates dominate the products and that the system is very reducing. The major gases are carbon monoxide and hydrogen, with lesser amounts of carbon dioxide and water. High vapor pressure metals are considered but were not analyzed using STEPSOL. STEPSOL does not make predictions of distribution of species between phases

  5. Uranium geochemistry on the Amazon shelf: Evidence for uranium release from bottom sediments

    International Nuclear Information System (INIS)

    McKee, B.A.; DeMaster, D.J.; Nittrouer, C.A.

    1987-01-01

    In Amazon-shelf waters, as salinity increases to 36.5 x 10 -3 , dissolved uranium activities increase to a maximum of 4.60 dpm 1 -1 . This value is much higher than the open-ocean value (2.50 dpm 1 -1 ), indicating a source of dissolved uranium to shelf waters in addition to that supplied from open-ocean and riverine waters. Uranium activities are much lower for surface sediments in the Amazon-shelf sea bed (mean: 0.69 ± .09 dpm g -1 ) than for suspended sediments in the Amazon river (1.82 dpm g -1 ). Data suggest that the loss of particulate uranium from riverine sediments is probably the result of uranium desorption from the ferric-oxyhydroxide coatings on sediment particles, and/or uranium release by mobilization of the ferric oxyhydroxides. The total flux of dissolved 238 U from the Amazon shelf (about 1.2 x 10 15 dpm yr -1 ) constitutes about 15% of uranium input to the world ocean, commensurate to the Amazon River's contribution to world river-water discharge. Measurement of only the riverine flux of dissolved 238 U underestimates, by a factor of about 5, the flux of dissolved 238 U from the Amazon shelf to the open ocean

  6. Nutrient scavenging in Upper Bear Creek from mine wastes: The birth and death of a productive reservoir

    International Nuclear Information System (INIS)

    Isphording, W.C.

    1994-01-01

    In 1978 the Tennessee Valley Authority constructed a reservoir on Upper Bear Creek in northern Alabama for the purpose of flood control. Secondary objectives were to provide a recreational site and one that would also benefit the local economy. Prior to flooding of the stream valley, however, extensive coal mining activities were carried out and the waste materials from these operations were left adjacent to the area to be flooded. In spite of an ambitious fish stocking program, within two years the reservoir was found to be near sterile. Biologists attributed the demise of the fish (and flora) to a combination of high silt loads, high acidity, and heavy metal poisoning from adjacent mine tailings. A detailed investigation was recently funded to confirm the above conclusions. The results indicated that, while there was some evidence of heavy metal poisoning, none of the other presumed causes were important. The principal culprit, however, was simply a lack of the basic nutrient phosphorus in the lake waters. The cause of this was ultimately traced to the absorption of available phosphorus onto suspended particles of iron oxy-hydroxides. The oxy-hydroxides originated by breakdown of iron sulfides that were abundantly present in the mine tailings. It is therefore likely that this phenomenon occurs in many lakes, ponds, and reservoirs adjacent to abandoned coal mines and that acid mine drainage may be, in many cases, only one of several mitigating factors causing sterility and destruction of the aquatic habitat

  7. Microbial Diversity and Characteristics in Anaerobic Environments in KURT Groundwater

    International Nuclear Information System (INIS)

    Roh, Yul; Oh, Jong Min; Rhee, Sung Keun; Yong, Jong Joong

    2008-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxide, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  8. Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange

    Science.gov (United States)

    Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.

    2017-02-01

    Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.

  9. Microbial Diversity in KURT Groundwater and Biomineralization Characteristics

    International Nuclear Information System (INIS)

    Roh, Yul; Rhee, Sung Keun; Oh, Jong Min; Park, Byung Jun

    2009-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxides, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  10. Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohui [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Um, Wooyong [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Pohang University of Science and Technology (POSTECH), Pohang, South Korea; Wang, Zheming [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Reinoso-Maset, Estela [Sierra; Washton, Nancy M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Mueller, Karl T. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Perdrial, Nicolas [Department; Department; O’Day, Peggy A. [Sierra; Chorover, Jon [Department

    2017-09-21

    The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford’s cribs, USA. During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67E-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42E-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

  11. Arsenic mobility in groundwater/surface water systems in carbonate-rich Pleistocene glacial drift aquifers (Michigan)

    International Nuclear Information System (INIS)

    Szramek, Kathryn; Walter, Lynn M.; McCall, Patti

    2004-01-01

    Within the Lower Peninsula of Michigan, groundwaters from the Marshall Formation (Mississippian) contain As derived from As-rich pyrites, often exceeding the World Heath Organization drinking water limit of 10 μg/L. Many Michigan watersheds, established on top of Pleistocene glacial drift derived from erosion of the underlying Marshall Formation, also have waters with elevated As. The Huron River watershed in southeastern Lower Michigan is a well characterized hydrogeochemical system of glacial drift deposits, proximate to the Marshall Fm. subcrop, which hosts carbonate-rich groundwaters, streams, and wetlands (fens), and well-developed soil profiles. Aqueous and solid phase geochemistry was determined for soils, soil waters, surface waters (streams and fens) and groundwaters from glacial drift aquifers to better understand the hydrogeologic and chemical controls on As mobility. Soil profiles established on the glacial drift exhibit enrichment in both Fe and As in the oxyhydroxide-rich zone of accumulation. The amounts of Fe and As present as oxyhydroxides are comparable to those reported from bulk Marshall Fm. core samples by previous workers. However, the As host in core samples is largely unaltered pyrite and arsenopyrite. This suggests that the transformation of Fe sulfides to Fe oxyhydroxides largely retains As and Fe at the oxidative weathering site. Groundwaters have the highest As values of all the waters sampled, and many were at or above the World Health limit. Most groundwaters are anaerobic, within the zones of Fe 3+ and As(V) reduction. Although reduction of Fe(III) oxyhydroxides is the probable source of As, there is no correlation between As and Fe concentrations. The As/Fe mole ratios in drift groundwaters are about an order of magnitude greater than those in soil profiles, suggesting that As is more mobile than Fe. This is consistent with the dominance of As(III) in these groundwaters and with the partitioning of Fe 2+ into carbonate cements. Soil

  12. Investigations of the Structure of Titanate Nanoscrolls

    International Nuclear Information System (INIS)

    Sheppard, D.A.; Buckley, C.E.

    2005-01-01

    Full text: Nanosized materials have attracted much research lately due to their unique properties and their potential application in nanoelectronic and optoelectronic devices. Nanostructured materials have also sparked interest as possible hydrogen storage candidates. Research at Curtin University has shown titanate nanoscrolls to absorb modest amounts of hydrogen at low temperatures. Whether or not this capacity can be improved will be dependent on a thorough understanding of the structure and the way it interacts with hydrogen. Titanate nanoscrolls are made via a soft chemical process that involves ageing TiO 2 powder in a concentrated NaOH solution. The resultant nanoscrolls, once filtered and washed, are typically 8-10 nm in diameter and hundreds of nanometers long. The walls consist of 3-5 layers and the diameter of the hollow centre is typically 5 nm. A number of different structures have been assigned to nanoscrolls produced via the soft chemical process. These include anatase, H 2 Ti 3 O 7 , lepidocrocite-type structure and H 2 Ti 4 O 9 .H 2 O. Many of these structures are similar, consisting of titanate type layers, and qualitatively reproduce the X-ray diffraction data. However, preliminary data suggests that these structures are inconsistent with neutron diffraction data. Here we attempt a more quantitative analysis of the structure than those published previously using neutron and X-ray diffraction. (authors)

  13. Structure reconstruction of TiO2-based multi-wall nanotubes: first-principles calculations.

    Science.gov (United States)

    Bandura, A V; Evarestov, R A; Lukyanov, S I

    2014-07-28

    A new method of theoretical modelling of polyhedral single-walled nanotubes based on the consolidation of walls in the rolled-up multi-walled nanotubes is proposed. Molecular mechanics and ab initio quantum mechanics methods are applied to investigate the merging of walls in nanotubes constructed from the different phases of titania. The combination of two methods allows us to simulate the structures which are difficult to find only by ab initio calculations. For nanotube folding we have used (1) the 3-plane fluorite TiO2 layer; (2) the anatase (101) 6-plane layer; (3) the rutile (110) 6-plane layer; and (4) the 6-plane layer with lepidocrocite morphology. The symmetry of the resulting single-walled nanotubes is significantly lower than the symmetry of initial coaxial cylindrical double- or triple-walled nanotubes. These merged nanotubes acquire higher stability in comparison with the initial multi-walled nanotubes. The wall thickness of the merged nanotubes exceeds 1 nm and approaches the corresponding parameter of the experimental patterns. The present investigation demonstrates that the merged nanotubes can integrate the two different crystalline phases in one and the same wall structure.

  14. Klimt artwork (Part II): material investigation by backscattering Fe-57 Mössbauer- and Raman- spectroscopy, SEM and p-XRF

    Energy Technology Data Exchange (ETDEWEB)

    Costa, B. F. O. [University of Coimbra, CFisUC, Physics Department (Portugal); Lehmann, R.; Wengerowsky, D. [Leibniz Universität Hannover, Institut für Anorganische Chemie (Germany); Blumers, M. [Joh. Gutenberg-Universität Mainz, Institut für Anorganische Chemie und Analytische Chemie (Germany); Sansano, A.; Rull, F. [Unidad Asociada UVA-CSIC Centro de Astrobiologia (Spain); Schmidt, H.-J. [Leibniz Universität Hannover, Institut für Anorganische Chemie (Germany); Dencker, F. [Hochschule Hannover, Fakultät II-Maschinenbau und Bioverfahrenstechnik (Germany); Niebur, A. [Technische Universität Dresden, Institut für Physikalische Chemie (Germany); Klingelhöfer, G. [Joh. Gutenberg-Universität Mainz, Institut für Anorganische Chemie und Analytische Chemie (Germany); Sindelar, R. [Hochschule Hannover, Fakultät II-Maschinenbau und Bioverfahrenstechnik (Germany); Renz, F., E-mail: renz@acd.uni-hannover.de [Leibniz Universität Hannover, Institut für Anorganische Chemie (Germany)

    2016-12-15

    In a rediscovered Klimt-artwork “Trompetender Putto” material tests have been conducted. We report studies on different points of the painting. The spots are of different colors, mainly taken in spots of the painting not restaurated. MIMOS II Fe-57 Mössbauer spectroscopy revealed mainly haematite and nano particle oxides in red and red/brown colors. Brown colors also contain crystallized goethite. In brown/ochre colors the same pigments as in brown colors are observed, but there is less quantity of goethite and more quantity of haematite. The green colors show Fe-rich clays, like celadonite or glauconite and or lepidocrocite as main component. Raman spectroscopy revealed cinnabar in red colors of the Scarf; and massicot in brown/ochre points, i.e. in the Left Wing of the “Putto”. With scanning electron microscopy, various layers of the original and of overpainting could be recognized. The investigations of sample 1 show three layers of colored materials, which were identified as zinc-white, cinnabar and galena as well as carbon compounds. In sample 2 four layers could be detected. These are identified (bottom to top) as gypsum and lead-white (layer 1), zinc-white (layer 2), lead-white and cinnabar (layer 3) and titanium-white (layer 4). The elementary composition was examined with the portable X-ray-fluorescence analysis for qualitative manner at different points.

  15. Analysis of corrosion products of carbon steel in wet bentonite

    International Nuclear Information System (INIS)

    Osada, Kazuo; Nagano, Tetsushi; Nakayama, Shinichi; Muraoka, Susumu

    1992-02-01

    As a part of evaluation of the long-term durability for the overpack containers for high-level radioactive waste, we have conducted corrosion tests for carbon steel in wet bentonite, a candidate buffer material. The corrosion rates were evaluated by weight difference of carbon steel and corrosion products were analyzed by Fourier transform infrared spectroscopy (FT-IR) and colorimetry. At 40degC, the corrosion rate of carbon steel in wet bentonite was smaller than that in pure water. At 95degC, however, the corrosion rate in wet bentonite was much higher than that in pure water. This high corrosion rate in wet bentonite at 95degC was considered to result from evaporation of moisture in bentonite in contact with the metal. This evaporation led to dryness and then to shrinkage of the bentonite, which generated ununiform contact of the metal with bentonite. Probably, this ununiform contact promoted the local corrosion. The locally corroded parts of specimen in wet bentonite at 95degC were analyzed by Fourier transform infrared microspectroscopy (micro-FT-IR), and lepidocrocite γ-FeO(OH) was found as well as goethite α-FeO(OH). In wet bentonite at 95degC, hematite α-Fe 2 O 3 was identified by means of colorimetry. (author)

  16. Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments

    Science.gov (United States)

    Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng

    2017-12-01

    Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.

  17. Interplay between black carbon and minerals contributes to long term carbon stabilization and mineral transformation

    Science.gov (United States)

    Liang, B.; Weng, Y. T.; Wang, C. C.; Chiang, C. C.; Liu, C. C.; Lehmann, J.

    2017-12-01

    Black carbon receives increasing global wide research attention due to its role in carbon sequestration, soil fertility enhancement and remediation application. Generally considered chemically stable in bulk, the reactive surface of BC can interplays with minerals and form strong chemical bondage, which renders physical protection of BC and contributes to its long term stabilization. Using historical BC-rich Amazonian Dark Earth (ADE), we probe the in-situ organo-mineral association and transformation of BC and minerals over a millennium scale using various synchrotron-based spectroscopic (XANES, FTIR) and microscopic (TXM) methods. Higher content of SRO minerals was found in BC-rich ADE compare to adjacent tropical soils. The iron signature found in BC-rich ADE was mainly ferrihydrite/lepidocrocite, a more reactive form of Fe compared to goethite, which was dominant in adjacent soil. Abundant nano minerals particles were observed in-situ associated with BC surface, in clusters and layers. The organo-mineral interaction lowers BC bioavailability and enhances its long-term stabilization in environment, while at the same time, transforms associated minerals into more reactive forms under rapid redox/weathering environment. The results suggest that mineral physical protection for BC sequestration may be more important than previous understanding. The scale up application of BC/biochar into agricultural systems and natural environments have long lasting impact on the in-situ transformation of associated minerals.

  18. Nature and Properties of Lateritic Soils Derived from Different Parent Materials in Taiwan

    Directory of Open Access Journals (Sweden)

    Tzu-Hsing Ko

    2014-01-01

    Full Text Available The objective of this study was to investigate the physical, chemical, and mineralogical composition of lateritic soils in order to use these soils as potential commercial products for industrial application in the future. Five lateritic soils derived from various parent materials in Taiwan, including andesite, diluvium, shale stone, basalt, and Pleistocene deposit, were collected from the Bt1 level of soil samples. Based on the analyses, the Tungwei soil is an alfisol, whereas other lateritic soils are ultisol. Higher pH value of Tungwei is attributed to the large amounts of Ca2+ and Mg2+. Loupi and Pingchen soils would be the older lateritic soils because of the lower active iron ratio. For the iron minerals, the magnetic iron oxides such as major amounts of magnetite and maghemite were found for Tamshui and Tungwei lateritic soils, respectively. Lepidocrocite was only found in Soka soil and intermediate amounts of goethite were detected for Loupi and Pingchen soils. After Mg-saturated and K-saturated processes, major amounts of mixed layer were observed in Loupi and Soka soils, whereas the montmorillonite was only detected in Tungwei soil. The investigation results revealed that the parent materials would play an important role during soil weathering process and physical, chemical, and mineralogy compositions strongly affect the formation of lateritic soils.

  19. Nature and Properties of Lateritic Soils Derived from Different Parent Materials in Taiwan

    Science.gov (United States)

    2014-01-01

    The objective of this study was to investigate the physical, chemical, and mineralogical composition of lateritic soils in order to use these soils as potential commercial products for industrial application in the future. Five lateritic soils derived from various parent materials in Taiwan, including andesite, diluvium, shale stone, basalt, and Pleistocene deposit, were collected from the Bt1 level of soil samples. Based on the analyses, the Tungwei soil is an alfisol, whereas other lateritic soils are ultisol. Higher pH value of Tungwei is attributed to the large amounts of Ca2+ and Mg2+. Loupi and Pingchen soils would be the older lateritic soils because of the lower active iron ratio. For the iron minerals, the magnetic iron oxides such as major amounts of magnetite and maghemite were found for Tamshui and Tungwei lateritic soils, respectively. Lepidocrocite was only found in Soka soil and intermediate amounts of goethite were detected for Loupi and Pingchen soils. After Mg-saturated and K-saturated processes, major amounts of mixed layer were observed in Loupi and Soka soils, whereas the montmorillonite was only detected in Tungwei soil. The investigation results revealed that the parent materials would play an important role during soil weathering process and physical, chemical, and mineralogy compositions strongly affect the formation of lateritic soils. PMID:24883366

  20. Comparison of color, chemical and mineralogical compositions of mine drainage sediments to pigment

    Energy Technology Data Exchange (ETDEWEB)

    Kirby, C.S. [Bucknell Univ., Lewisburg, PA (United States). Geology Dept.; Decker, S.M. [Boston College, MA (United States). Dept. of Geology and Geophysics; Macander, N.K. [Parsons Engineering Science, Fairfax, VA (United States)

    1999-03-01

    Forty-three untreated and actively and passively (wetland) treated coal mine drainage sediments and five yellow-red pigments were characterized using X-ray fluorescence, fusion-inductively coupled plasma atomic emission spectroscopy, X-ray diffraction, and tristimulus colorimeter. Primary crystalline iron-bearing phases were goethite and lepidocrocite, and iron phases converted to hematite upon heating. Quartz was nearly ubiquitous except for synthetic pigments. Gypsum, bassinite, calcite, and ettringite were found in active treatment sediments. Iron concentrations from highest to lowest were synthetic pigment>wetland sediment>natural pigment>active treatment (untreated sediments varied more widely), and manganese was highest in actively treated sediments. Loss on ignition was highest for passively treated sediments. No clear trends were observed between quantified color parameters (L*, a*, b*, and Redness Index) and chemical compositions. Because sediments from passive treatment are similar in chemistry, mineralogy, and color to natural pigments, the mine drainage sediments may be an untrapped resource for pigment. (orig.)

  1. Analysis of corrosion products of carbon steel in wet bentonite

    International Nuclear Information System (INIS)

    Osada, K.; Nagano, T.; Kozai, N.; Nakashima, S.; Nakayama, S.; Muraoka, S.

    1991-01-01

    The following conclusions were obtained; (1) At 40degC, the average corrosion rate of SS41 carbon steel in wet bentonite was 0.025 mm/y. This is smaller than the value of 0.042 mm/y obtained in pure water at 40degC. However, at 95degC, the corrosion rate of SS41 carbon steel in wet bentonite was 0.27 mm/y, which is much larger than that in pure water at 95degC. (2) At 95degC, γ-FeO(OH) (lepidocrocite) was formed only in wet bentonite, and it was absent in pure water. Evaporation of moisture resulted in the formation of partial covering of bentonite, which promoted local corrosion. Consequently, γ-FeO(OH) was considered to be formed. (3) In wet bentonite at 95degC, α-Fe 2 O 3 (hematite) can be identified by means of colorimetry. The color of corrosion products is orangish, indicating the contribution of α-Fe 2 O 3 in iron hydroxides. (author)

  2. Degradation of bis- p -nitrophenyl phosphate using zero-valent iron nanoparticles

    International Nuclear Information System (INIS)

    Valle-Orta, Maiby; Guerrero, Rubén Saldivar; Díaz, David; Dubé, Inti Zumeta; Quiñonez, José Luis Ortiz

    2017-01-01

    Phosphate esters are employed in some agrochemical formulations and have long life time in the Environment. They are neurotoxic to mammals and it is very difficult to hydrolyze them. It is easy to find papers in the literature dealing with transition metal complexes used in the hydrolysis processes of organophosphorous compounds. However, there are few reports related with degradation of phosphate esters with inorganic nanoparticles. In this work bis-4-nitrophenyl phosphate (BNPP) was used as an agrochemical agent model. The BNPP interaction with zero-valent iron nanoparticles (ZVI NPs), in aqueous media, was searched. The concentration of BNPP was 1000 times higher than the ZVI NPs concentration. The average size of the used iron nanoparticles was 10.2 ± 3.2 nm. The BNPP degradation process was monitored by means of UV-visible method. Initially, the BNPP hydrolysis happens through the P-O bonds breaking-off under the action of the ZVI NPs. Subsequently, the nitro groups were reduced to amine groups. The overall process takes place in 10 minutes. The reaction products were identified employing standard substances in adequate concentrations. The iron by-products were isolated and characterized by X-RD. These iron derivatives were identified as magnetite (Fe 3 O 4 ) and/or maghemite (γ-Fe 2 O 3 ) and lepidocrocite (γ-FeOOH). A suggested BNPP degradation mechanism will be discussed. (paper)

  3. Field sludge characterization obtained from inner of pipelines

    Energy Technology Data Exchange (ETDEWEB)

    Nava, N.; Sosa, E.; Alamilla, J.L. [Instituto Mexicano del Petroleo, Programa de Integridad de Ductos, Eje Central Lazaro Cardenas Norte 152, San Bartolo Atepehuacan, C.P. 07730 (Mexico); Knigth, C. [PEMEX Refinacion, Avenida Marina Nacional 329, Edificio B-2, Piso 11, C.P. 11311 (Mexico); Contreras, A. [Instituto Mexicano del Petroleo, Programa de Integridad de Ductos, Eje Central Lazaro Cardenas Norte 152, San Bartolo Atepehuacan, C.P. 07730 (Mexico)], E-mail: acontrer@imp.mx

    2009-11-15

    Physicochemical characterization of sludge obtained from refined hydrocarbons transmission pipeline was carried out through Moessbauer spectroscopy and X-ray diffraction. The Moessbauer and X-ray patterns indicate the presence of corrosion products composed of different iron oxide and sulfide phases. Hematite ({alpha}-Fe{sub 2}O{sub 3}), magnetite (Fe{sub 3}O{sub 4}), maghemite ({gamma}-Fe{sub 2}O{sub 3}), magnetic and superparamagnetic goethite ({alpha}-FeOOH), pyrrhotite (Fe{sub 1-x}S), akaganeite ({beta}-FeOOH), and lepidocrocite ({gamma}-FeOOH) were identified as corrosion products in samples obtained from pipeline transporting Magna and Premium gasoline. For diesel transmission pipeline, hematite, magnetite, and magnetic goethite were identified. Corrosion products follow a simple reaction mechanism of steel dissolution in aerated aqueous media at a near-neutral pH. Chemical composition of the corrosion products depends on H{sub 2}O and sulfur inherent in fluids (traces). These results can be useful for decision-making with regard to pipeline corrosion control.

  4. Effects of blending of desalinated and conventionally treated surface water on iron corrosion and its release from corroding surfaces and pre-existing scales.

    Science.gov (United States)

    Liu, Haizhou; Schonberger, Kenneth D; Peng, Ching-Yu; Ferguson, John F; Desormeaux, Erik; Meyerhofer, Paul; Luckenbach, Heidi; Korshin, Gregory V

    2013-07-01

    This study examined effects of blending desalinated water with conventionally treated surface water on iron corrosion and release from corroding metal surfaces and pre-existing scales exposed to waters having varying fractions of desalinated water, alkalinities, pH values and orthophosphate levels. The presence of desalinated water resulted in markedly decreased 0.45 μm-filtered soluble iron concentrations. However, higher fractions of desalinated water in the blends were also associated with more fragile corroding surfaces, lower retention of iron oxidation products and release of larger iron particles in the bulk water. SEM, XRD and XANES data showed that in surface water, a dense layer of amorphous ferrihydrite phase predominated in the corrosion products. More crystalline surface phases developed in the presence of desalinated water. These solid phases transformed from goethite to lepidocrocite with increased fraction of desalinated water. These effects are likely to result from a combination of chemical parameters, notably variations of the concentrations of natural organic matter, calcium, chloride and sulfate when desalinated and conventionally treated waters are blended. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Corrosion products of reinforcement in concrete in marine and industrial environments

    International Nuclear Information System (INIS)

    Vera, R.; Villarroel, M.; Carvajal, A.M.; Vera, E.; Ortiz, C.

    2009-01-01

    The corrosion products formed on embedded steel in concrete under simulated marine and industrial conditions and natural marine environment were studied. A 0.50 water/cement ratio concrete was used and 3.5% NaCl and 180 g L -1 of H 2 SO 4 with 70 ppm of chloride ions solutions were used to simulate the synthetic medium. The initial electrochemical variables of the steel and pH, chlorides and sulfates profiles were measured according to the concrete depth. The morphology of the corrosive attack was determined via scanning electron microscopy (SEM), and the composition of the corrosion products was determined using an X-ray analyzer and an X-ray diffractometer (XRD). The protective power of the corrosion products was evaluated through anodic polarization curves in a saturated Ca(OH) 2 solution. The results from XRD and SEM show that all the resulting corrosion products correspond to lepidocrocite, goethite and magnetite mixtures; moreover, akaganeite was also identified under natural and simulated marine environments. Siderite was only detected in samples exposed to a natural marine environment. Concerning the protective nature of the corrosion products, these show lower performance in a simulated industrial environment, where the corrosion rate of the steel is up to 1.48 μm year -1

  6. Corrosion study of steels exposed over five years to the humid tropical atmosphere of Panama

    Energy Technology Data Exchange (ETDEWEB)

    Jaén, Juan A., E-mail: juan.jaen@up.ac.pa [Departamento de Química Física, Edificio de Laboratorios Científicos-VIP (Panama); Iglesias, Josefina [Laboratorio de Análisis Industriales y Ciencias Ambientales (Panama)

    2017-11-15

    The results of assessing five-year corrosion of low-carbon and conventional weathering steels exposed to the Panamanian tropical atmosphere is presented. Two different test sites, one in Panama City: 5 km from the shoreline of the Pacific Ocean, and another in the marine environment of Fort Sherman, Caribbean coast of Panama; namely, Fort Sherman Coastal site: 100 m from coastline. The corrosion products, formed in the skyward and earthward faces in the studied tropical environment, were mainly identified using room temperature and low temperature (15 K) Mössbauer spectroscopy, and ATR-FTIR. In all samples, lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) were the main constituents. Some maghemite (γ-Fe{sub 2}O{sub 3}), was also identified in Tocumen by Mössbauer spectroscopy and traces of feroxyhyte (δ-FeOOH) using ATR-FTIR. The corrosion rate values obtained are discussed in light of the atmospheric exposure conditions and atmospheric pollutants.

  7. Corrosion Inhibition of Cold-rolled Low Carbon Steel with Pulse Fiber Laser Ablation in Water

    Science.gov (United States)

    Chan, Sze Ney; Wong, Wai Yin; Walvekar, Rashmi; Kadhum, Abdul Amir H.; Khalid, Mohammad; Lim, Kean Long

    2018-04-01

    This study aims at the use of a fiber laser for modifying the surface properties of cold-rolled low carbon steel via a pulse laser ablation technique in water. The effect on the corrosion behavior of the fiber laser-treated metal surface was investigated in NaCl and HCl environments. Electrochemical tests showed significant improvement in the corrosion resistance of the laser-treated sample in NaCl, with an increase in open-circuit potential (OCP) from - 0.65 to - 0.60 V and an inhibition efficiency of 89.22% as obtained from the impedance study. Such improvement was less significant in an acidic environment. Lower corrosion rates of 20.9 mpy and 5.819 × 103 mpy were obtained for the laser-treated samples in neutral and acidic electrolytes, respectively, than the corrosion rates obtained for the as-received samples (33.2 mpy and 11.98 × 103 mpy). Morphological analysis indicated a passive film built by spherical grains of regular size on the metal surface after laser treatment. The corrosion inhibition effects in NaCl were evident by the nonexistence of the common corrosion products of lepidocrocite and crystalline structures that were seen on as-received samples; only polyhedral crystals with micrograins grown on them were seen covering the laser-treated surface. Therefore, the laser treatment using a fiber laser source improved the corrosion resistance of cold-rolled low carbon steel.

  8. Mechanical Properties of K Basin Sludge Constituents and Their Surrogates

    International Nuclear Information System (INIS)

    Delegard, Calvin H.; Schmidt, Andrew J.; Chenault, Jeffrey W.

    2004-01-01

    A survey of the technical literature was performed to summarize the mechanical properties of inorganic components in K Basins sludge. The components included gibbsite, ferrihydrite, lepidocrocite and goethite, hematite, quartz, anorthite, calcite, basalt, Zircaloy, aluminum, and, in particular, irradiated uranium metal and uranium dioxide. Review of the technical literature showed that information on the hardness of uranium metal at irradiation exposures similar to those experienced by the N Reactor fuel present in the K Basins (typically up to 3000 MWd/t) were not available. Measurements therefore were performed to determine the hardness of coupons taken from three irradiated N Reactor uranium metal fuel elements taken from K Basins. Hardness values averaged 30 ± 8 Rockwell C units, similar to values previously reported for uranium irradiated to ∼1200 MWd/t. The physical properties of candidate uranium metal and uranium dioxide surrogates were gathered and compared. Surrogates having properties closest to those of irradiated uranium metal appear to be alloys of tungsten. The surrogate for uranium dioxide, present both as particles and agglomerates in actual K Basin sludge, likely requires two materials. Cerium oxide, CeO2, was identified as a surrogate of the smaller UO2 particles while steel grit was identified for the UO2 agglomerates

  9. Effects of Si as alloying element on corrosion resistance of weathering steel

    International Nuclear Information System (INIS)

    Mejía Gómez, J.A.; Antonissen, J.; Palacio, C.A.; De Grave, E.

    2012-01-01

    Highlights: ► Weathering steels with different concentrations of Si as alloying element were exposed to laboratory atmospheric conditions. ► The iron oxides formed as corrosion products were characterized and analyzed by XRD, TEM and Mössbauer spectroscopy. ► Silicon affects the corrosion resistance of weathering steels. ► Silicon promotes the formation of goethite as corrosion product with small particle size. - Abstract: The corrosion resistance in saline conditions of weathering steel with different concentrations of Si (1, 2 and 3 wt.%) exposed to dip dry tests (simulating wet/dry cycles of atmospheric corrosion) was studied by weight loss, X-ray diffraction, Mössbauer spectroscopy and transmission electron microscopy. The results showed that the steels exhibit better corrosion performance with increasing Si concentration. The formation of Fe-oxides such as goethite, lepidocrocite and magnetite was observed. Superparamagnetic goethite is the dominant phase in the rust developed on the Si steels, indicating that Si favors the formation of goethite with small particle size.

  10. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    Science.gov (United States)

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

  11. The use of SEM/EDS method in mineralogical analysis of ordinary chondritic meteorite

    Directory of Open Access Journals (Sweden)

    Breda Mirtič

    2009-12-01

    Full Text Available The aim of this study was to evaluate the potential of scanning electron microscopy coupled with energy dispersiveX-ray spectroscopy (SEM/EDS for determination of mineral phases according to their stoichiometry and assessment of mineral composition of ordinary chondritic meteorite. For the purposes of this study, H3 type ordinary chondritic meteorite Abbott was selected. SEM/EDS allows identification and characterisation of mineralphases, whose size is below the resolution of an optical microscope. Mineral phases in chondrules and interstitial matrix were located in backscattered electron (BSE mode and were assessed from atomic proportions of constituent elements, obtained by the EDS analysis. SEM/EDS analyses of mineral phases showed that Abbott meteorite is characterised by Fe-rich (Fe, Ni-alloy kamacite, Fe-sulphide troilite or pyrrhotite, chromite, Mg-rich olivine, orthopyroxene bronzite or hypersthene, clinopyroxene Al-diopside, acid plagioclase oligoclase, accessory mineral chlorapatite and secondary minerals Fe-hydroxides (goethite or lepidocrocite. Results of semi-quantitative analyses confirmed that most of analysed mineralphases conform well to stoichiometric minerals with minor deviations of oxygen from stoichiometric proportions. Comparison between mineral phases in chondrules and interstitial matrix was also performed, however it showed no significant differences in elemental composition.Differences in chemical composition between minerals in interstitial matrix and chondrules are sometimes too small to be discernedby the SEM/EDS, therefore knowledge of SEM/EDS capabilities is important for correct interpretation of chondrite formation.

  12. Corrosion products of reinforcement in concrete in marine and industrial environments

    Energy Technology Data Exchange (ETDEWEB)

    Vera, R. [Instituto de Quimica, Facultad de Ciencias, Pontificia Universidad Catolica de Valparaiso, Avenida Brasil 2950, Casilla 4059, Valparaiso (Chile)], E-mail: rvera@ucv.cl; Villarroel, M. [Instituto de Quimica, Facultad de Ciencias, Pontificia Universidad Catolica de Valparaiso, Avenida Brasil 2950, Casilla 4059, Valparaiso (Chile); Carvajal, A.M. [Facultad de Ingenieria, Escuela de Construccion Civil, Pontificia Universidad Catolica de Chile, Av. Vicuna Mackenna 4860, Macul, Santiago (Chile); Vera, E.; Ortiz, C. [Universidad Pedagogica y Tecnologica de Colombia, Avenida Central Norte, Km 2, Tunja (Colombia)

    2009-03-15

    The corrosion products formed on embedded steel in concrete under simulated marine and industrial conditions and natural marine environment were studied. A 0.50 water/cement ratio concrete was used and 3.5% NaCl and 180 g L{sup -1} of H{sub 2}SO{sub 4} with 70 ppm of chloride ions solutions were used to simulate the synthetic medium. The initial electrochemical variables of the steel and pH, chlorides and sulfates profiles were measured according to the concrete depth. The morphology of the corrosive attack was determined via scanning electron microscopy (SEM), and the composition of the corrosion products was determined using an X-ray analyzer and an X-ray diffractometer (XRD). The protective power of the corrosion products was evaluated through anodic polarization curves in a saturated Ca(OH){sub 2} solution. The results from XRD and SEM show that all the resulting corrosion products correspond to lepidocrocite, goethite and magnetite mixtures; moreover, akaganeite was also identified under natural and simulated marine environments. Siderite was only detected in samples exposed to a natural marine environment. Concerning the protective nature of the corrosion products, these show lower performance in a simulated industrial environment, where the corrosion rate of the steel is up to 1.48 {mu}m year{sup -1}.

  13. Mineralogy and geochemistry of clayey dump materials from Troyanovo-2 mine, East Maritza Basin (Bulgaria)

    International Nuclear Information System (INIS)

    Milakovska, Z.; Goettlicher, J.; Gasharova, B.; Pohlmann-Lortz, M.

    2005-01-01

    Eleven samples of macroscopic different types of surface dump materials (black, gray-green and ochreous clays and clay mixtures) which were heaped during different stages of open-pit coal mining were studied. Montmorillonite ((Na,Ca) 0.33 (Al,Mg) 2 Si 4 O 10 (OH) 2 ), illite (K(Al, Mg, Fe) 2 AlSi 3 O 10 (OH) 2 ), calcite (CaCO 3 ), halloysite (Al 2 Si 2 O 5 (OH) 4 ), and less frequently kaolinite (Si 4 Al 4 O 10 (OH) 8 ) and quartz (SiO 2 ) are the main primary minerals identified. Primary sulfide minerals determined are pyrite (FeS 2 ) (detected in three samples) and arsenopyrite (FeAsS) - in two samples. Gypsum (CaSO 4 x2H 2 O) is the most widespread secondary mineral followed by goethite (FeOOH) and hematite (Fe 2 O 3 ). Na-rich jarosite (ideal: NaFe 3 (SO 4 ) 2 (OH) 6 ) was identified in two samples, lepidocrocite (γ-FeOOH) - only in one. One sample is free of secondary minerals. The mineralogical study shows that oxidation processes of the surface dump materials are not finished yet and pyrite is still present in samples stored 20 years ago. Main factors contributing to the slow rate of oxidation process are clay minerals, low sulfide content (prerequisite for a low oxidation potential), and calcite that contributes to the acidity neutralising potential of the clayey materials. (authors)

  14. Enhanced Cr(VI) removal from groundwater by Fe0-H2O system with bio-amended iron corrosion

    DEFF Research Database (Denmark)

    Yin, Weizhao; Li, Yongtao; Wu, Jinhua

    2017-01-01

    Abstract A one-pot bio-iron system was established to investigate synergetic abiotic and biotic effects between iron and microorganisms on Cr(VI) removal. More diverse iron corrosion and reactive solids, such as green rusts, lepidocrocite and magnetite were found in the bio-iron system than...... transfer on the solid phase. The results also showed that the reduction of Cr(VI) by microorganisms was insignificant, indicating the adsorption/co-precipitation of Cr by iron oxides on iron surface was responsible for the overall Cr(VI) removal. Our study demonstrated that the bio-amended iron corrosion...... in the Fe0-H2O system, leading to 4.3 times higher Cr(VI) removal efficiency in the bio-iron system than in the Fe0-H2O system. The cycling experiment also showed that the Cr(VI) removal capacity of Fe0 in the bio-iron system was 12.4 times higher than that in the Fe0-H2O system. A 62 days of life...

  15. The nature of rusts and corrosion characteristics of low alloy and plain carbon steels in three kinds of concrete pore solution with salinity and different pH

    International Nuclear Information System (INIS)

    Singh, J.K.; Singh, D.D.N.

    2012-01-01

    Highlights: ► LAS rebars corrode 2–3 times slower than PCS in concrete pore solution and mortars. ► Raman and XRD studies show that goethite and maghemite phases of rusts formed on LAS. ► On PCS unstable phases of lepidocrocite and akaganite are formed. ► EIS confirms more stable rust on LAS than on PCS. ► A model is proposed to explain formation of passive film on surface of steels. - Abstract: Correlation of corrosion characteristics and nature of rusts on low alloy (LA) and plain carbon (PC) steels exposed in simulated concrete pore solution of different pH is studied. Rusts formed under wet/dry conditions are examined by Raman spectroscopy and X-ray diffraction. LA rust is more adherent compared to PC as confirmed by measurement of weight in gain and electrochemical studies. EIS results show improvement in protective properties of steels with passage of time. Both steels are found prone to pitting attack in chloride contaminated pore solution. Rebars embedded in concrete exhibit same trend as recorded in solution exposure tests.

  16. Interruption with the Migration of Iodide by GR(CT)

    International Nuclear Information System (INIS)

    Min, J. H.; Lee, J. K.; Jeong, J. T.

    2012-01-01

    The purpose of this study is to understand the influence of green rust on the migration of iodide. GR(CT) would be major corrosion product of iron near the seawater or saline layer in underground. The GR(CT) may play an important role in the retardation of the iodide migration in a deep geological environment due to it's anionic exchange reaction. In underground radioactive waste repository, the corrosion of iron canisters would be proceed as follows; Fe(II) and/or Fe(III) dissolved from iron containers → Fe(II)(OH) 2 and/or Fe(III)(OH) 3 → Green rust → Lepidocrocite or Magnetite → Goetite etc. Generally, the green rust has known to exist in environments close to the Fe(Π)/Fe(ΠΙ) transition zone or between the oxidized layer and reduced layer in the underground. As anion exchanger and strong reducer, the green rusts can affect the migration of anions, reactions involving green rusts were poorly studied in relation to the safety assessment of radioactive waste repository

  17. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

    Science.gov (United States)

    Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

    2015-11-03

    Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

  18. Weathering rind formation in buried terrace cobbles during periods of up to 300ka

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Nishimoto, S.; Yamamoto, H.; Katsuta, N.

    2011-01-01

    Highlights: → Weathering rinds in sandstone and basalt cobbles buried for up to 300 ka have been investigated. → The aim was to determine the formation process and elemental mass balances during rind development. → Elemental mass balances across the rinds were determined by using open system mass balance (τ i,j ) calculations. → The formation rates are slower than the tropical areas due to the lower rainfall in the studied area. - Abstract: Weathering rinds formed in Mesozoic sandstone and basalt cobbles buried in terrace deposits for up to 300 ka have been investigated. The aim was to determine the formation process and elemental mass balances during rind development. The ages of terraces distributed in the western part of Fukui prefecture, central Japan have been determined as 50 ka, 120 ka and 300 ka based on a tephro-stratigraphic method. Detailed investigations across the weathering rinds, consisting of microscopic observations, porosity measurements, and mineralogical and geochemical analyses using X-ray diffractometry (XRD), X-ray fluorescence (XRF), secondary X-ray analytical microscopy (SXAM), scanning electron microanalyser (SEM) and electron probe microanalysis (EPMA) have been carried out. The results revealed that the Fe concentrations in the weathering rind of a basalt cobble slightly decreased from the cobble's surface (rim) towards the unweathered core. In contrast, in a sandstone cobble formed under the same environmental conditions over the same period of time there is an Fe-rich layer at some distance below the cobble's surface. Elemental mass balances across the rinds were determined by using open system mass balance (τ i,j ) calculations and show that the Fe was precipitated as Fe-oxyhydroxides in the basalt cobbles, although Fe was slightly removed from the rims. In sandstone cobbles, on the other hand, Fe migrated along a Fe concentration gradient by diffusion and precipitated as Fe-oxyhydroxide minerals to form the weathering rinds

  19. Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

    Science.gov (United States)

    Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

    2017-09-01

    The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery

  20. Detailed characterization and preliminary adsorption model for materials for an intermediate-scale reactive-transport experiment

    International Nuclear Information System (INIS)

    Ward, D.B.; Bryan, C.R.

    1994-01-01

    An experiment involving migration of fluid and tracers (Li, Br, Ni) through a 6-m-high x 3-m-dia caisson Wedron 510 sand, is being carried out for Yucca Mountain Site Characterization Project. Sand's surface chemistry of the sand was studied and a preliminary surface-complexation model of Ni adsorption formulated for transport calculations. XPS and leaching suggest that surface of the quartz sand is partially covered by thin layers of Fe-oxyhydroxide and Ca-Mg carbonate and by flakes of kaolinite. Ni adsorption by the sand is strongly pH-dependent, showing no adsorption at pH 5 and near-total adsorption at pH 7. Location of adsorption edge is independent of ionic strength and dissolved Ni concentration; it is shifted to slightly lower pH with higher pCO2 and to slightly higher pH by competition with Li. Diminished adsorption at alkiline pH with higher pCO2 implies formation of dissolved Ni-carbonato complexes. Ni adsorption edges for goethite and quartz, two components of the sand were also measured. Ni adsorption on pure quartz is only moderately pH-dependent and differs in shape and location from that of the sand, whereas Ni adsorption by goethite is strongly pH-dependent. A triple-layer surface-complexation model developed for goethite provides a good fit to the Ni-adsorption curve of the sand. Based on this model, the apparent surface area of the Fe-oxyhydroxide coating is estimated to be 560 m 2 /g, compatible with its occurrence as amorphous Fe-oxyhydroxide. Potentiometric titrations on sand also differ from pure quartz and suggest that effective surface area of sand may be much greater than that measured by N 2 -BET gas adsorption. Attempts to model the adsorption of bulk sand in terms of properties of pure end member components suggest that much of the sand surface is inert. Although the exact Ni adsorption mechanisms remain ambiguous, this preliminary adsorption model provides an initial set of parameters that can be used in transport calculations

  1. THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS

    Energy Technology Data Exchange (ETDEWEB)

    Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.; Fakra, Sirine C.; Beny, Jean Michel; Foster, Andrea L.

    2010-07-16

    Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the

  2. The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

    Science.gov (United States)

    Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

    2014-12-01

    Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

  3. On the role of clay minerals in the disposal of radioactive waste in a clay geological formation; Les mineraux argileux. Leur role et importance dans un site de stockage de dechets radioactifs en couche argileuse profonde

    Energy Technology Data Exchange (ETDEWEB)

    Clauer, N. [Centre National de la Recherche Scientifique (CNRS), Centre de Geochimie de la Surface, 67 - Strasbourg (France)

    2005-05-01

    Clay minerals represent appropriate candidates in the search of geological sites and man-made barriers for potential underground storage of nuclear waste, because of their cation-exchange capabilities and swelling properties. However, this statement needs also to take into consideration other aspects such as physical parameters specific (imbrication of the mineral aggregates, occurrence of oxy-hydroxides and/or organic matter), or not of the rocks (temperature, compaction, etc), and the evolutionary history of the target units as they might indirectly modify the above potentials. Alternatively, original micro-discontinuities (micro-fractures) or those induced by the construction of the site do not appear to represent potential drains for fluid escapes, at least over long distances. The few examples presented here emphasize also that one should be careful about generalizing any conclusion, and that analytical data acquisition should be privileged in order to control better the reliability of the results and the potentials of the applied method. (author)

  4. High heterogeneity in soil composition and quality in different mangrove forests of Venezuela.

    Science.gov (United States)

    Otero, X L; Méndez, A; Nóbrega, G N; Ferreira, T O; Meléndez, W; Macías, F

    2017-09-18

    Mangrove forests play an important role in biogeochemical cycles of metals, nutrients, and C in coastal ecosystems. However, these functions could be strongly affected by the mangrove soil degradation. In this study, we performed an intensive sampling characterizing mangrove soils under different types of environment (lagoon/gulf) and vegetation (Rhizophora/Avicennia/dead mangrove) in the Venezuelan coast. To better understand the spatial heterogeneity of the composition and characteristics of the soils, a wide range of the soil attributes were analyzed. In general, the soils were anoxic (Eh mangroves presented a low Fe Pyrite content due to a limitation in the Fe oxyhydroxide contents, especially in soils with higher organic C content (TOC > 15%). Finally, the dead mangrove showed significantly lower amounts of TOC and fibers (in comparison to the well-preserved mangrove forest), which indicates that the C pools in mangrove soils are highly sensitive also to natural impact, such as ENSO.

  5. Determination of the hydrogen-bond network and the ferrimagnetic structure of a rockbridgeite-type compound, {Fe^{2+Fe^{3+}_{3.2}(Mn^{2+}, Zn)_{0.8}(PO_{4})_{3}(OH)_{4.2}(HOH)_{0.8}}}

    Science.gov (United States)

    Röska, B.; Park, S.-H.; Behal, D.; Hess, K.-U.; Günther, A.; Benka, G.; Pfleiderer, C.; Hoelzel, M.; Kimura, T.

    2018-06-01

    Applying neutron powder diffraction, four unique hydrogen positions were determined in a rockbridgeite-type compound, . Its honeycomb-like H-bond network running without interruption along the crystallographic axis resembles those in alkali sulphatic and arsenatic oxyhydroxides. They provide the so-called dynamically disordered H-bond network over which protons are superconducting in a vehicle mechanism. This is indicated by dramatic increases of dielectric constant and loss factor at room temperature. The relevance of static and dynamic disorder of OH and HOH groups are explained in terms of a high number of structural defects at octahedral chains alternatingly half-occupied by cations. The structure is built up by unusual octahedral doublet, triplet, and quartet clusters of aliovalent 3d transition metal cations, predicting complicate magnetic ordering and interaction. The ferrimagnetic structure below the Curie temperature –83 K could be determined from the structure analysis with neutron diffraction data at 25 K.

  6. The development of portable equipment to study physical and chemical phases in natural waters

    International Nuclear Information System (INIS)

    Breward, N.; Peachey, D.

    1988-08-01

    A direct and relatively non-invasive method of measuring the speciation of dissolved metals in groundwaters has been developed. The equipment relies on a series of columns containing DAEA cellulose, cation exchange resin and anion exchange resin to extract sequentially and respectively colloids, cationic and anionic species. Organic colloids are eluted from the DAEA cellulose with dilute caustic soda while the inorganic colloids (Fe/Al oxyhydroxide phase) are stripped with dilute mineral acid. A further advantage of this scheme is the ability to concentrate the phases by at least a factor of ten. Applications to the groundwaters of the natural analogue sites currently under study by BGS will offer a means of validating thermodynamic databases used in modelling speciation of radionuclides such as uranium and thorium. (author)

  7. Matrix-encapsulated waste forms: application to idealized systems, commercial and SRP/INEL wastes, hydrated radiophases and encapsulant phases

    International Nuclear Information System (INIS)

    Roy, R.; Vance, E.R.; McCarthy, G.J.; White, W.B.

    1981-01-01

    This paper describes the encapsulation strategy as applied to microscopic-scale encapsulation in ceramics composed of micron-sized grains of possibly more leachable radiophases intimately surrounded by micron-sized grains of more insoluble phases. The encapsulation approach should be valid, almost axiomatic, for defense waste. However, there are still problems to be investigated experimentally. These are (a) because of the dilution, it is difficult to confirm the geometry of the radionuclide-bearing phases relative to that of the matrix: one almost has to use the inverse approach by making leach measurements, (b) deciding between using the highly reactive oxyhydroxide sludges themselves or sintered calcine to be coated, (c) verification of the insolubility of the encapsulant phases in a variety of groundwaters, and (d) the production of ceramics of near-zero porosity, using hot-isostatic pressing, or incorporation in either silicate or phosphate cements

  8. An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

    KAUST Repository

    Garcia Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Wei, Nini; Anjum, Dalaver H.; Clo, Alain M.; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

    2017-01-01

    For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

  9. Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition

    Science.gov (United States)

    Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty

    2004-07-01

    Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are

  10. Selective geochemistry of iron in mangrove soils in a semiarid tropical climate: effects of the burrowing activity of the crabs Ucides cordatus and Uca maracoani

    Science.gov (United States)

    Araújo, J. M. C.; Otero, X. L.; Marques, A. G. B.; Nóbrega, G. N.; Silva, J. R. F.; Ferreira, T. O.

    2012-08-01

    Bioturbation by crabs may affect processes associated with organic matter decomposition in mangrove soils. This study examines how two crabs ( Uca maracoani and Ucides cordatus), which are of substantial ecological and economic importance in semiarid coastal areas of Brazil, affect biogeochemical processes in mangrove soils. For this purpose, the physicochemical and geochemical parameters of the soils at different sites were analyzed. The redox potential was always positive at bioturbated sites (+12 to +218 mV), indicating more oxidizing conditions conducive to the oxidation of pyrite and precipitation of oxyhydroxides. In contrast, anoxic conditions prevailed at the control site (Eh mangrove soils, being capable of enhancing organic matter decomposition and also shifting the dominant pathway of organic matter degradation.

  11. Trace metal concentrations in tropical mangrove sediments, NE Brazil.

    Science.gov (United States)

    Miola, Brígida; Morais, Jáder Onofre de; Pinheiro, Lidriana de Souza

    2016-01-15

    Sediment cores were taken from the mangroves of the Coreaú River estuary off the northeast coast of Brazil. They were analyzed for grain size, CaCO3, organic matter, and trace metal (Cd, Pb, Zn, Cu, Al, and Fe) contents. Mud texture was the predominant texture. Levels of trace metals in surface sediments indicated strong influence of anthropogenic processes, and diagenetic processes controlled the trace metal enrichment of core sediments of this estuary. The positive relationships between trace metals and Al and Fe indicate that Cu, Zn, Pb, and Cd concentrations are associated mainly with Al and Fe oxy-hydroxides and have natural sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. A simplified physics-based model for nickel hydrogen battery

    Science.gov (United States)

    Liu, Shengyi; Dougal, Roger A.; Weidner, John W.; Gao, Lijun

    This paper presents a simplified model of a nickel hydrogen battery based on a first approximation. The battery is assumed uniform throughout. The reversible potential is considered primarily due to one-electron transfer redox reaction of nickel hydroxide and nickel oxyhydroxide. The non-ideality due to phase reactions is characterized by the two-parameter activity coefficients. The overcharge process is characterized by the oxygen reaction. The overpotentials are lumped to a tunable resistive drop to fit particular battery designs. The model is implemented in the Virtual Test Bed environment, and the characteristics of the battery are simulated and in good agreement with the experimental data within the normal operating regime. The model can be used for battery dynamic simulation and design in a satellite power system, an example of which is given.

  13. Arsenic species and chemistry in groundwater of southeast Michigan

    International Nuclear Information System (INIS)

    Kim, M.-J.; Nriagu, Jerome; Haack, Sheridan

    2002-01-01

    Most of the arsenic detected was arsenite [As(III)]. - Groundwater samples, taken from 73 wells in 10 counties of southeast Michigan in 1997 had arsenic concentrations in the range of 0.5 to 278 μg/l, the average being 29 μg/l. About 12% of these wells had arsenic concentrations that exceeded the current USEPA's maximum contaminant level of 50 μg/l. Most (53-98%) of the arsenic detected was arsenite [As(III)] and other observations supported the arsenic species distribution (low redox potential and DO). In shallow groundwater ( 15 m), the concentration of arsenic is possibly controlled by reductive dissolution of arsenic-rich iron hydroxide/oxyhydroxide and dissolution of arsenic sulfide minerals

  14. Seasonal Arsenic Accumulation in Stream Sediments at a Groundwater Discharge Zone

    DEFF Research Database (Denmark)

    MacKay, Allison A.; Gan, Ping; Yu, Ran

    2014-01-01

    Seasonal changes in arsenic and iron accumulation rates were examined in the sediments of a brook that receives groundwater discharges of arsenic and reduced iron. Clean glass bead columns were deployed in sediments for known periods over the annual hydrologic cycle to monitor changes in arsenic...... and iron concentrations in bead coatings. The highest accumulation rates occurred during the dry summer period (July-October) when groundwater discharges were likely greatest at the sample locations. The intermediate flow period (October-March), With higher surface water: levels, was associated with losses...... of arsenic and iron from bead column coatings at. depths below 2-6 cm. Batch incubations indicated iron releases from solids to be induced by biological reduction of iron (oxy)hydroxide solids. Congruent arsenic releases during incubation were limited by the high arsenic sorption capacity (0.536 mg...

  15. Timescales of carbon turnover in soils with mixed crystalline mineralogies

    Science.gov (United States)

    Khomo, Lesego; Trumbore, Susan E.; Bern, Carleton R.; Chadwick, Oliver A.

    2017-01-01

    Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay

  16. Development of techniques and models for the determination of redox potentials of saline solutions; Entwicklung von Methoden und Modellen zur Bestimmung des Redoxpotentials salinarer Loesungen

    Energy Technology Data Exchange (ETDEWEB)

    Hagemann, Sven; Bischofer, Barbara; Scharge, Tina; Schoenwiese, Dagmar

    2014-03-15

    The mobility of radionuclides and heavy metals in aqueous systems depends significantly on their oxidation state. Under saline conditions the measurement of pH values and redox potential are distorted/falsified by solution-specific and hardly assessable ion diffusion effects at the reference electrode. The secure prognosis of redox properties is an essential prerequisite for the calculation of the expected heavy metal and radionuclide concentrations in case of a hypothetical solution ingress in an underground disposal facility. The evaluation of the existing data base shows that there are large uncertainties even for the solubility of widespread oxides and oxy-hydroxides like goethite or hematite. The redox properties of natural systems are determined by the solubility of metastable ferrous intermediate products like ferrihydrite, ''green rust'' or jarosite. The work is aimed to establish a consistent data base with information on these phases and ferrous solute species.

  17. Linkage between speciation of Cd in mangrove sediment and its bioaccumulation in total soft tissue of oyster from the west coast of India.

    Science.gov (United States)

    Chakraborty, Parthasarathi; Ramteke, Darwin; Gadi, Subhadra Devi; Bardhan, Pratirupa

    2016-05-15

    This study established a mechanistic linkage between Cd speciation and bioavailability in mangrove system from the west coast of India. High bioaccumulation of Cd was found in the oyster (Crassostrea sp.) even at low Cd loading in the bottom sediment. Bioaccumulation of Cd in the oyster gradually increased with the increasing concentrations of water soluble, exchangeable and carbonate/bicarbonate forms of Cd in the sediments. Fe/Mn oxyhydroxide phase was found to control Cd bioavailability in the sediment system. Cd-associated with sedimentary organic matter was bioavailable and organic ligands in the sediments were poor chelating agents for Cd. This study suggests that bioaccumulation of Cd in oyster (Crassostrea sp.) depends not on the total Cd concentration but on the speciation of Cd in the system. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Mass balance of arsenic fluxes in rivers impacted by gold mining activities in Paracatu (Minas Gerais State, Brazil).

    Science.gov (United States)

    Bidone, Edison; Cesar, Ricardo; Santos, Maria Carla; Sierpe, Ricardo; Silva-Filho, Emmanuel Vieira; Kutter, Vinicius; Dias da Silva, Lílian I; Castilhos, Zuleica

    2018-03-01

    Arsenic (As) is a dangerous and carcinogenic element and drinking water is its main pathway of human exposure. Gold mines are widely recognized as important sources of As pollution. This work proposes the assessment of As distribution along watersheds surrounding "Morro do Ouro" gold mine (Paracatu, southeastern Brazil). A balance approach between filtered As fluxes (As river segments was applied. Ultrafiltration procedure was used to categorize As into the following classes: particulate > 0.1 μm, colloidal  10 kDa, dissolved  1 kDa, and truly dissolved river segment that suggests As accumulation in sediments along the rivers in both urban and rural areas, mainly due to SPM sedimentation and sorption by Fe oxyhydroxides. Ultrafiltration shattering showed concentrations of decreasing As with particle size; the SPM load (> 0.1 μm) was almost one order higher to dissolved load (< 1 kDa).

  19. Characterization of electrocoagulation for removal of chromium and arsenic

    Energy Technology Data Exchange (ETDEWEB)

    Parga, J.R.; Valverde, V. [Institute of Technology of Saltillo, Dept. of Metallurgy and Materials Science, V. Carranza 2400, Saltillo Coah., C.P. 25280 (Mexico); Cocke, D.L.; Gomes, J.A.G.; Kesmez, M.; Moreno, H. [Lamar University, Gill Chair of Chemistry and Chemical Engineering, Beaumont, TX 77710 (United States); Weir, M.; Mencer, D. [Wilkes University, Dept. of Chemistry, Wilkes-Barre, PA 18766 (United States)

    2005-05-01

    Protection of the global environment and, in particular, providing a sustainable source of clean water is a necessity for human survival. The wide use of heavy metals by modern industries has generated by-products containing heavy metals. Specifically, large quantities of chromium and arsenic containing compounds are being discharged into the environment. This study has been conducted to determine the feasibility of an electrocoagulation (EC) process using air injection to remove these inorganic elements with iron electrodes. Powder X-ray diffraction, scanning electron microscopy, and transmission Moessbauer spectroscopy were used to characterize the solid products formed at iron electrodes during EC. The results of this study suggest that magnetite particles and amorphous iron oxyhydroxides are present in the examined EC products. The field pilot-scale study demonstrated the removal of Cr(VI)/Cr(III) and As(III)/As(V) with an efficiency of more than 99 % from both wastewater and wells. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

  20. Adsorption studies of water on copper, nickel, and iron: assessment of the polarization model

    International Nuclear Information System (INIS)

    Lee, S.; Staehle, R.W.

    1997-01-01

    In the atmospheric corrosion of copper, nickel, and iron, the adsorption of water affects the corrosion rates. Knowledge of water adsorption and metal oxyhydroxide formation is important in understanding the atmospheric corrosion process. The purposes of the present research were (i) to measure the adsorption of water on metal surfaces as a function of temperature and relative humidity (RH) and (ii) to assess Bradley's polarization model of adsorption. In the present research, the quartz-crystal microbalance (QCM) technique was used to measure the mass changes of copper, nickel, and iron at 0 to 100% relative humidity and 7 to 90 C under nitrogen and air environments. Less water was adsorbed on copper, nickel, and iron which form oxides than on gold. The amount of water adsorption was similar on copper, nickel, and iron under N 2 and air carrier gases. Functional relationship was first proposed as a way to include dipole/induced dipole interactions between the adsorbents and water layers. (orig.)

  1. Carbohydrate and alditol analysis by high-performance anion-exchange chromatography coupled with electrochemical detection at a cobalt-modified electrode.

    Science.gov (United States)

    Casella, Innocenzo G; Contursi, Michela

    2003-07-01

    A cobalt oxyhydroxide film dispersed on a carbon electrode surface was characterized and proposed as an amperometric sensor for determination of alditols and carbohydrates in flowing streams. Complex mixtures of carbohydrates were separated by anion-exchange chromatography using a moderately alkaline solution as mobile phase. The cobalt modified electrode (GC-Co) was employed under a constant applied potential of 0.5 V (vs Ag/AgCl). Under these experimental conditions the detection limits (S/N=3) for all analyzed electroactive molecules ranged between 0.3 micromol L(-1) and 1.5 micromol L(-1) and the dynamic linear ranges spanned generally three orders of magnitude above the relevant detection limits. Analytical determinations of carbohydrates and alditols in red and white wines, are reported.

  2. The movement of water, arsenic, and radium at a Chalk River waste management area

    International Nuclear Information System (INIS)

    Killey, R.W.D.; Myrand, D.

    1985-05-01

    Area F is a storage site at CRNL for 119 000 tonnes of soil contaminated with low levels of arsenic and radium-226. The site was closed in 1979, and a clayey silt cover was installed in an attempt to minimize infiltration of available precipitation. Results of studies in 1980 and 1983 are used to show that the low-permeability cover has been largely ineffective in reducing infiltration. Radium has remained immobile, but arsenic is being transported by infiltrating waters into unsaturated sands beneath the contaminated soil. Iron oxyhydroxide coatings on the sand grains are sorbing the transported arsenic, and have reduced dissolved arsenic concentrations in pore waters in the sands to natural background levels

  3. Development of techniques and models for the determination of redox potentials of saline solutions; Entwicklung von Methoden und Modellen zur Bestimmung des Redoxpotentials salinarer Loesungen

    Energy Technology Data Exchange (ETDEWEB)

    Hagemann, Sven; Bischofer, Barbara; Scharge, Tina; Schoenwiese, Dagmar

    2014-03-15

    The mobility of radionuclides and heavy metals in aqueous systems depends significantly on their oxidation state. Under saline conditions the measurement of pH values and redox potential are distorted/falsified by solution-specific and hardly assessable ion diffusion effects at the reference electrode. The secure prognosis of redox properties is an essential prerequisite for the calculation of the expected heavy metal and radionuclide concentrations in case of a hypothetical solution ingress in an underground disposal facility. The evaluation of the existing data base shows that there are large uncertainties even for the solubility of widespread oxides and oxy-hydroxides like goethite or hematite. The redox properties of natural systems are determined by the solubility of metastable ferrous intermediate products like ferrihydrite, ''green rust'' or jarosite. The work is aimed to establish a consistent data base with information on these phases and ferrous solute species.

  4. Aluminium, gallium, indium and thallium

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    Aluminium can exist in a number of oxyhydroxide mineral phases including corundum, diaspore, boehmite and gibbsite. The stability constants at zero ionic strength reported for Al(OH) 3 (aq) vary linearly with respect to the inverse of absolute temperature. A full suite of thermodynamic parameters is available for all aluminium phases and hydrolysis species. Gallium hydrolyses to a greater extent than aluminium, with the onset of hydrolysis reactions occurring just above a pHof 1. In fact, even though aluminium has the smallest ionic radius of this series of metals, it has the weakest hydrolysis species and oxide/hydroxide phases.This is due to the presence of stabilising d-orbitals in the heavier metals, gallium, indium and thallium(III). There are few available data for the stability constants of indium(III) hydrolysis species. Of those that are available, the range in the proposed stability constants covers many orders of magnitude.

  5. Synthesis and magnetic properties of SmOOH crystals

    Energy Technology Data Exchange (ETDEWEB)

    Samata, Hiroaki, E-mail: samata@maritime.kobe-u.ac.jp [Graduate School of Maritime Sciences, Kobe University, Fukaeminami, Higashinada, Kobe, Hyogo 658-0022 (Japan); Hanioka, Masashi [Graduate School of Maritime Sciences, Kobe University, Fukaeminami, Higashinada, Kobe, Hyogo 658-0022 (Japan); Ozawa, Tadashi C. [Materials Development Group, Superconducting Properties Unit, National Institute for Materials Science, Sengen, Tsukuba, Ibaraki 305-0047 (Japan)

    2016-01-15

    Samarium oxyhydroxide (SmOOH) crystals were synthesized using a flux method. The as-grown crystals were yellowish, transparent, and elongated with a maximum length of approximately 1.0 mm. SmOOH adopts a monoclinic structure in the space group P2{sub 1}/m with a=0.4356 nm, b=0.3766 nm, c=0.6139 nm, and β=108.464°. The magnetic susceptibility of the SmOOH crystals exhibited typical Van Vleck paramagnetism, and the experimental data at temperatures above 200 K were in close agreement with the calculated results using a spin-orbit coupling constant λ=443 K (308 cm{sup −1}). - Highlights: • SmOOH crystals were synthesized via flux method and characterized. • Magnetic susceptibilities above 200 K agreed with theoretical Van Vleck values. • Discrepancies were observed at lower temperatures based on the crystalline field.

  6. Accelerated growth of oxide film on aluminium alloys under steam: Part II: Effects of alloy chemistry and steam vapour pressure on corrosion and adhesion performance

    DEFF Research Database (Denmark)

    Din, Rameez Ud; Bordo, Kirill; Jellesen, Morten Stendahl

    2015-01-01

    The steam treatment of aluminium alloys with varying vapour pressure of steamresulted in the growth of aluminium oxyhydroxide films of thickness range between 450 - 825nm. The surface composition, corrosion resistance, and adhesion of the produced films was characterised by XPS, potentiodynamic p...... of the vapour pressure of the steam. The accelerated corrosion and adhesion tests on steam generated oxide films with commercial powder coating verified that the performance of the oxide coating is highly dependent on the vapour pressure of the steam....... polarization, acetic acid salt spray, filiform corrosion test, and tape test. The oxide films formed by steam treatment showed good corrosion resistance in NaCl solution by significantly reducing anodic and cathodic activities. The pitting potential of the surface treated with steam was a function...

  7. Geochemical assessment of heavy metals pollution in surface sediments of Vellar and Coleroon estuaries, southeast coast of India.

    Science.gov (United States)

    Nethaji, S; Kalaivanan, R; Arya Viswam; Jayaprakash, M

    2017-02-15

    Surface sediments were collected from Vellar and Coleroon estuaries for determine sediment texture, calcium carbonate, organic matter and heavy metals. Pollution indices such as pollution load index (PLI), contamination factor (CF), enrichment factor (EF) and geo-accumulation index (I geo ) were done for this study to know the level of heavy metals pollution in the estuarine ecosystem. Pearson correlation matrix and factor were used to assess the relationship and source of heavy metals in the estuarine sediments. The results of PLI values reveal that the study area was polluted by all the heavy metals. The calculated values of CF and I geo followed the decreasing order Cu>Ni>Pb>Co>Cr>Zn>Mn>Fe and illustrate that Cu, Ni and Pb are contaminated due to anthropogenic sources in both estuaries. Correlation and factor analysis suggest that FeMn oxyhydroxides, organic matter and fine particles are responsible for high concentration of heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India

    International Nuclear Information System (INIS)

    Ayyamperumal, T.; Jonathan, M.P.; Srinivasalu, S.; Armstrong-Altrin, J.S.; Ram-Mohan, V.

    2006-01-01

    An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar. - Both natural and anthropogenic factors are affecting metals in sediments

  9. Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

    Science.gov (United States)

    Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

    2016-02-01

    The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

  10. Predicting corrosion product transport in nuclear power stations using a solubility-based model for flow-accelerated corrosion

    International Nuclear Information System (INIS)

    Burrill, K.A.; Cheluget, E.L.

    1995-01-01

    A general model of solubility-driven flow-accelerated corrosion of carbon steel was derived based on the assumption that the solubilities of ferric oxyhydroxide and magnetite control the rate of film dissolution. This process involves the dissolution of an oxide film due to fast-flowing coolant unsaturated in iron. The soluble iron is produced by (i) the corrosion of base metal under a porous oxide film and (ii) the dissolution of the oxide film at the fluid-oxide film interface. The iron released at the pipe wall is transferred into the bulk flow by turbulent mass transfer. The model is suitable for calculating concentrations of dissolved iron in feedtrain lines. These iron levels were used to calculate sludge transport rates around the feedtrain. The model was used to predict sludge transport rates due to flow accelerated corrosion of major feedtrain piping in a CANDU reactor. The predictions of the model compare well with plant measurements

  11. Geochemical modelling of the sorption of tetravalent radioelements

    International Nuclear Information System (INIS)

    Bond, K.A.; Tweed, C.J.

    1991-05-01

    The results of an experimental study of the sorption of a range of tetravalent radioelements, plutonium (IV), tin (IV), thorium(IV) and uranium(IV), onto clay at pH8 and pH11 have been successfully simulated using a triple layer sorption model. The model has been incorporated into HARPHRQ, a geochemical program based on PHREEQE. The model has been parameterised using data for sorption onto ferric oxyhydroxide and goethite. The effects of hydroxycarboxylic acids on the sorption process have also been investigated experimentally. It was generally observed that in the presence of 2x10 -3 M gluconate, sorption was reduced by up two orders of magnitude. The model has satisfactorily simulated these lower sorptivities, through assuming competing sorption and complexation reactions. This work, therefore, further confirms the need to take account of such organic materials in safety assessment modelling. (author)

  12. Preliminary characterization of materials for a reactive transport model validation experiment

    International Nuclear Information System (INIS)

    Siegel, M.D.; Ward, D.B.; Cheng, W.C.; Bryant, C.; Chocas, C.S.; Reynolds, C.G.

    1993-01-01

    The geochemical properties of a porous sand and several tracers (Ni, Br, and Li) have been characterized for use in a caisson experiment designed to validate sorption models used in models of inactive transport. The surfaces of the sand grains have been examined by a combination of techniques including potentiometric titration, acid leaching, optical microscopy, and scanning electron microscopy with energy-dispersive spectroscopy. The surface studies indicate the presence of small amounts of carbonate, kaolinite and iron-oxyhydroxides. Adsorption of nickel, lithium and bromide by the sand was measured using batch techniques. Bromide was not sorbed by the sand. A linear (K d ) or an isotherm sorption model may adequately describe transport of Li; however, a model describing the changes of pH and the concentrations of other solution species as a function of time and position within the caisson and the concomitant effects on Ni sorption may be required for accurate predictions of nickel transport

  13. 230Th/238U and 226Ra/230Th fractionation in young basaltic glasses from the East Pacific Rise

    International Nuclear Information System (INIS)

    Reinitz, I.; Turekian, K.K.

    1989-01-01

    Mid-ocean ridge basalt (MORB) glasses treated to remove manganese and iron oxyhydroxide coatings containing U and Th decay chain nuclides sequestered from the ambient aqueous environment show little fractionation of ( 230 Th) from ( 238 U), but extensive enrichment of ( 226 Ra) over ( 230 Th). Chronometry based on ( 230 Th)-( 238 U) disequilibrium yields a mean age of 151,000 ± 55,000 (2σ) years ago for Th-U fractionation, from a source region with Th/U (atom ratio) = 1.58 ± 0.43 (2σ). ( 226 Ra) excesses over ( 230 Th) indicate an enrichment event more recent than the fractionation of Th from U. ( 226 Ra/ 230 Th) correlates well with K/U, providing a rough means of estimating the age since eruption of MORB glasses. (orig.)

  14. Foam separation of Cu (II) and Ni(II) from aqueous solutions and simulated wastewaters

    International Nuclear Information System (INIS)

    Shakir, K.; Beheir, Sh.G.; Aziz, M.

    2003-01-01

    Batch experiments on the removal of Cu(II) and Ni(II) from aqueous solutions were performed through two foam separation techniques: precipitate flotation (PTF) an adsorbing colloid flotation (ACF). In ACF, Fe(III), oxyhydroxide was used as co precipitant and/or adsorbing colloid and sodium lauryl sulfate was used as a collector. ACF required a lower collector concentration than PTF. foreign ions were found to decrease the percent removal, the extent of decrease being higher by divalent ions than that by monovalent ones. However, the percent removal could be improved, even in presence of foreign ions, by addition of Al(II) as an activator. High removals could be attained for Cu(II) and Ni(II) from simulated wastewaters containing different concentrations of both metal ions. The addition of concentrations below the limits recommended by the egyptian regulations for environmental discharge

  15. Metal speciation in agricultural soils adjacent to the Irankuh Pb-Zn mining area, central Iran

    Science.gov (United States)

    Mokhtari, Ahmad Reza; Roshani Rodsari, Parisa; Cohen, David R.; Emami, Adel; Dehghanzadeh Bafghi, Ali Akbar; Khodaian Ghegeni, Ziba

    2015-01-01

    Mining activities are a significant potential source of metal contamination of soils in surrounding areas, with particular concern for metals dispersed into agricultural area in forms that are bioavailable and which may affect human health. Soils in agricultural land adjacent to Pb-Zn mining operations in the southern part of the Irankuh Mountains contain elevated concentrations for a range of metals associated with the mineralization (including Pb, Zn and As). Total and partial geochemical extraction data from a suite of 137 soil samples is used to establish mineralogical controls on ore-related trace elements and help differentiate spatial patterns that can be related to the effects of mining on the agricultural land soils from general geological and environmental controls. Whereas the patterns for Pb, Zn and As are spatially related to the mining operations they display little correlation with the distribution of secondary Fe + Mn oxyhydroxides or carbonates, suggesting dispersion as dust and in forms with limited bioavailability.

  16. Science.gov (United States)

    2018-05-01

    The main reactions considered in OM mineralization during early diagenesis of sediment are listed in Table 1. Under oxidant-depleted conditions, fermentation of metabolizable OM of general formula CxHyOz can yield acetate, CO2 and H2 (r1). Note that reaction r1 takes into account any source of CO2 during fermentation including the partial degradation of high molecular weight OM (HMW OM) into lower molecular weight OM (LMW OM; Corbett et al., 2013; Corbett et al., 2015). The products of this reaction yield CH4 via either acetate fermentation (r2) or hydrogenotrophy (r3). In addition, when electron acceptors (EAs), i.e., Fe(III), SO42-, and partially oxidized HS, are present, CH4 (r4) and OM (r5) can be oxidized to produce CO2. Here, nitrate and Mn oxyhydroxides were not considered as oxidants, owing to the very low concentration of the former (values (SI ≥ 0.5).

  17. Selective Dissolution Techniques, X-Ray Diffraction and Moessbauer Spectroscopy Studies of Forms of Fe in Particle-Size Fractions of an Entic Haplustoll

    International Nuclear Information System (INIS)

    Acebal, S. G.; Aguirre, M. E.; Santamaria, R. M.; Mijovilovich, A.; Petrick, S.; Saragovi, C.

    2003-01-01

    Particle-size fractions (o = mean diameter, 5-2 μm, 2-1 μm, and 57 Fe Moessbauer spectroscopy (MS). Quartz, feldspar, smectite, illite and interstratified illite-smectite are the dominant minerals whereas Fe oxides and oxy-hydroxides are present in low concentration but increase as particle size decreases. Poorly crystallized oxides (highly Al-substituted hematite and goethite) amounts are lower, comparable to or slightly higher than the hematite amounts in the o 5-2 μm, 2-1 μm and 3+ and Fe 2+ are associated to the clay minerals and/or hydroxyl-interlayered 2:1 type material present; part of this Fe 3+ is located in the hydroxy-interlayers its amount being higher in the smallest fraction. Any possible changes after the PY and NaOH treatments were not detected by MS.

  18. Mineralogical study on agricultural soils using mossbauer spectrometry

    International Nuclear Information System (INIS)

    Ceron L, M.L.; Fabian S, J.; Bravo C, J.

    1999-01-01

    Iron (Fe) compounds are very common in nature. In the case of soils, they occur in the form of Fe sesquioxides, such as oxides, hydroxides and oxyhydroxides, as well as substitution cations in clay minerals. These minerals occur in crystalline and amorphous states. The isotopic selective nature of mossbauer spectroscopy (nuclear gamma resonance) allows the indentification of minerals containing Fe even when they are present in low concentrations and in amorphous state. In this work we report the preliminary results of a current study of soil samples collected from the area of Chinchero, Cusco. The experimental data were obtained by mossbauer spectroscopy and x-ray diffraction; these data were complemented with data reported by other workers. Standard procedures were used for sample preparation and the mossbauer spectra were taken at room and liquid nitrogen temperatures

  19. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy

    DEFF Research Database (Denmark)

    Boisen Staal, Line; Lipton, Andrew S.; Zorin, Vadim

    2014-01-01

    Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg1−xGax(OH)2(NO3)x·yH2O] was investigated using solid-state 1H and 71Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg3single bondOH, Mg2Gasingle...... analysis show that the synthesized MgGa LDH׳s had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH)4]− complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of Gasingle bondOsingle bond...

  20. Geochemistry and jasper beds from the Ordovician Løkken ophiolite, Norway: origin of proximal and distal siliceous exhalites

    Science.gov (United States)

    Grenne, Tor; Slack, John F.

    2005-01-01

    Stratiform beds of jasper (hematitic chert), composed essentially of SiO2 (69-95 wt %) and Fe2O3 (3-25 wt %), can be traced several kilometers along strike in the Ordovician L??kken ophiolite, Norway. These siliceous beds are closely associated with volcanogenic massive sulfide (VMS) deposits and are interpreted as sea-floor gels that were deposited by fallout from hydrothermal plumes in silica-rich seawater, in which plume-derived Fe oxyhydroxide particles promoted flocculation and rapid settling of large (???200 ??m) colloidal particles of silica-iron oxyhydroxide. Concentrations of chalcophile elements in the jasper beds are at the parts per million level implying that sulfide particle fallout was insignificant and that the Si-Fe gel-forming plumes were mainly derived from intermediate- (100??-250??C) to high-temperature (>250??) white smoker-type vents with high Fe/S ratios. The interpreted setting is similar to that of the Lau basin, where high-temperature (280??-334??C) white smoker venting alternates or overlaps with sulfide mound-forming black smoker venting. Ratios of Al, Sc, Th, Hf, and REE to iron are very low and show that the detrital input was <0.1 percent of the bulk jasper. Most jasper beds are enriched in U, V, P, and Mo relative to the North American Shale Composite, reflecting a predominantly seawater source, whereas REE distribution patterns (positive Eu and negative Ce anomalies) reflect variable mixing of hydrothermal solutions with oxic seawater at dilution ratios of ???102 to 104. Trace element variations in the gel precursor to the jasper are thought to have been controlled by coprecipitation and/or adsorption by Fe oxyhydroxide particles that formed by the oxidation of hydrothermal Fe2+ within the variably seawater-diluted hydrothermal plume(s). Thick jasper layers near the H??ydal VMS orebody show distinct positive As/Fe and Sb/Fe anomalies that are attributed to near-vent rapid settling of Si-Fe particles derived from As- and Sb

  1. Stabilization of arsenic and chromium polluted soils using water treatment residues

    DEFF Research Database (Denmark)

    Nielsen, Sanne Skov

    water and can be used as a soil amendment to decrease the mobility of CCA in contaminated soil. Stabilization with Fe-WTR was tested at the Collstrop site in Hillerød, Denmark. The site has been polluted with a wide range of wood impregnation agents including CCA during 40 years of wood impregnating...... of contaminants. Arsenic, chromium and copper cannot be degraded and existing methods for cleaning the soil are rarely used as they are expensive and technically demanding. Chemical stabilization of polluted soil is an alternative method for soil remediation, especially metal contamination, and consists in adding...... or other sorbents. Iron water treatment residues mainly consist of ferrihydrite, an oxidized iron oxy-hydroxide with a high reactivity and a large specific surface area with a high capacity for adsorption. Iron water treatment residues (Fe-WTR) are a by-product from treatment of groundwater to drinking...

  2. Geochemical distribution and fate of arsenic in water and sediments of rivers from the Hokusetsu area, Japan

    Directory of Open Access Journals (Sweden)

    Emilie Even

    2017-02-01

    New hydrological insights for the region: The geochemical mapping showed that As in river water exceeded the maximum limit concentration of 10 ppb in several places. The highest As levels (waters and sediments correlated well with the surface geologies, concentrating in a halo around granitic intrusion and nearby faults. The isotopic analysis of sulfur revealed the occurrence of two kinds of sulfide mineralizations responsible for As contamination: one from Late Paleozoic submarine volcanism in sedimentary rocks, and one from Late Cretaceous igneous activities in contact-metamorphosed rocks disseminated with sulfides. The transport of As along river courses occurred mainly as a dissolved species rather than absorbed on Fe/Mn/Al particles, signifying the least role of iron oxy-hydroxides in As adsorption.

  3. Radium, uranium and metals in acidic or alkaline uranium mill

    International Nuclear Information System (INIS)

    Somot, St.

    1997-01-01

    Uranium mill study sites have been chosen in function of their different characteristics: deposits age, treatment nature (alkaline or acid), mill origin. The realization of specific drilling allowed the simultaneous study of the interstitial water and the solid fraction of samples, cut at determined deep. A radiation imbalance between 230 Th and 226 Ra is observed in the acid treatment residues. The trace elements concentration spectrum is directly bound to the nature of the ore. Diamagnetic evolutions are observed in residues. The uranium concentrations are higher in carbonated waters than in calcic sulfated waters. The selective sequential lixiviation showed that the 226 Ra activity of the interstitial water is controlled by the Gypsum in acid treatment residues. In other hand in the alkaline treatment waters, the carbonates occur. The Ra retention is largely bound to the Fe and Mn oxy-hydroxides. (A.L.B.)

  4. Identification and effects of anthropogenic emissions of U and Th on the composition of sediments in a river/estuarine system in Southern Spain

    International Nuclear Information System (INIS)

    Martinez-Aguirre, A.; Garcia-Leon, M.

    1994-01-01

    A study of the distribution of natural radionuclides in different fractions of river bottom sediments has been carried out. The study has shown that the majority of the total U in the sediment is located in the non-residual fraction of the sediment, while Th is more suitable to be present in the residual fraction of the sediments. Also, it has been found that coprecipitation with amorphous ferromanganese oxyhydroxides is the main process of incorporation of U- and Th-isotopes from the water column to suspended matter or bottom sediments. The distribution of the radionuclides and the analysis of some relevant activity ratios in different fractions of sediments has made an unequivocal connection between the enhanced U content in river sediments and the waste discharged into the Odiel and Tinto rivers by the operation in the vicinity of phosphate fertilizer industries. (Author)

  5. Timescales of carbon turnover in soils with mixed crystalline mineralogies

    Science.gov (United States)

    Khomo, Lesego; Trumbore, Susan; Bern, Carleton R.; Chadwick, Oliver A.

    2017-01-01

    Organic matter-mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40-70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9-47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had

  6. Low Temperature Synthesis, Chemical and Electrochemical Characterization of LiNi(x)Co(1-x)O2 (0 less than x less than 1)

    Science.gov (United States)

    Nanjundaswamy, K. S.; Standlee, D.; Kelly, C. O.; Whiteley, R. V., Jr.

    1997-01-01

    A new method of synthesis for the solid solution cathode materials LiNi(x)Co(1-x)O2 (0 less than x less than 1) involving enhanced reactions at temperatures less than or equal to 700 deg. C, between metal oxy-hydroxide precursors MOOH (M = Ni, Co) and Li-salts (Li2CO3, LiOH, and LiNO3) has been investigated. The effects of synthesis conditions and sources of Li, on phase purity, microstructure, and theoretical electrochemical capacity (total M(3+) content) are characterized by powder X-ray diffraction analysis, scanning electron microscopy, chemical analysis and room temperature magnetic susceptibility. An attempt has been made to correlate the electrochemical properties with the synthesis conditions and microstructure.

  7. An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

    KAUST Repository

    Garcia Esparza, Angel T.

    2017-04-13

    For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

  8. Corrosion-resistant amorphous alloy ribbons for electromagnetic filtration of iron rusts from water

    International Nuclear Information System (INIS)

    Kawashima, Asahi; Asami, Katsuhiko; Sato, Takeaki; Hashimoto, Koji

    1985-01-01

    An attempt was made to use corrosion-resistant amorphous Fe-9Cr-13P-7C alloy ribbons as an electromagnetic filter material for trapping various iron rusts suspended in water at 40 0 C. The ferrimagnetic Fe 3 O 4 rust was trapped with the 100 % efficiency and paramagnetic rusts such as α-Fe 2 O 3 , α-FeOOH and amorphous ferric oxyhydroxide were trapped with certain efficiencies at the magnetic field strength of 0.5-10 kOe. The regeneration of the filter by back-washing was easy. The trapping capacity of electromagnetic filter was proportional to the edge length of the filter material where the high magnetic field strength existed. Therefore, melt-spun thin and narrow amorphous alloy ribbons having the high corrosion resistance have the potential utility as electromagnetic filter material. (author)

  9. Metal cycling during sediment early diagenesis in a water reservoir affected by acid mine drainage

    DEFF Research Database (Denmark)

    Torres, Ester; Ayora, Carlos; Canovas, C. R.

    2013-01-01

    The discharge of acid mine drainage (AMD) into a reservoir may seriously affect the water quality. To investigate the metal transfer between the water and the sediment, three cores were collected from the Sancho Reservoir (Iberian Pyrite Belt, SW Spain) during different seasons: turnover event......; oxic, stratified period; anoxic and under shallow perennially oxic conditions. The cores were sliced in an oxygen-free atmosphere, after which pore water was extracted by centrifugation and analyzed. A sequential extraction was then applied to the sediments to extract the water-soluble, monosulfide......, low crystallinity Fe(III)-oxyhydroxide, crystalline Fe(III)-oxide, organic, pyrite and residual phases. The results showed that, despite the acidic chemistry of the water column (pH

  10. Descriptions of the Animas River-Cement Creek confluence and mixing zone near Silverton, Colorado, during the late summers of 1996 and 1997

    Science.gov (United States)

    Schemel, Laurence E.; Cox, Marisa H.

    2005-01-01

    Acidic waters from Cement Creek discharge into the circum-neutral Animas River in a high-elevation region of the San Juan Mountains near Silverton, Colorado. Cement Creek is acidic and enriched in metals and sulfate because it is fed by discharges from abandoned mines and natural mineral deposits. Mixing with the Animas River raises the pH and produces precipitates of iron and aluminum (oxy)hydroxides, which in turn can adsorb other metals. This confluence was studied in 1996 and 1997 to better understand mixing and sorption processes which are common during the neutralization of acidic streams. The photographs in this report show flow braiding and other features that influenced the way the two streams mixed during the late summers of the two years. They also show 'banding' due to incomplete mixing and 'opalescence' due to chemical reactions and the formation of colloidal-size particles in the mixing zone.

  11. Monodispersed macroporous architecture of nickel-oxide film as an anode material for thin-film lithium-ion batteries

    International Nuclear Information System (INIS)

    Wu, Mao-Sung; Lin, Ya-Ping

    2011-01-01

    A nickel-oxide film with monodispersed open macropores was prepared on a stainless-steel substrate by electrophoretic deposition of a polystyrene-sphere monolayer followed by anodic electrodeposition of nickel oxy-hydroxide. The deposited films convert to cubic nickel oxide after annealing at 400 o C for 1 h. Galvanostatic charge and discharge results indicate that the nickel-oxide film with monodispersed open macropores is capable of delivering a higher capacity than the bare nickel-oxide film, especially in high-rate charge and discharge processes. The lithiation capacity of macroporous nickel oxide reaches 1620 mA h g -1 at 1 C current discharge and decreases to 990 mA h g -1 at 15 C current discharge. The presence of monodispersed open macropores in the nickel-oxide film might facilitate the electrolyte penetration, diffusion, and migration. Electrochemical reactions between nickel oxide and lithium ions are therefore markedly improved by this tailored film architecture.

  12. Shelf-to-basin iron shuttling enhances vivianite formation in deep Baltic Sea sediments

    Science.gov (United States)

    Reed, Daniel C.; Gustafsson, Bo G.; Slomp, Caroline P.

    2016-01-01

    Coastal hypoxia is a growing and persistent problem largely attributable to enhanced terrestrial nutrient (i.e., nitrogen and phosphorus) loading. Recent studies suggest phosphorus removal through burial of iron (II) phosphates, putatively vivianite, plays an important role in nutrient cycling in the Baltic Sea - the world's largest anthropogenic dead zone - yet the dynamics of iron (II) phosphate formation are poorly constrained. To address this, a reactive-transport model was used to reconstruct the diagenetic and depositional history of sediments in the Fårö basin, a deep anoxic and sulphidic region of the Baltic Sea where iron (II) phosphates have been observed. Simulations demonstrate that transport of iron from shelf sediments to deep basins enhances vivianite formation while sulphide concentrations are low, but that pyrite forms preferentially over vivianite when sulphate reduction intensifies due to elevated organic loading. Episodic reoxygenation events, associated with major inflows of oxic waters, encourage the retention of iron oxyhydroxides and iron-bound phosphorus in sediments, increasing vivianite precipitation as a result. Results suggest that artificial reoxygenation of the Baltic Sea bottom waters could sequester up to 3% of the annual external phosphorus loads as iron (II) phosphates, but this is negligible when compared to potential internal phosphorus loads due to dissolution of iron oxyhydroxides when low oxygen conditions prevail. Thus, enhancing vivianite formation through artificial reoxygenation of deep waters is not a viable engineering solution to eutrophication in the Baltic Sea. Finally, simulations suggest that regions with limited sulphate reduction and hypoxic intervals, such as eutrophic estuaries, could act as important phosphorus sinks by sequestering vivianite. This could potentially alleviate eutrophication in shelf and slope environments.

  13. Iron Availability in Tropical Soils and Iron Uptake by Plants

    Directory of Open Access Journals (Sweden)

    Guilherme Furlan Mielki

    Full Text Available ABSTRACT Given the increase in crop yields and the expansion of agriculture in low fertility soils, deficiency of micronutrients, such as iron, in plants grown in tropical soils has been observed. The aim of this study was to evaluate Fe availability and Fe uptake by corn (Zea mays L. plants in 13 different soils, at two depths. Iron was extracted by Mehlich-1, Mehlich-3, and CaCl2 (Fe-CC and was fractionated in forms related to low (Feo and high (Fed crystallinity pedogenic oxyhydroxides, and organic matter (Fep using ammonium oxalate, dithionite-citrate, and sodium pyrophosphate, respectively. In order to relate Fe availability to soil properties and plant growth, an experiment was carried out in a semi-hydroponic system in which part of the roots developed in a nutrient solution (without Fe and part in the soil (the only source of Fe. Forty-five days after seeding, we quantified shoot dry matter and leaf Fe concentration and content. Fed levels were high, from 5 to 132 g kg-1, and Feo and Fe-CC levels were low, indicating the predominance of Fe as crystalline oxyhydroxides and a low content of Fe readily available to plants. The extraction solutions showed significant correlations with various soil properties, many common to both, indicating that they act similarly. The correlation between the Mehlich-1 and Mehlich-3 extraction solutions was highly significant. However, these two extraction methods were inefficient in predicting Fe availability to plants. There was a positive correlation between dry matter and Fe levels in plant shoots, even within the ranges considered adequate in the soil and in the plant. Dry matter production and leaf Fe concentration and content were positively correlated with Fep concentration, indicating that the Fe fraction related to soil organic matter most contributes to Fe availability to plants.

  14. Arsenic pollution and fractionation in sediments and mine waste samples from different mine sites

    Energy Technology Data Exchange (ETDEWEB)

    Larios, Raquel; Fernandez-Martinez, Rodolfo [Unidad de Espectroscopia, Division de Quimica, Departamento de Tecnologia, CIEMAT. Av. Complutense, 40, E-28040 Madrid (Spain); Alvarez, Rodrigo [Dpto. de Explotacion y Prospeccion de Minas, Universidad de Oviedo, ETS de Ingenieros de Minas, C/Independencia, 13, E-33004 Oviedo (Spain); Rucandio, Isabel, E-mail: isabel.rucandio@ciemat.es [Unidad de Espectroscopia, Division de Quimica, Departamento de Tecnologia, CIEMAT. Av. Complutense, 40, E-28040 Madrid (Spain)

    2012-08-01

    A characterization of arsenic pollution and its associations with solid mineral phases in sediments and spoil heap samples from four different abandoned mines in Spain is performed. Three of them were mercury mines located in the same mining district, in the province of Asturias, and the other one, devoted to arsenic mining, is in the province of Leon. A sequential extraction procedure, especially developed for arsenic, was applied for the study of arsenic partitioning. Very high total arsenic concentrations ranging 300-67,000 mg{center_dot}kg{sup -1} were found. Arsenic fractionation in each mine is broadly in accordance with the mineralogy of the area and the extent of the mine workings. In almost all the studied samples, arsenic appeared predominantly associated with iron oxyhydroxides, especially in the amorphous form. Sediments from cinnabar roasted piles showed a higher arsenic mobility as a consequence of an intense ore treatment, posing an evident risk of arsenic spread to the surroundings. Samples belonging to waste piles where the mining activity was less intense presented a higher proportion of arsenic associated with structural minerals. Nevertheless, it represents a long-term source of arsenic to the environment. - Highlights: Black-Right-Pointing-Pointer Arsenic fractionation in sediments from different mining areas is evaluated. Black-Right-Pointing-Pointer A sequential extraction scheme especially designed for arsenic partitioning is applied. Black-Right-Pointing-Pointer As associations with mineral pools is in accordance to the mineralogy of each area. Black-Right-Pointing-Pointer As distribution and mobility in each area depends on the extent of mining activity. Black-Right-Pointing-Pointer As occurs mainly associated with amorphous iron oxyhydroxides in all samples.

  15. Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand

    International Nuclear Information System (INIS)

    Wilson, N.J.; Craw, D.; Hunter, K.

    2004-01-01

    A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb 2 S 3 ) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS 2 ). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb 2 O 3 ). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 μg/l) and As (ca. 7 μg /l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment. - High levels of antimony in primitive smelter soils remain largely immobile on the metre scale

  16. Hydrological and geochemical constraints on the mechanism of formation of arsenic contaminated groundwater in Sonargaon, Bangladesh

    Energy Technology Data Exchange (ETDEWEB)

    Itai, Takaaki [Institute for Study of the Earth' s Interior, Okayama University, Misasa, Tottori 682-0193 (Japan)], E-mail: itai-epss@hiroshima-u.ac.jp; Masuda, Harue [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Seddique, Ashraf A. [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh); Mitamura, Muneki [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Maruoka, Teruyuki [Department of Integrative Environmental Science, University of Tsukuba, Tsukuba, Ibaraki 305-8572 (Japan); Li, Xiaodong [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Kusakabe, Minoru [Institute for Study of the Earth' s Interior, Okayama University, Misasa, Tottori 682-0193 (Japan); Dipak, Biswas K. [Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh); Farooqi, Abida [Department of Geosciences, Osaka-City University, Sugimoto-tyo, Sumiyoshi, Osaka 558-8585 (Japan); Yamanaka, Toshiro [Department of Earth Systems Science, Okayama University, 3-1-1 Tsushima-naka Okayama 700-8530 (Japan); Nakaya, Shinji [Department of Civil Engineering, Shinshu University, Wakazato, Nagano 380-8553 (Japan); Matsuda, Jun-ichi [Department of Earth and Space Science, Osaka University, 1-1 Machikaneyama-tyo, Toyonaka-shi, Osaka 560-0043 (Japan); Ahmed, Kazi Matin [Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh)

    2008-11-15

    The geochemical characteristics and hydrological constraints of high As groundwater in Sonargaon, in mid-eastern Bangladesh were investigated in order to ascertain the mechanism of As release into the groundwaters from host sediments in the Ganges-Brahmaputra delta. Samples of groundwater were collected from ca. 230 tube wells in both the rainy and dry seasons. Similar to previous studies, high As groundwater was found in the Holocene unconfined aquifer but not in the Pleistocene aquifer. Groundwaters in the Holocene aquifer were of the Ca-Mg-HCO{sub 3} type with major solutes derived from chemical weathering of detrital minerals such as plagioclase and biotite. Groundwater with high As was generally characterized by high NH{sub 4}{sup +}, possibly derived from the agricultural application of fertilizer as suggested by the small variation of {delta}{sup 15}N{sub NH4} (mostly 2-4 per mille ). Concentrations of Fe changed between the rainy and dry seasons by precipitation/dissolution of Fe oxyhydroxide and siderite, whilst there was not an apparent concomitant change in As. Inhomogeneous spatial distribution of {delta}{sup 18}O in the Holocene unconfined aquifer indicates poor mixing of groundwater in the horizontal direction. Spatial variation of redox conditions is associated with localized variations in subsurface permeability and the recharge/discharge cycle of groundwater. Hydrogeochemical data presented in this paper suggest that reduction of Fe oxyhydroxide is not the only mechanism of As mobilization, and chemical weathering of biotite and/or other basic minerals in the Holocene aquifer could also be important as a primary cause of As mobilization.

  17. The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy

    International Nuclear Information System (INIS)

    Aiuppa, Alessandro; D'Alessandro, Walter; Federico, Cinzia; Palumbo, Barbara; Valenza, Mariano

    2003-01-01

    This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas-water-rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 μg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO 4 -rich ''steam heated groundwaters''. In the HCO 3 - groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H 2 S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxy-hydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable

  18. Hydrogeochemistry of Groundwater and Arsenic Adsorption Characteristics of Subsurface Sediments in an Alluvial Plain, SW Taiwan

    Directory of Open Access Journals (Sweden)

    Libing Liao

    2016-12-01

    Full Text Available Many studies were conducted to investigate arsenic mobilization in different alluvial plains worldwide. However, due to the unique endemic disease associated with arsenic (As contamination in Taiwan, a recent research was re-initiated to understand the transport behavior of arsenic in a localized alluvial plain. A comprehensive approach towards arsenic mobility, binding, and chemical speciation was applied to correlate groundwater hydrogeochemistry with parameters of the sediments that affected the As fate and transport. The groundwater belongs to a Na-Ca-HCO3 type with moderate reducing to oxidizing conditions (redox potential = −192 to 8 mV. Groundwater As concentration in the region ranged from 8.89 to 1131 μg/L with a mean of 343 ± 297 μg/L, while the As content in the core sediments varied from 0.80 to 22.8 mg/kg with a mean of 9.9 ± 6.2 mg/kg. A significant correlation was found between As and Fe, Mn, or organic matter, as well as other elements such as Ni, Cu, Zn, and Co in the core sediments. Sequential extraction analysis indicated that the organic matter and Fe/Mn oxyhydroxides were the major binding pools of As. Batch adsorption experiments showed that the sediments had slightly higher affinity for As(III than for As(V under near neutral pH conditions and the As adsorption capacity increased as the contents of Fe oxyhydroxides as well as the organic matter increased.

  19. Biogeochemistry of Arsenic in Groundwater Flow Systems: The Case of Southern Louisiana

    Science.gov (United States)

    Johannesson, K. H.; Yang, N.; Datta, S.

    2017-12-01

    Arsenic (As) is a highly toxic and carcinogenic metalloid that can cause serious health effects, including increased risk of cancers, infant mortality, and reduced intellectual and motor function in children to populations chronically exposed to As. Recent estimates suggest that more than 140 million people worldwide are drinking As-contaminated groundwater (i.e., As ≥ 10 µg kg-1), and the most severely affected region is the Ganges-Brahmaputra-Meghna delta in Bangladesh and India (i.e., Bengal Basin). Arsenic appears to be mobilized to Bengal Basin groundwaters by reductive dissolution of Fe oxides in aquifer sediments with the source of the labile organic matter occurring in the aquifer sediments. Studies within the lower Mississippi River delta of southern Louisiana (USA) also reveal high As concentrations (up to 640 µg kg-1) in shallow groundwaters. It is not known what affects, if any, the elevated groundwater As has had on local communities. The regional extent of high As shallow groundwaters is controlled, in part, by the distribution of Holocene sediments, deltaic deposits, and organic-rich sediments, similar to the Bengal Basin. Field and laboratory studies suggest that As is largely of geogenic origin, and further that microbial reduction of Fe(III)/Mn(IV) oxides/oxyhydroxides within the sediments contributes the bulk of the As to the groundwaters. Incubation studies are supported by biogeochemical reactive transport modeling, which also indicates reductive dissolution of metal oxides/oxyhydroxides as the likely source of As to these groundwaters. Finally, reactive transport modeling of As in shallow groundwaters suggests that sorption to aquifer mineral surfaces limits the transport of As after mobilization, which may explain, in part, the heterogeneous distribution of As in groundwaters of southern Louisiana and, perhaps, the Bengal Basin.

  20. Occurrence and geochemical behavior of arsenic in a coastal aquifer–aquitard system of the Pearl River Delta, China

    International Nuclear Information System (INIS)

    Wang, Ya; Jiao, Jiu Jimmy; Cherry, John A.

    2012-01-01

    Elevated concentrations of arsenic, up to 161 μg/L, have been identified in groundwater samples from the confined basal aquifer underlying the aquitard of the Pearl River Delta (PRD). Both aquatic arsenic in pore water and solid arsenic in the sediments in the basal aquifer and aquitard were identified. Arsenic speciation of groundwater in the basal aquifer was elucidated on a pH-Eh diagram. In the PRD, arsenic is enriched in groundwater having both low and high salinity, and arsenic enriched groundwater is devoid of dissolved oxygen, has negative Eh values, is slightly alkaline, and has abnormally high concentrations of ammonium and dissolved organic carbon, but low concentrations of nitrate and nitrite. Results of geochemical and hydrochemical analyses and sequential extraction analysis suggest that reductive dissolution of iron oxyhydroxide could be one of the important processes that mobilized solid arsenic. We speculate that mineralization of sedimentary organic matter could also contribute to aquatic arsenic. Scanning electron microscope analysis confirms that abundant authigenic pyrite is present in the sediments. Sulphate derived from paleo-seawater served as the important sulfur source for authigenic pyrite formation. Co-precipitation of arsenic with authigenic pyrite significantly controlled concentrations of aquatic arsenic in the coastal aquifer–aquitard system. - Highlights: ► Coastal aquifer and aquitard are treated as an integrate system. ► Both aquatic arsenic and solid arsenic are observed. ► Aquatic arsenic is derived from reductive dissolution of iron oxyhydroxide. ► Aquatic arsenic can also derived from mineralization of sedimentary organic matter. ► Co-precipitation of arsenic with authigenic pyrite is significant in such a system.

  1. Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals.

    Science.gov (United States)

    Kerisit, Sebastien; Bylaska, Eric J; Massey, Michael S; McBriarty, Martin E; Ilton, Eugene S

    2016-11-21

    Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation states (VI, V, and IV) and charge compensation schemes were varied. Simulated trajectories were used to calculate the U L III -edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO 2 ), and constrained the S 0 2 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to addition of one electron into the solid (-1 H + , +1 e - ). The ability of AIMD to model higher energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with

  2. Impact of termite activity on soil environment: A perspective from their soluble chemical components

    International Nuclear Information System (INIS)

    Semhi, K.; Chaudhuri, S.; Clauer, N.; Boeglin, J. L.

    2008-01-01

    An investigation on varied types of termite mounds relative to the nearby soils that are not inhabited by the termites in different places of Cameroon show that the activity of the termites is increasing the contents of most major and some trace elements in the termite mounds, except for Si and sometimes Fe, Mn, Na and K. These released elements are relocated into newly formed mineral phases that are dissolved by either H 2 O dilute HCl leaching. The Ca and Mn released by the termite activity testify for crystallization of Ca-Mg carbonates and phosphates as well as of Fe oxy-hydroxides and/or Mn hydroxides. Termite activity also induces an increase in the lanthanide contents, the mound materials being especially enriched in light lanthanides relative to the corresponding soils without termite activity. The shapes of the patterns support precipitation of Mn-Fe oxy-hydroxides and Ca carbonates-phosphates. The increased amounts of Eu and Ce linked to termite activity seem to relate to the occurrence of reducing agents that are released by the termites, modifying Eu +3 into Eu +2 and Ce +4 into Ce +3 , favoring in turn selective incorporation of Eu +2 and Ce +3 in the new phases of the termite mounds. Another consequence of the termite activity is the precipitation of H 2 O and HCl extractable phases having low Sr/Ca ratios. Even if the K/Rb values of the termite mounds are typical for common soil-forming silicate minerals, their relocation by an inorganic process alone does not explain an abnormally high ratio in the H 2 O leachable mineral phases. It was also shown that the main source for K and Rb of the dissolved phases is not only the interlayer site of clay particles, but also nutrients immobilized in and by the termites

  3. Geochemical characterization of arsenic-rich coal-combustion ashes buried under agricultural soils and the release of arsenic

    International Nuclear Information System (INIS)

    Veselská, Veronika; Majzlan, Juraj; Hiller, Edgar; Peťková, Katarína; Jurkovič, Ľubomír; Ďurža, Ondrej; Voleková-Lalinská, Bronislava

    2013-01-01

    Highlights: ► Sources, mineralogy and mobility of As in coal-combustion ashes were investigated. ► After a dam failure in 1965, the spilled ashes were buried under agricultural soils. ► Primary carriers of As within coal-combustion ashes are aluminosilicate glasses. ► The most probable secondary carriers of labile As are oxyhydroxides of Si, Al, and Fe. ► Arsenic stored in ashes is a long-term contamination source for the environment. - Abstract: A combination of geochemical and mineralogical methods was used to determine the concentrations, mobility, and sources of As in coal-combustion ashes and soils in the vicinity of a thermal power plant at Nováky, central Slovakia. Fresh lagooned ash, ashes buried under agricultural soils for 45 a, and the overlying soils, contain high concentrations of As ranging from 61 to 1535 mg/kg. There is no differences in the water extractable percentages of As between the fresh lagooned ash and buried ashes, which range from 3.80% to 6.70% of the total As. This small amount of As may perhaps reside on the surfaces of the ash particles, as postulated in the earlier literature, but no evidence was found to support this claim. Electron microprobe analyses show that the dominant primary As carriers are the aluminosilicate glasses enriched in Ca and Fe. The acid NH 4 + -oxalate extraction hints that the oxyhydroxides of Si, Al, and Fe are the most probable secondary carriers of labile As. The X-ray absorption spectroscopy (XAS) analyses show that As in the lagooned and buried ashes occurs mostly as As(V). The long-term burial of the coal-combustion ash under agricultural soil did not cause any major change of its chemical composition or As lability compared to the fresh lagooned ash

  4. Sulfate migration in a river affected by acid mine drainage from the Dabaoshan mining area, South China.

    Science.gov (United States)

    Chen, Meiqin; Lu, Guining; Guo, Chuling; Yang, Chengfang; Wu, Jingxiong; Huang, Weilin; Yee, Nathan; Dang, Zhi

    2015-01-01

    Sulfate, a major component of acid mine drainage (AMD), its migration in an AMD-affected river which located at the Dabaoshan mine area of South China was investigated to pursue the remediation strategy. The existing factors of relatively low pH values of 2.8-3.9, high concentrations of SO4(2-) (∼1940 mg L(-1)) and Fe(3+) (∼112 mg L(-1)) facilitated the precipitation of schwertmannite (Fe8O8(OH)6SO4·nH2O) in the upstream river. Geochemical model calculations implied the river waters were supersaturated, creating the potential for precipitation of iron oxyhydroxides. These minerals evolved from schwertmannite to goethite with the increasing pH from 2.8 to 5.8 along the river. The concentration of heavy metals in river waters was great reduced as a result of precipitation effects. The large size of the exchangeable sulfate pool suggested that the sediments had a strong capacity to bind SO4(2-). The XRD results indicated that schwertmannite was the predominant form of sulfate-bearing mineral phases, which was likely to act as a major sulfate sink by incorporating water-borne sulfate into its internal structure and adsorbing it onto its surface. The small size of reduced sulfur pools and strong oxidative status in the surface sediments further showed that SO4(2-) shifting from water to sediment in form of sulfate reduction was not activated. In short, precipitation of sulfate-rich iron oxyhydroxides and subsequent SO4(2-) adsorption on these minerals as well as water dilution contributed to the attenuation of SO4(2-) along the river waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Occurrence and geochemical behavior of arsenic in a coastal aquifer-aquitard system of the Pearl River Delta, China

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ya [Department of Earth Sciences, The University of Hong Kong, Hong Kong (China); Jiao, Jiu Jimmy, E-mail: jjiao@hku.hk [Department of Earth Sciences, The University of Hong Kong, Hong Kong (China); Cherry, John A. [School of Engineering, University of Guelph, Guelph, ON, Canada N1G 2W1 (Canada)

    2012-06-15

    Elevated concentrations of arsenic, up to 161 {mu}g/L, have been identified in groundwater samples from the confined basal aquifer underlying the aquitard of the Pearl River Delta (PRD). Both aquatic arsenic in pore water and solid arsenic in the sediments in the basal aquifer and aquitard were identified. Arsenic speciation of groundwater in the basal aquifer was elucidated on a pH-Eh diagram. In the PRD, arsenic is enriched in groundwater having both low and high salinity, and arsenic enriched groundwater is devoid of dissolved oxygen, has negative Eh values, is slightly alkaline, and has abnormally high concentrations of ammonium and dissolved organic carbon, but low concentrations of nitrate and nitrite. Results of geochemical and hydrochemical analyses and sequential extraction analysis suggest that reductive dissolution of iron oxyhydroxide could be one of the important processes that mobilized solid arsenic. We speculate that mineralization of sedimentary organic matter could also contribute to aquatic arsenic. Scanning electron microscope analysis confirms that abundant authigenic pyrite is present in the sediments. Sulphate derived from paleo-seawater served as the important sulfur source for authigenic pyrite formation. Co-precipitation of arsenic with authigenic pyrite significantly controlled concentrations of aquatic arsenic in the coastal aquifer-aquitard system. - Highlights: Black-Right-Pointing-Pointer Coastal aquifer and aquitard are treated as an integrate system. Black-Right-Pointing-Pointer Both aquatic arsenic and solid arsenic are observed. Black-Right-Pointing-Pointer Aquatic arsenic is derived from reductive dissolution of iron oxyhydroxide. Black-Right-Pointing-Pointer Aquatic arsenic can also derived from mineralization of sedimentary organic matter. Black-Right-Pointing-Pointer Co-precipitation of arsenic with authigenic pyrite is significant in such a system.

  6. Arsenic pollution and fractionation in sediments and mine waste samples from different mine sites

    International Nuclear Information System (INIS)

    Larios, Raquel; Fernández-Martínez, Rodolfo; Álvarez, Rodrigo; Rucandio, Isabel

    2012-01-01

    A characterization of arsenic pollution and its associations with solid mineral phases in sediments and spoil heap samples from four different abandoned mines in Spain is performed. Three of them were mercury mines located in the same mining district, in the province of Asturias, and the other one, devoted to arsenic mining, is in the province of León. A sequential extraction procedure, especially developed for arsenic, was applied for the study of arsenic partitioning. Very high total arsenic concentrations ranging 300–67,000 mg·kg −1 were found. Arsenic fractionation in each mine is broadly in accordance with the mineralogy of the area and the extent of the mine workings. In almost all the studied samples, arsenic appeared predominantly associated with iron oxyhydroxides, especially in the amorphous form. Sediments from cinnabar roasted piles showed a higher arsenic mobility as a consequence of an intense ore treatment, posing an evident risk of arsenic spread to the surroundings. Samples belonging to waste piles where the mining activity was less intense presented a higher proportion of arsenic associated with structural minerals. Nevertheless, it represents a long-term source of arsenic to the environment. - Highlights: ► Arsenic fractionation in sediments from different mining areas is evaluated. ► A sequential extraction scheme especially designed for arsenic partitioning is applied. ► As associations with mineral pools is in accordance to the mineralogy of each area. ► As distribution and mobility in each area depends on the extent of mining activity. ► As occurs mainly associated with amorphous iron oxyhydroxides in all samples.

  7. Ferric Iron Reduction by Bacteria Associated with the Roots of Freshwater and Marine Macrophytes†

    Science.gov (United States)

    King, G. M.; Garey, Meredith A.

    1999-01-01

    In vitro assays of washed, excised roots revealed maximum potential ferric iron reduction rates of >100 μmol g (dry weight)−1 day−1 for three freshwater macrophytes and rates between 15 and 83 μmol (dry weight)−1 day−1 for two marine species. The rates varied with root morphology but not consistently (fine root activity exceeded smooth root activity in some but not all cases). Sodium molybdate added at final concentrations of 0.2 to 20 mM did not inhibit iron reduction by roots of marine macrophytes (Spartina alterniflora and Zostera marina). Roots of a freshwater macrophyte, Sparganium eurycarpum, that were incubated with an analog of humic acid precursors, anthroquinone disulfate (AQDS), reduced freshly precipitated iron oxyhydroxide contained in dialysis bags that excluded solutes with molecular weights of >1,000; no reduction occurred in the absence of AQDS. Bacterial enrichment cultures and isolates from freshwater and marine roots used a variety of carbon and energy sources (e.g., acetate, ethanol, succinate, toluene, and yeast extract) and ferric oxyhydroxide, ferric citrate, uranate, and AQDS as terminal electron acceptors. The temperature optima for a freshwater isolate and a marine isolate were equivalent (approximately 32°C). However, iron reduction by the freshwater isolate decreased with increasing salinity, while reduction by the marine isolate displayed a relatively broad optimum salinity between 20 and 35 ppt. Our results suggest that by participating in an active iron cycle and perhaps by reducing humic acids, iron reducers in the rhizoplane of aquatic macrophytes limit organic availability to other heterotrophs (including methanogens) in the rhizosphere and bulk sediments. PMID:10508065

  8. Control of arsenic mobilization in paddy soils by manganese and iron oxides.

    Science.gov (United States)

    Xu, Xiaowei; Chen, Chuan; Wang, Peng; Kretzschmar, Ruben; Zhao, Fang-Jie

    2017-12-01

    Reductive mobilization of arsenic (As) in paddy soils under flooded conditions is an important reason for the relatively high accumulation of As in rice, posing a risk to food safety and human health. The extent of As mobilization varies widely among paddy soils, but the reasons are not well understood. In this study, we investigated As mobilization in six As-contaminated paddy soils (total As ranging from 73 to 122 mg kg -1 ) in flooded incubation and pot experiments. Arsenic speciation in the solution and solid phases were determined. The magnitude of As mobilization into the porewater varied by > 100 times among the six soils. Porewater As concentration correlated closely with the concentration of oxalate-extractable As, suggesting that As associated with amorphous iron (oxyhydr)oxides represents the potentially mobilizable pool of As under flooded conditions. Soil containing a high level of manganese oxides showed the lowest As mobilization, likely because Mn oxides retard As mobilization by slowing down the drop of redox potential upon soil flooding and maintaining a higher arsenate to arsenite ratio in the solid and solution phases. Additions of a synthetic Mn oxide (hausmannite) to two paddy soils increased arsenite oxidation, decreased As mobilization into the porewater and decreased As concentrations in rice grain and straw. Consistent with previous studies using simplified model systems or pure mineral phases, the present study shows that Mn oxides and amorphous Fe (oxyhydr)oxides are important factors controlling reductive As mobilization in As-contaminated paddy soils. In addition, this study also suggests a potential mitigation strategy using exogenous Mn oxides to decrease As uptake by rice in paddy soils containing low levels of indigenous Mn oxides, although further work is needed to verify its efficacy and possible secondary effects under field conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Influence of pyrolysis temperature and hardwood species on resulting biochar properties and their effect on azimsulfuron sorption as compared to other sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Trigo, Carmen, E-mail: carmentrigo1@gmail.com [Department of Soil, Water & Climate, University of Minnesota, 1991 Upper Buford Circle, St. Paul, MN 55108 (United States); Cox, Lucia, E-mail: lcox@irnase.csic.es [Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNASE-CSIC), P.O. Box 1052, 41080 Seville (Spain); Spokas, Kurt, E-mail: kurt.spokas@ars.usda.gov [USDA-Agricultural Research Service, 1991 Upper Buford Circle, Rm. 439, St. Paul, MN 55108 (United States)

    2016-10-01

    Azimsulfuron is an acidic herbicide with a high water solubility which makes risk of groundwater contamination a concern. Various wood based biochars produced at different pyrolysis temperatures were characterized along with their sorption capacity for the herbicide azimsulfuron. In addition, we compared sorption on biochars with sorption on mineral sorbents such as clay minerals and iron oxides. In biochar formed at high temperatures (500 °C and 700 °C), FT-IR studies confirmed the increase in aromaticity. Scanning electron microscope (SEM) images of the biochars showed differences in the macroporous structure and lower size pores at higher temperatures. SSA (Specific Surface Area) of the biochars increased with pyrolysis temperature and, for all different biochars, this resulted in higher sorption of azimsulfuron. In the case of mineral sorbents, sorption is not related to SSA. Higher sorption is observed in a montmorillonite, of lower SSA, than in mixture of clay minerals with 30% smectite (w/w). On the contrary as with the clays, sorption on the two iron oxyhydroxides increased with SSA. Desorption studies showed hysteresis. Leaching studies showed no effect on azimsulfuron retention on soil column amended with apple wood biochar, while a reduction of azimsulfuron in leachates in soil columns amended with the modified montmorillonite and alder wood biochar (500 °C). Total retention was shown for alder wood biochar. - Highlights: • Use of biochars and mineral sorbents to mitigate azimsulfuron water contamination • Sorption relates with SSA for biochar and iron oxyhydroxide but not for clays. • Higher sorption values for biochar pyrolysis at 700 °C than mineral sorbents • Different effects on leaching for apple wood biochar, SW-Fe and alder wood biochar.

  10. Genesis of the gossan at the Las Cruces Ore Deposit (SW Spain). Groundwater-Rock Interaction.

    Science.gov (United States)

    Scheiber, L.; Ayora, C.; Vázquez-Suñé, E.; Soler, A.

    2016-12-01

    The Las Cruces deposit has sparked an interest in the scientific community due to the exceptional genesis and mineralogical composition. The original gossan formed by goethite and hematite has been replaced by siderite and galena rock. The current gossan composition is as the result of the interaction of groundwater that circulates through the Niebla-Posadas aquifer and a gossan formed by Fe-oxyhydroxides. The groundwater conditions promoted the reductive dissolution of Pb-bearing goethite by the organic matter degradation and the formation of siderite and galena. Hydrochemical and isotopic characteristics of groundwater endorses this hypothesis. Thus, negative Eh values, the existence of H2S and the tendency to light sulfate isotope values show the reducing conditions of groundwater. The key role of the organic matter degradation is marked by the high ammonium, boron and dissolved organic carbon (DOC) concentrations together the light δ13C values, both in groundwater and siderite. The siderite precipitation is confirmed by the high pH values (up to 10), the low amount of Fe (<10ppb) and the thermodynamic calculations. The Fe-oxyhydroxides are a high adsorption capacity which is capable of absorbing metals as arsenic, lead and antimony. The reductive dissolution of these minerals involves the release of these metal to groundwater. Then, the groundwater rich in sulfur and an excess of lead produce the galena precipitation. The likeness between the δ34S values, both the gossan and groundwater, reveals that the sulfur of the galena come from the currently groundwater. A reactive transport model confirm that the present day groundwater flux and composition is able to form the siderite rock in less than 1Ma, with no external supply of reactants. The limiting factor of the process is the Dissolved Organic Carbon (DOC) concentration in groundwater, i.e., higher concentrations would decrease the formation time, whereas the result is not sensitive to flow conditions.

  11. Cooperative research in coal liquefaction. Final report, May 1, 1991--April 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Huffman, G.P. [ed.

    1996-03-01

    Extensive research continued on catalysts based on novel anion-treated (mainly sulfated) oxides and oxyhydroxides of iron [Fe{sub x}O{sub y}/SO{sub 4}]. In addition, sulfated oxides of tin as well as molybdenum promoted iron oxides were used. Incorporation of small amounts of sulfate, molybdate, or tungstate anions by wet precipitation/impregnation methods was found to increase the surface acidic character of iron oxides; more importantly, it reduced the grain sizes significantly with corresponding increases in specific surface areas. These anion-treated iron and tin oxides were more active for direct coal liquefaction and coal-heavy oil coprocessing than their untreated counterparts. With these catalyst systems, higher conversion levels are obtained as compared to the soluble precursors of iron and molybdenum at the same catalyst metalloading (3500 ppm iron and 50 ppm molybdenum with respect to coal). Sulfated iron oxides and oxyhydroxides were equally active as coal liquefaction catalysts. The sulfate, molybdate, and tungstate anions were found to have similar promotional effects on the properties and activities of iron oxides. One step in the synthesis of anion-treated iron and tin oxides is precipitation as hydroxides using either urea or ammonium hydroxide. The catalysts prepared using urea as a precipitation agent were more reproducible than those using ammonium, hydroxide in terms of activities and properties. These catalysts/catalyst precursors were characterized by several techniques to determine their physical (size and structure related) and chemical (acidity) properties. Sulfated and molybdated iron oxides were found to have grain sizes as small as 10-20 nm. An attempt was made to correlate the physicochemical properties of these catalysts with their activity for coal liquefaction.

  12. Influence of pyrolysis temperature and hardwood species on resulting biochar properties and their effect on azimsulfuron sorption as compared to other sorbents

    International Nuclear Information System (INIS)

    Trigo, Carmen; Cox, Lucia; Spokas, Kurt

    2016-01-01

    Azimsulfuron is an acidic herbicide with a high water solubility which makes risk of groundwater contamination a concern. Various wood based biochars produced at different pyrolysis temperatures were characterized along with their sorption capacity for the herbicide azimsulfuron. In addition, we compared sorption on biochars with sorption on mineral sorbents such as clay minerals and iron oxides. In biochar formed at high temperatures (500 °C and 700 °C), FT-IR studies confirmed the increase in aromaticity. Scanning electron microscope (SEM) images of the biochars showed differences in the macroporous structure and lower size pores at higher temperatures. SSA (Specific Surface Area) of the biochars increased with pyrolysis temperature and, for all different biochars, this resulted in higher sorption of azimsulfuron. In the case of mineral sorbents, sorption is not related to SSA. Higher sorption is observed in a montmorillonite, of lower SSA, than in mixture of clay minerals with 30% smectite (w/w). On the contrary as with the clays, sorption on the two iron oxyhydroxides increased with SSA. Desorption studies showed hysteresis. Leaching studies showed no effect on azimsulfuron retention on soil column amended with apple wood biochar, while a reduction of azimsulfuron in leachates in soil columns amended with the modified montmorillonite and alder wood biochar (500 °C). Total retention was shown for alder wood biochar. - Highlights: • Use of biochars and mineral sorbents to mitigate azimsulfuron water contamination • Sorption relates with SSA for biochar and iron oxyhydroxide but not for clays. • Higher sorption values for biochar pyrolysis at 700 °C than mineral sorbents • Different effects on leaching for apple wood biochar, SW-Fe and alder wood biochar

  13. Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

    Science.gov (United States)

    Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

    2011-12-28

    Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

  14. Characteristics and origin of rock varnish from the hyperarid coastal deserts of northern Peru

    Science.gov (United States)

    Jones, Charles E.

    1991-01-01

    The characteristics of a new type of rock varnish from the hyperarid coastal deserts of northern Peru, combined with laboratory experiments on associated soil materials, provide new insights into the formation of rock varnish. The Peruvian varnish consists of an Fe-rich, Mn-poor component covering up to 95% of a varnished surface and a Fe-rich, Mn-rich component found only in pits and along cracks and ridges. The alkaline soils plus the catalytic Fe oxyhydroxides that coat much of the varnish surfaces make the Peruvian situation ideal for physicochemical precipitation of Mn. However, the low Mn content of the dominant Fe-rich, Mn-poor component suggests that such precipitation is minor. This, plus the presence of abundant bacteria in the Mn-rich varnish and the recorded presence of Mn-precipitating bacteria in varnish elsewhere, suggests that bacteria are almost solely responsible for Mn-precipitation in rock varnish. A set of experiments involving Peruvian soil samples in contact with water-CO 2 solutions indicates that natural fogs or dews release Mn but not Fe when they come in contact with eolian materials on rock surfaces. This mechanism may efficiently provide Mn to bacteria on varnishing surfaces. The lack of Fe in solution suggests that a large but unknown proportion of Fe in varnish may be in the form of insoluble Fe oxyhydroxides sorbed onto the clay minerals that form the bulk of rock varnish. The results of this study do not substantively change R. I. Dorn's paleoenvironmental interpretations of varnish Mn:Fe ratios, but they do suggest areas for further inquiry.

  15. A phase III study of the efficacy and safety of a novel iron-based phosphate binder in dialysis patients.

    Science.gov (United States)

    Floege, Jürgen; Covic, Adrian C; Ketteler, Markus; Rastogi, Anjay; Chong, Edward M F; Gaillard, Sylvain; Lisk, Laura J; Sprague, Stuart M

    2014-09-01

    Efficacy of PA21 (sucroferric oxyhydroxide), a novel calcium-free polynuclear iron(III)-oxyhydroxide phosphate binder, was compared with that of sevelamer carbonate in an open-label, randomized, active-controlled phase III study. Seven hundred and seven hemo- and peritoneal dialysis patients with hyperphosphatemia received PA21 1.0-3.0 g per day and 348 received sevelamer 4.8-14.4 g per day for an 8-week dose titration, followed by 4 weeks without dose change, and then 12 weeks maintenance. Serum phosphorus reductions at week 12 were -0.71 mmol/l (PA21) and -0.79 mmol/l (sevelamer), demonstrating non-inferiority of, on average, three tablets of PA21 vs. eight of sevelamer. Efficacy was maintained to week 24. Non-adherence was 15.1% (PA21) vs. 21.3% (sevelamer). The percentage of patients that reported at least one treatment-emergent adverse event was 83.2% with PA21 and 76.1% with sevelamer. A higher proportion of patients withdrew owing to treatment-emergent adverse events with PA21 (15.7%) vs. sevelamer (6.6%). Mild, transient diarrhea, discolored feces, and hyperphosphatemia were more frequent with PA21; nausea and constipation were more frequent with sevelamer. After 24 weeks, 99 hemodialysis patients on PA21 were re-randomized into a 3-week superiority analysis of PA21 maintenance dose in 50 patients vs. low dose (250 mg per day (ineffective control)) in 49 patients. The PA21 maintenance dose was superior to the low dose in maintaining serum phosphorus control. Thus, PA21 was effective in lowering serum phosphorus in dialysis patients, with similar efficacy to sevelamer carbonate, a lower pill burden, and better adherence.

  16. Arsenic mobilization in a freshening groundwater system formed within glaciomarine deposits

    International Nuclear Information System (INIS)

    Cavalcanti de Albuquerque, R.; Kirste, D.

    2012-01-01

    Arsenic release to groundwater and conditions favoring As mobility are investigated in a system of aquifers formed within unconsolidated Quaternary sediments. The studied groundwater system is comprised of unconfined aquifers formed in glaciofluvial sediments with Ca–Mg–HCO 3 groundwater, and confined aquifers formed within glaciomarine sediments with high As (above 10 μg/L) Na–HCO 3 or Na–Cl groundwater. A positive relationship of As concentrations with the Na/(Ca + Mg) ratio of groundwater indicates that As release occurs in glaciomarine sediments concurrent to cation exchange reactions related to groundwater freshening. Arsenic is mobile in confined aquifers as a result of groundwater basic pH which prevents arsenate from adsorbing to mineral surfaces, and reducing conditions that favor speciation to arsenite. Selected extractions applied to sediment core samples indicate that As occurs in sediments predominantly in sulfide minerals and in Mn oxides and/or Fe oxyhydroxides. General positive relationships between As and the reduced species Fe 2+ , NH 3 and dissolved S 2− suggest that As release occurs at increasingly reducing conditions. Despite likely As release via Fe oxyhydroxide reductive dissolution, Fe remains at relatively low concentrations in groundwater (up to 0.37 mg/L) as a result of possible Fe adsorption and Fe reprecipitation as carbonate minerals favored by basic pH and high alkalinity. The presence of S 2− in some samples, a negative relationship between δ 34 S of SO 4 and SO 4 2- concentrations, and a positive relationship between δ 34 S and δ 18 O of SO 4 indicate that groundwater in confined aquifers is undergoing bacterial SO 4 reduction.

  17. Application of zero-valent iron nanoparticles for the removal of aqueous zinc ions under various experimental conditions.

    Directory of Open Access Journals (Sweden)

    Wen Liang

    Full Text Available Application of zero-valent iron nanoparticles (nZVI for Zn²⁺ removal and its mechanism were discussed. It demonstrated that the uptake of Zn²⁺ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn²⁺ could be removed within 2 h. The pH value and dissolved oxygen (DO were the important factors of Zn²⁺ removal by nZVI. The DO enhanced the removal efficiency of Zn²⁺. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxyhydroxide, which could show high adsorption affinity. The removal efficiency of Zn²⁺ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn²⁺ by nZVI because the existing H⁺ inhibited the formation of iron (oxyhydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn²⁺ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn²⁺ were higher than Cd²⁺. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn²⁺.

  18. Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

    Energy Technology Data Exchange (ETDEWEB)

    Pušnik, Klementina; Goršak, Tanja [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, 1000 Ljubljana (Slovenia); Drofenik, Miha [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Faculty of Chemistry and Chemical Engineering, University of Maribor, 2000 Maribor (Slovenia); Makovec, Darko [Department for Materials Synthesis, Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, 1000 Ljubljana (Slovenia)

    2016-09-01

    There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe{sup 3+}/Fe{sup 2+} ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles’ formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe{sup 3+} ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH. - Highlights: • Co-precipitation of Fe{sup 3+}/Fe{sup 2+} ions in the presence of aspartic amino acid (Asp). • Through analysis of nanoparticle formation mechanism. • Presence of Asp changes the mechanism of the nanoparticles’ formation. • Asp forms a coordination complex with the Fe{sup 3+} ions. • Asp impedes the formation of iron oxyhydroxide phase and suppresses the growth of iron-oxide nanoparticles. • The aspartic-acid-absorbed nanoparticles form stable aqueous suspensions.

  19. Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

    International Nuclear Information System (INIS)

    Pušnik, Klementina; Goršak, Tanja; Drofenik, Miha; Makovec, Darko

    2016-01-01

    There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe 3+ /Fe 2+ ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles’ formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe 3+ ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH. - Highlights: • Co-precipitation of Fe 3+ /Fe 2+ ions in the presence of aspartic amino acid (Asp). • Through analysis of nanoparticle formation mechanism. • Presence of Asp changes the mechanism of the nanoparticles’ formation. • Asp forms a coordination complex with the Fe 3+ ions. • Asp impedes the formation of iron oxyhydroxide phase and suppresses the growth of iron-oxide nanoparticles. • The aspartic-acid-absorbed nanoparticles form stable aqueous suspensions.

  20. Beyond clay - using selective extractions to improve predictions of soil carbon content

    Science.gov (United States)

    Rasmussen, C.; Berhe, A. A.; Blankinship, J. C.; Crow, S. E.; Druhan, J. L.; Heckman, K. A.; Keiluweit, M.; Lawrence, C. R.; Marin-Spiotta, E.; Plante, A. F.; Schaedel, C.; Schimel, J.; Sierra, C. A.; Thompson, A.; Wagai, R.; Wieder, W. R.

    2016-12-01

    A central component of modern soil carbon (C) models is the use of clay content to scale the relative partitioning of decomposing plant material to respiration and mineral stabilized soil C. However, numerous pedon to plot scale studies indicate that other soil mineral parameters, such as Fe- or Al-oxyhydroxide content and specific surface area, may be more effective than clay alone for predicting soil C content and stabilization. Here we directly address the following question: Are there soil physicochemical parameters that represent mineral C association and soil C content that can replace or be used in conjunction with clay content as scalars in soil C models. We explored the relationship of soil C content to a number of soil physicochemical and physiographic parameters using the National Cooperative Soil Survey database that contains horizon level data for > 62,000 pedons spanning global ecoregions and geographic areas. The data indicated significant variation in the degree of correlation among soil C, clay and Fe-/Al-oxyhydroxides with increasing moisture variability. Specifically, dry, water-limited systems (PET/MAP > 1) presented strong positive correlations between clay and soil C, that decreased significantly to little or no correlation in wet, energy-limited systems (PET/MAP soil C to oxalate extractable Al+Fe increased significantly with increasing moisture availability. This pattern was particularly well expressed for subsurface B horizons. Multivariate analyses indicated similar patterns, with clear climate and ecosystem level variation in the degree of correlation among soil C and soil physicochemical properties. The results indicate a need to modify current soil C models to incorporate additional C partitioning parameters that better account for climate and ecoregion variability in C stabilization mechanisms.

  1. High-level waste glass field burial tests at CRNL

    International Nuclear Information System (INIS)

    Melnyk, T.W.; Walton, F.B.; Johnson, H.L.

    1983-06-01

    In 1960 June, 25 nepheline syenite-based glass hemispheres containing the fission products 137 Cs, 90 Sr, 144 Ce and 106 Ru were buried below the water table in fluvial sand at the Chalk River Nuclear Laboratories of Atomic Energy of Canada Limited. Soil and groundwater concentrations of 90 Sr and 137 Cs have been determined since then and the data have been interpreted using kinetically limited migration models to deduce the leaching history of the glass for these burial conditions. The leaching history derived from the field data is compared to laboratory leaching of samples from a glass hemisphere retrieved in 1978, and also to pre-burial laboratory leaching of identical hemispheres. The time dependence of the leach rates observed for the buried specimens suggests that leaching is being inhibited by the formation of a protective surface layer, although no direct observation of this layer has been made. Using an average leach rate of 5.6 x 10 -14 kg/(m 2 .s) derived from the field data for the period 1966 to 1977, it is estimated that it would require approximately 20 million years to dissolve the glass hemispheres. The effect of the kinetic limitations of the fission-product/fluvial-sand interactions is discussed with respect to the migration of 90 Sr and 137 Cs over a 20-a time scale. It is concluded that kinetically limited sorption by oxyhydroxides rather than equilibrium ion exchange controls the long-term migration of 90 Cr; the action of the oxyhydroxides immobilizes the 90 Sr on the longer time scale. Cesium is initially rapidly bound to the micaceous fraction of the sand. On a longer time scale, slow remobilization of 137 Cs in particulate form is observed and is believed to be related to bacterial action

  2. Fe-Ni-bearing serpentines from the saprolite horizon of Caribbean Ni-laterite deposits: new insights from thermodynamic calculations

    Science.gov (United States)

    Villanova-de-Benavent, Cristina; Domènech, Cristina; Tauler, Esperança; Galí, Salvador; Tassara, Santiago; Proenza, Joaquín A.

    2017-10-01

    Fe-Ni-bearing serpentine from the saprolite horizon is the main Ni ores in hydrous silicate-type Ni laterites and formed by chemical weathering of partially serpentinized ultramafic rocks under tropical conditions. During lateritization, Mg, Si, and Ni are leached from the surface and transported downwards. Fe2+ is oxidized to Fe3+ and fixed as insoluble Fe-oxyhydroxides (mostly goethite) that incorporate Ni. This Ni is later leached from goethite and incorporated in secondary serpentine and garnierite. As a result, a serpentine-dominated saprolite horizon forms over the ultramafic protolith, overlapped by a Fe-oxyhydroxide-dominated limonite horizon. The serpentine from the protolith (serpentine I) is of hydrothermal origin and yields similar Ni (0.10-0.62 wt.% NiO) and lower Fe (mostly 1.37-5.81 wt.% FeO) concentrations than the primary olivine. In contrast, Fe-Ni-bearing serpentine from the saprolite (serpentine II) shows significantly higher and variable Fe and Ni contents, typically ranging from 2.23 to 15.59 wt.% Fe2O3 and from 1.30 to 7.67 wt.% NiO, suggesting that serpentine get enriched in Fe and Ni under supergene conditions. This study presents detailed mineralogical, textural, and chemical data on this serpentine II, as well as new insights by thermodynamic calculations assuming ideal solution between Fe-, Ni- and Mg-pure serpentines. The aim is to assess if at atmospheric pressure and temperature Fe-Ni-bearing serpentine can be formed by precipitation. Results indicate that the formation of serpentine II under atmospheric pressure and temperature is thermodynamically supported, and pH, Eh, and the equilibrium constant of the reaction are the parameters that affect the results more significantly.

  3. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    Science.gov (United States)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  4. Negative impact of oxygen molecular activation on Cr(VI) removal with core–shell Fe@Fe2O3 nanowires

    International Nuclear Information System (INIS)

    Mu, Yi; Wu, Hao; Ai, Zhihui

    2015-01-01

    Highlights: • The presence of oxygen inhibited Cr(VI) removal efficiency with nZVI by near 3 times. • Cr(VI) removal with nZVI was related to adsorption, reduction, co-precipitation, and adsorption reactions. • Molecular oxygen activation competed donor electrons from Fe 0 core and surface bound Fe(II) of nZVI. • Thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell of nZVI leaded to the electron transfer inhibition. - Abstract: In this study, we demonstrate that the presence of oxygen molecule can inhibit Cr(VI) removal with core–shell Fe@Fe 2 O 3 nanowires at neutral pH of 6.1. 100% of Cr(VI) removal was achieved by the Fe@Fe 2 O 3 nanowires within 60 min in the anoxic condition, in contrast, only 81.2% of Cr(VI) was sequestrated in the oxic condition. Removal kinetics analysis indicated that the presence of oxygen could inhibit the Cr(VI) removal efficiency by near 3 times. XRD, SEM, and XPS analysis revealed that either the anoxic or oxic Cr(VI) removal was involved with adsorption, reduction, co-precipitation, and re-adsorption processes. More Cr(VI) was bound in a reduced state of Cr(III) in the anoxic process, while a thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell, leading to inhibiting the electron transfer, was found under the oxic process. The negative impact of oxygen molecule was attributed to the oxygen molecular activation which competed with Cr(VI) adsorbed for the consumption of donor electrons from Fe 0 core and ferrous ions bound on the iron oxides surface under the oxic condition. This study sheds light on the understanding of the fate and transport of Cr(VI) in oxic and anoxic environment, as well provides helpful guide for optimizing Cr(VI) removal conditions in real applications

  5. Fractionation of fulvic acid by iron and aluminum oxides: influence on copper toxicity to Ceriodaphnia dubia

    Science.gov (United States)

    Smith, Kathleen S.; Ranville, James F.; Lesher, Emily K.; Diedrich, Daniel J.; McKnight, Diane M.; Sofield, Ruth M.

    2014-01-01

    This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

  6. Modelling metal-humic substances-surface systems: reasons for success, failure and possible routes for peace of mind

    International Nuclear Information System (INIS)

    Reiller, P.E.

    2012-01-01

    Iron oxides and oxy-hydroxides are commonly of considerable importance in the sorption of ions onto rocks, soils and sediments. They can be the controlling sorptive phases even if they are present in relatively small quantities. In common with other oxides and clay minerals, the sorption pH-edge of metals is directly linked to their hydrolysis: the higher the residual charge on the metal ion, the lower the pH-edge. Modelling of this process has been successfully carried out using different microscopic or macroscopic definitions of the interface (e.g. surface complexation or ion exchange models that may or may not include mineralogical descriptions). The influence of organic material on the sorption of many metals is of significant. This organic material includes simple organic molecules and more complex exo-polymeric substances (e.g. humic substances) produced by the decay of natural organic matter. Sorption of this organic material to mineral surfaces has been the subject of a large body of work. The various types of organic substances do not share the same affinities for mineral surfaces in general, and for iron oxides and oxy-hydroxides in particular. In those cases in which successful models of the component binary systems (i.e. metal-surface, metal-organic, organic-surface) have been developed, the formation of mixed surface complexes, the evolution of the surface itself, the addition order in laboratory systems, and the evolution of natural organic matter fractions during sorption, have often precluded a satisfactory description of metal-surface-organic ternary systems over a sufficiently wide range of parameter values (i.e. pH, ionic strength, concentration of humic substances). This manuscript describes the reasons for some successes and failures in the modelling of the ternary systems. Promising recent advances and possible methods of providing more complete descriptions of these intricate systems are also discussed. (author)

  7. Storage and stability of biochar-derived carbon and total organic carbon in relation to minerals in an acid forest soil of the Spanish Atlantic area.

    Science.gov (United States)

    Fernández-Ugalde, Oihane; Gartzia-Bengoetxea, Nahia; Arostegi, Javier; Moragues, Lur; Arias-González, Ander

    2017-06-01

    Biochar can largely contribute to enhance organic carbon (OC) stocks in soil and improve soil quality in forest and agricultural lands. Its contribution depends on its recalcitrance, but also on its interactions with minerals and other organic compounds in soil. Thus, it is important to study the link between minerals, natural organic matter and biochar in soil. In this study, we investigated the incorporation of biochar-derived carbon (biochar-C) into various particle-size fractions with contrasting mineralogy and the effect of biochar on the storage of total OC in the particle-size fractions in an acid loamy soil under Pinus radiata (C3 type) in the Spanish Atlantic area. We compared plots amended with biochar produced from Miscanthus sp. (C4 type) with control plots (not amended). We separated sand-, silt-, and clay-size fractions in samples collected from 0 to 20-cm depth. In each fraction, we analyzed clay minerals, metallic oxides and oxy-hydroxides, total OC and biochar-C. The results showed that 51% of the biochar-C was in fractions fractions (0.2-2μm, 0.05-0.2μm, fractions, as it occurred with the vermiculitic phases and metallic oxides and oxy-hydroxides. Biochar also affected to the distribution of total OC among particle-size fractions. Total OC concentration was greater in fractions 2-20μm, 0.2-2μm, 0.05-0.2μm in biochar-amended plots than in control plots. This may be explained by the adsorption of dissolved OC from fraction organic matter already occurred in the first year. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Ironstone deposits hosted in Eocene carbonates from Bahariya (Egypt)-New perspective on cherty ironstone occurrences

    Science.gov (United States)

    Afify, A. M.; Sanz-Montero, M. E.; Calvo, J. P.

    2015-11-01

    This paper gives new insight into the genesis of cherty ironstone deposits. The research was centered on well-exposed, unique cherty ironstone mineralization associated with Eocene carbonates from the northern part of the Bahariya Depression (Egypt). The economically important ironstones occur in the Naqb Formation (Early Eocene), which is mainly formed of shallow marine carbonate deposits. Periods of lowstand sea-level caused extensive early dissolution (karstification) of the depositional carbonates and dolomitization associated with mixing zones of fresh and marine pore-water. In faulted areas, the Eocene carbonate deposits were transformed into cherty ironstone with preservation of the precursor carbonate sedimentary features, i.e. skeletal and non-skeletal grain types, thickness, bedding, lateral and vertical sequential arrangement, and karst profiles. The ore deposits are composed of iron oxyhydroxides, mainly hematite and goethite, chert in the form of micro- to macro-quartz and chalcedony, various manganese minerals, barite, and a number of subordinate sulfate and clay minerals. Detailed petrographic analysis shows that quartz and iron oxides were coetaneous and selectively replaced carbonates, the coarse dolomite crystals having been preferentially transformed into quartz whereas the micro-crystalline carbonates were replaced by the iron oxyhydroxides. A number of petrographic, sedimentological and structural features including the presence of hydrothermal-mediated minerals (e.g., jacobsite), the geochemistry of the ore minerals as well as the structure-controlled location of the mineralization suggest a hydrothermal source for the ore-bearing fluids circulating through major faults and reflect their proximity to centers of magmatism. The proposed formation model can contribute to better understanding of the genetic mechanisms of formation of banded iron formations (BIFs) that were abundant during the Precambrian.

  9. Topotactic growth, selective adsorption, and adsorption-driven photocatalysis of protonated layered titanate nanosheets.

    Science.gov (United States)

    Wu, Qili; Yang, Xianfeng; Liu, Jia; Nie, Xin; Huang, Yongliang; Wen, Yuping; Khan, Javid; Khan, Wasim U; Wu, Mingmei; An, Taicheng

    2014-10-22

    Layered titanates with selective adsorption ability and adsorption-driven photocatalytic property can be quite attractive due to their potential applications in water purification. In this work, lepidocrocite-like layered protonated titanate (H2Ti2O5·H2O, denoted as HTO) nanosheets were successfully synthesized by an ion-exchange process. It turns out that this layered structure displays an abundant and selective adsorption toward the fluoroquinolone pharmaceutical compared with some large dye molecules due to a size selectivity of the interlayer spacing of HTO and the molecular horizontal size, as well as their electrostatic interaction. The uptake ability of HTO could be readily controlled through adjusting the pH values of adsorbate solution, and the maximum uptake capacity was achieved at the pH value of about 5.5 for ciprofloxacin (CIP) and 6.5 for moxifloxacin (MOX). The adsorption amount of smaller nalidixic acid (NAL) showed an increasing tendency as the pH value decreased. Moreover, the two-dimensional layered crystal structure also permits such HTO nanosheets to have a large percentage of (010) faces exposed, which is considerably provided by the interlayer surfaces of these nanosheets. The (010) surface has a similar Ti and O atomic arrangement as to the highly reactive anatase TiO2(001) one. Due to these specific characteristics, these HTO nanosheets show excellent photocatalytic activity in degrading CIP under UV light irradiation as well as possess a superior adsorption ability to remove CIP from aqueous solution selectively and efficiently. The photocatalytic reaction is believed to be mainly conducted on the active anatase (001)-like interlayer (010) surfaces of the layered structures since the as-prepared HTO performs an adsorption-driven molecular recognitive photocatalytic reaction.

  10. Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yubing [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Ding, Congcong; Cheng, Wencai [Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke, E-mail: xkwang@ipp.ac.cn [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

    2014-09-15

    Graphical abstract: - Highlights: • Sorption and in-situ reduction of U(VI) is observed. • The composites are more effective for U(VI) removal and solidification. • The inner-sphere surface complexes are observed. - Abstract: The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH{sup −} groups of rGO and the massive enrichment of Fe{sup 2+} on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the U-C (at ∼2.9 Å) and U-Fe (at ∼3.2 Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management.

  11. Coupled Effect of Ferrous Ion and Oxygen on the Electron Selectivity of Zerovalent Iron for Selenate Sequestration.

    Science.gov (United States)

    Qin, Hejie; Li, Jinxiang; Yang, Hongyi; Pan, Bingcai; Zhang, Weiming; Guan, Xiaohong

    2017-05-02

    Although the electron selectivity (ES) of zerovalent iron (ZVI) for target contaminant and its utilization ratio (UR) decide the removal capacity of ZVI, little effort has been made to improve them. Taking selenate [Se(VI)] as a target contaminant, this study investigated the coupled influence of aeration gas and Fe(II) on the ES and UR of ZVI. Oxygen was necessary for effective removal of Se(VI) by ZVI without Fe(II) addition. Due to the application of 1.0 mM Fe(II), the ES of ZVI was increased from 3.2-3.6% to 6.2-6.8% and the UR of ZVI was improved by 5.0-19.4% under aerobic conditions, which resulted in a 100-180% increase in the Se(VI) removal capacity by ZVI. Se(VI) reduction by Fe 0 was a heterogeneous redox reaction, and the enrichment of Se(VI) on ZVI surface was the first step of electron transfer from Fe 0 core to Se(VI). Oxygen promoted the generation of iron (hydr)oxides, which facilitated the enrichment of Se(VI) on the ZVI particle surface. Therefore, the high oxygen fraction (25-50%) in the purging gas resulted in only a slight decrease in the ES of ZVI. Fe(II) addition resulted in a pH drop and promoted the generation of lepidocrocite and magnetite, which benefited Se(VI) adsorption and the following electron transfer from underlying Fe 0 to surface-located Se(VI).

  12. Fe biomineralization mirrors individual metabolic activity in a nitrate-dependent Fe(II-oxidizer

    Directory of Open Access Journals (Sweden)

    Jennyfer eMIOT

    2015-09-01

    Full Text Available Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is however thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had however never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry (NanoSIMS. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with 13C-acetate, we provide evidences of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasm encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a strategy of survival in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern

  13. Study of archaeological iron objects by PGAA, Mössbauer spectroscopy and X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, F. E., E-mail: fwagner@tum.de [Technische Universität München, Physik- Department E15 (Germany); Gebhard, R. [Archäologische Staatssammlung München (Germany); Häusler, W.; Wagner, U. [Technische Universität München, Physik- Department E15 (Germany); Albert, P.; Hess, H. [Archäologische Staatssammlung München (Germany); Révay, Z.; Kudejová, P.; Kleszcz, K. [Technische Universität München, Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II) (Germany)

    2016-12-15

    Archaeological iron objects often corrode rapidly after their excavation, even though they have survived long times of burial in the ground. Chlorine that accumulates during burial is thought to play a major role in this destructive post-excavation corrosion. It is therefore important for the conservation of such objects to determine the chlorine content in a non-destructive manner and, if necessary, to remove the chlorine from the artefacts by appropriate methods. Such methods are leaching in alkaline solutions or heating in a reducing atmosphere at temperatures up to 800 {sup ∘}C. We have studied the efficiency of the heating method using prompt gamma activation analysis (PGAA) for monitoring the Cl content and Mössbauer spectroscopy at room temperature (RT) and 4.2 K as well as X-ray diffraction to study the mineralogical transformations of the rust layers. The heat treatments were performed a N{sub 2}/H{sub 2} (90/10) mixture at temperatures up to 750 {sup ∘}C. As test specimens sections of iron rods from the Celtic oppidum of Manching (Bavaria) were used. The initial Cl contents of the pieces varied in the range of several hundred ppm, referring to the iron mass. Annealing for 24 h at 350, 550 and 750 {sup ∘}C was found to reduce the Cl contents of the specimens, to about 70, 30 and 15 % of the original values, respectively. The rust consists mainly of goethite with admixtures of magnetite, lepidocrocite and akaganeite, which is thought to be a major carrier of chlorine, probably together with iron chlorides. Much of the goethite is so fine-grained that it does not split magnetically at RT. Annealing converts the rust mainly to maghemite at 350 {sup ∘}C, to magnetite at 550 {sup ∘}C and to wüstite plus magnetite and metallic iron at 750 {sup ∘}C. Pure akaganeite behaves in nearly the same manner.

  14. GEOCHEMICAL CONTROLS ON NUCLEAR MAGNETIC RESONANCE MEASUREMENTS

    International Nuclear Information System (INIS)

    Knight, Rosemary

    2008-01-01

    Proton nuclear magnetic resonance (NMR) is used in the Earth Sciences as a means of obtaining information about the molecular-scale environment of fluids in porous geological materials. Laboratory experiments were conducted to advance our fundamental understanding of the link between the NMR response and the geochemical properties of geological materials. In the first part of this research project, we studied the impact of both the surface-area-to-volume ratio (S/V) of the pore space and the surface relaxivity on the NMR response of fluids in sand-clay mixtures. This study highlighted the way in which these two parameters control our ability to use NMR measurements to detect and quantify fluid saturation in multiphase saturated systems. The second part of the project was designed to explore the way in which the mineralogic form of iron, as opposed to simply the concentration of iron, affects the surface relaxation rate and, more generally, the NMR response of porous materials. We found that the magnitude of the surface relaxation rate was different for the various iron-oxide minerals because of changes in both the surface-area-to-volume ratio of the pore space, and the surface relaxivity. Of particular significance from this study was the finding of an anomalously large surface relaxivity of magnetite compared to that of the other iron minerals. Differences in the NMR response of iron minerals were seen in column experiments during the reaction of ferrihydrite-coated quartz sand with aqueous Fe(II) solutions to form goethite, lepidocrocite and magnetite; indicating the potential use of NMR as a means of monitoring geochemical reactions. The final part of the research project investigated the impact of heterogeneity, at the pore-scale, on the NMR response. This work highlighted the way in which the geochemistry, by controlling the surface relaxivity, has a significant impact on the link between NMR data and the microgeometry of the pore space.

  15. Study of archaeological iron objects by PGAA, Mössbauer spectroscopy and X-ray diffraction

    International Nuclear Information System (INIS)

    Wagner, F. E.; Gebhard, R.; Häusler, W.; Wagner, U.; Albert, P.; Hess, H.; Révay, Z.; Kudejová, P.; Kleszcz, K.

    2016-01-01

    Archaeological iron objects often corrode rapidly after their excavation, even though they have survived long times of burial in the ground. Chlorine that accumulates during burial is thought to play a major role in this destructive post-excavation corrosion. It is therefore important for the conservation of such objects to determine the chlorine content in a non-destructive manner and, if necessary, to remove the chlorine from the artefacts by appropriate methods. Such methods are leaching in alkaline solutions or heating in a reducing atmosphere at temperatures up to 800 "∘C. We have studied the efficiency of the heating method using prompt gamma activation analysis (PGAA) for monitoring the Cl content and Mössbauer spectroscopy at room temperature (RT) and 4.2 K as well as X-ray diffraction to study the mineralogical transformations of the rust layers. The heat treatments were performed a N_2/H_2 (90/10) mixture at temperatures up to 750 "∘C. As test specimens sections of iron rods from the Celtic oppidum of Manching (Bavaria) were used. The initial Cl contents of the pieces varied in the range of several hundred ppm, referring to the iron mass. Annealing for 24 h at 350, 550 and 750 "∘C was found to reduce the Cl contents of the specimens, to about 70, 30 and 15 % of the original values, respectively. The rust consists mainly of goethite with admixtures of magnetite, lepidocrocite and akaganeite, which is thought to be a major carrier of chlorine, probably together with iron chlorides. Much of the goethite is so fine-grained that it does not split magnetically at RT. Annealing converts the rust mainly to maghemite at 350 "∘C, to magnetite at 550 "∘C and to wüstite plus magnetite and metallic iron at 750 "∘C. Pure akaganeite behaves in nearly the same manner.

  16. Column study of enhanced Cr(VI) removal and longevity by coupled abiotic and biotic processes using Fe0 and mixed anaerobic culture.

    Science.gov (United States)

    Zhong, Jiawei; Yin, Weizhao; Li, Yongtao; Li, Ping; Wu, Jinhua; Jiang, Gangbiao; Gu, Jingjing; Liang, Hao

    2017-10-01

    In this study, Fe 0 and mixed anaerobic culture were integrated in one column to investigate the coupled abiotic and biotic effects on hexa-valent chromium (Cr(VI)) removal and column longevity with an abiotic Fe 0 column in the control experiments. According to the breakthrough study, a slower Cr(VI) breakthrough rate of 0.19 cm/PV was observed in the biotic Fe 0 column whereas the value in the abiotic Fe 0 column was 0.30 cm/PV, resulting in 64% longer life-span and 62% higher Cr(VI) removal capacity in the biotic Fe 0 column than the abiotic one. The solid phase characterization by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) confirmed that this enhancement was attributed to the higher consumption of iron and greater production of diverse reactive minerals (e.g., green rust, magnetite and lepidocrocite) induced by the synergistic interaction of Fe 0 and anaerobic culture, providing more reactive sites for Cr(VI) adsorption, reduction and co-precipitation. Furthermore, the decreasing breakthrough rates and growing iron corrosion along the biotic Fe 0 column demonstrated an inhomogeneous distribution of reactive zones in the column and its latter 3/5 section was considered to be the most reactive area for Cr(VI) removal. These results indicate that the inoculation of microorganisms in Fe 0 -based permeable reactive barriers will enable this technology a higher removal capacity and longer life-span for the remediation of Cr(VI)-contaminated groundwater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Potential toxic elements in stream sediments, soils and waters in an abandoned radium mine (central Portugal).

    Science.gov (United States)

    Antunes, I M H R; Neiva, A M R; Albuquerque, M T D; Carvalho, P C S; Santos, A C T; Cunha, Pedro P

    2018-02-01

    The Alto da Várzea radium mine (AV) exploited ore and U-bearing minerals, such as autunite and torbernite. The mine was exploited underground from 1911 to 1922, closed in 1946 without restoration, and actually a commercial area is deployed. Stream sediments, soils and water samples were collected between 2008 and 2009. Stream sediments are mainly contaminated in As, Th, U and W, which is related to the AV radium mine. The PTEs, As, Co, Cr, Sr, Th, U, W, Zn, and electrical conductivity reached the highest values in soils collected inside the mine influence. Soils are contaminated with As and U and must not be used for any purpose. Most waters have pH values ranging from 4.3 to 6.8 and are poorly mineralized (EC = 41-186 µS/cm; TDS = 33-172 mg/L). Groundwater contains the highest Cu, Cr and Pb contents. Arsenic occurs predominantly as H 2 (AsO 4 ) - and H(AsO 4 ) 2- . Waters are saturated in goethite, haematite and some of them also in lepidocrocite and ferrihydrite, which adsorbs As (V). Lead is divalent in waters collected during the warm season, being mobile in these waters. Thorium occurs mainly as Th(OH) 3 (CO 3 ) - , Th(OH) 2 (CO 3 ) and Th(OH) 2 (CO 3 ) 2 2- , which increase water Th contents. Uranium occurs predominantly as UO 2 CO 3 , but CaUO 2 (CO 3 ) 3 2- and CaUO 2 (CO 3 ) 3 also occur, decreasing its mobility in water. The waters are contaminated in NO 2 - , Mn, Cu, As, Pb and U and must not be used for human consumption and in agricultural activities. The water contamination is mainly associated with the old radium mine and human activities. A restoration of the mining area with PTE monitoring is necessary to avoid a public hazard.

  18. Deposition of Coating to Protect Waste Water Reservoir in Acidic Solution by Arc Thermal Spray Process

    Directory of Open Access Journals (Sweden)

    Han-Seung Lee

    2018-01-01

    Full Text Available The corrosion characteristics of 304 stainless steel (SS and titanium (Ti coatings deposited by the arc thermal spray process in pH 4 solution were assessed. The Ti-sprayed coating exhibits uniform, less porous, and adherent coating morphology compared to the SS-sprayed coating. The electrochemical study, that is, electrochemical impedance spectroscopy (EIS, revealed that as exposure periods to solution were increased, the polarization resistance (Rp decreased and the charge transfer resistance (Rct increased owing to corrosion of the metallic surface and simultaneously at the same time the deposition of oxide films/corrosion on the SS-sprayed surface, while Ti coating transformed unstable oxides into the stable phase. Potentiodynamic studies confirmed that both sprayed coatings exhibited passive tendency attributed due to the deposition of corrosion products on SS samples, whereas the Ti-sprayed sample formed passive oxide films. The Ti coating reduced the corrosion rate by more than six times compared to the SS coating after 312 h of exposure to sulfuric acid- (H2SO4- contaminated water solution, that is, pH 4. Scanning electron microscope (SEM results confirmed the uniform and globular morphology of the passive film on the Ti coating resulting in reduced corrosion. On the other hand, the corrosion products formed on SS-sprayed coating exhibit micropores with a net-like microstructure. X-ray diffraction (XRD revealed the presence of the composite oxide film on Ti-sprayed samples and lepidocrocite (γ-FeOOH on the SS-coated surface. The transformation of TiO and Ti3O into TiO2 (rutile and anatase and Ti3O5 after 312 h of exposure to H2SO4 acid reveals the improved corrosion resistance properties of Ti-sprayed coating.

  19. In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal.

    Science.gov (United States)

    Dubrawski, Kristian L; Mohseni, Madjid

    2013-09-15

    In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1-25 mA/cm(2) and CLR in a range of 12-300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm(2)) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe3O4) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Evaluation of corrosiveness grade of the main pipeline system within the machine-room of the Cen Juragua

    International Nuclear Information System (INIS)

    Camacho C, J.; Corvo P, F.

    1998-01-01

    It is realized a study of the corrosion process and the products formed over the carbon steel in different points of the machine-room of the Electronuclear plant of Juragua (Cuba) particularly in the pipelines considering the specific characteristics of corrosion under roof which has been less studied. The determination of corrosiveness grade was carried out by gravimetric methods (lost and gain weight) in the different coats of the machine-room not existing a correlation between them in according to results with those ones obtained by Infrared Spectroscopy, in which there is not a correlation between the band intensities (lepidocrocite/ goethite) and the corrosion; however both explain different parts of corrosive process. Also it is realized the corrosion products analysis by chemical methods and by Atomic Absorption Spectrometry, obtaining the concentration of the major anions and cations of importance for the corrosion, not existing a meaning correlation between them and the corrosion velocity by what it was determined the absorption isotherms, obtaining as result a microporous structure in the formed oxides which was capable to retain and to absorb water and pollutants which could be this the main cause of corrosion. By analyzing the high concentration of iron and the low concentration of the remainder anions and cations it is possible to make the traditional chemical washes which are less expensive and greater effectiveness. All the obtained results are very important to assure the conditions of the pipelines systems installed at the presence of Government and Foreign organizations which are interested for the protection and conservation measures in the pipelines system. (Author)

  1. Study of archaeological iron objects by PGAA, Mössbauer spectroscopy and X-ray diffraction

    Science.gov (United States)

    Wagner, F. E.; Gebhard, R.; Häusler, W.; Wagner, U.; Albert, P.; Hess, H.; Révay, Z.; Kudejová, P.; Kleszcz, K.

    2016-12-01

    Archaeological iron objects often corrode rapidly after their excavation, even though they have survived long times of burial in the ground. Chlorine that accumulates during burial is thought to play a major role in this destructive post-excavation corrosion. It is therefore important for the conservation of such objects to determine the chlorine content in a non-destructive manner and, if necessary, to remove the chlorine from the artefacts by appropriate methods. Such methods are leaching in alkaline solutions or heating in a reducing atmosphere at temperatures up to 800 ∘C. We have studied the efficiency of the heating method using prompt gamma activation analysis (PGAA) for monitoring the Cl content and Mössbauer spectroscopy at room temperature (RT) and 4.2 K as well as X-ray diffraction to study the mineralogical transformations of the rust layers. The heat treatments were performed a N2/H2 (90/10) mixture at temperatures up to 750 ∘C. As test specimens sections of iron rods from the Celtic oppidum of Manching (Bavaria) were used. The initial Cl contents of the pieces varied in the range of several hundred ppm, referring to the iron mass. Annealing for 24 h at 350, 550 and 750 ∘C was found to reduce the Cl contents of the specimens, to about 70, 30 and 15 % of the original values, respectively. The rust consists mainly of goethite with admixtures of magnetite, lepidocrocite and akaganeite, which is thought to be a major carrier of chlorine, probably together with iron chlorides. Much of the goethite is so fine-grained that it does not split magnetically at RT. Annealing converts the rust mainly to maghemite at 350 ∘C, to magnetite at 550 ∘C and to wüstite plus magnetite and metallic iron at 750 ∘C. Pure akaganeite behaves in nearly the same manner.

  2. WATEQ3 geochemical model: thermodynamic data for several additional solids

    International Nuclear Information System (INIS)

    Krupka, K.M.; Jenne, E.A.

    1982-09-01

    Geochemical models such as WATEQ3 can be used to model the concentrations of water-soluble pollutants that may result from the disposal of nuclear waste and retorted oil shale. However, for a model to competently deal with these water-soluble pollutants, an adequate thermodynamic data base must be provided that includes elements identified as important in modeling these pollutants. To this end, several minerals and related solid phases were identified that were absent from the thermodynamic data base of WATEQ3. In this study, the thermodynamic data for the identified solids were compiled and selected from several published tabulations of thermodynamic data. For these solids, an accepted Gibbs free energy of formation, ΔG 0 /sub f,298/, was selected for each solid phase based on the recentness of the tabulated data and on considerations of internal consistency with respect to both the published tabulations and the existing data in WATEQ3. For those solids not included in these published tabulations, Gibbs free energies of formation were calculated from published solubility data (e.g., lepidocrocite), or were estimated (e.g., nontronite) using a free-energy summation method described by Mattigod and Sposito (1978). The accepted or estimated free energies were then combined with internally consistent, ancillary thermodynamic data to calculate equilibrium constants for the hydrolysis reactions of these minerals and related solid phases. Including these values in the WATEQ3 data base increased the competency of this geochemical model in applications associated with the disposal of nuclear waste and retorted oil shale. Additional minerals and related solid phases that need to be added to the solubility submodel will be identified as modeling applications continue in these two programs

  3. Lead corrosion and transport in simulated secondary feedwater

    Energy Technology Data Exchange (ETDEWEB)

    McGarvey, G.B. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Ross, K.J.; McDougall, T.E. [Atomic Energy of Canada Limited, Pinawa, Manitoba (Canada); Turner, C.W. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada)

    1998-07-01

    The ubiquitous presence of lead at trace levels in secondary feedwater is a concern to all operators of steam generators and has prompted laboratory studies of its interaction with Inconel 600, Inconel 690, Monel 400 and Incoloy 800. Acute exposures of steam generator alloys to high levels of,lead in the laboratory and in the field have accelerated the degradation of these alloys. There is some disagreement over the role of lead when the exposure is to chronic levels. It has been proposed that most of the present degradation of steam generator tubes is due to low levels of lead although few if any failures have been experimentally linked to lead when sub-parts per billion levels are present in the feedwater. One reason for the difficulty in assigning the role of the lead is related to its possible immobilization on the surfaces of corrosion products or iron oxide films in the feedwater system. We have measured lead adsorption profiles on the three principal corrosion products in the secondary feedwater; magnetite, lepidocrocite and hematite. In all cases, essentially complete adsorption of the lead is achieved at pH values less than that of the feedwater (9-10). If lead is maintained in this adsorbed state, it may be more chemically benign than lead that is free to dissolve in the feedwater and subsequently adsorb on steam generator tube surfaces. In this paper, we report on lead adsorption onto simulated corrosion products under simulated feedwater conditions and propose a physical model for the transport and fate of lead under operating conditions. The nature of lead adsorption onto the surfaces of different corrosion products will be discussed. The desorption behaviour of lead from iron oxide surfaces following different treatment conditions will be used to propose a model for tile transport and probable fate of lead in the secondary feedwater system. (author)

  4. Lead corrosion and transport in simulated secondary feedwater

    Energy Technology Data Exchange (ETDEWEB)

    McGarvey, G.B. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Ross, K.J.; McDougall, T.E. [Atomic Energy of Canada Limited, Pinawa, Manitoba (Canada); Turner, C.W

    1999-07-01

    The ubiquitous presence of lead at trace levels in secondary feedwater is a concern to all operators of steam generators and has prompted laboratory studies of its interaction with Inconel 600, Inconel 690, Monel 400 and Incoloy 800. Acute exposures of steam generator alloys to high levels of lead in the laboratory and in the field have accelerated the degradation of these alloys. There is some disagreement over the role of lead when the exposure is to chronic levels. It has been proposed that most of the present degradation of steam generator tubes is caused by low levels of lead although few, if any, failures have been experimentally linked to lead when it is present in sub-parts per billion in the feedwater. One reason for the difficulty in assigning the role of the lead is related to its possible immobilization on the surfaces of corrosion products or iron oxide films in the feedwater system. We have measured lead adsorption profiles on the 3 principal corrosion products in the secondary feedwater: magnetite, lepidocrocite and hematite. In all cases, essentially complete adsorption of the lead is achieved at pH values that are lower than the pH of the feedwater (9 to 10). If lead is maintained in this adsorbed state, it may be more chemically benign than lead that is free to dissolve in the feedwater and subsequently adsorb on steam generator tube surfaces. In this paper, we report on lead adsorption onto simulated corrosion products under simulated feedwater conditions and propose a physical model for the transport and fate of lead under operating conditions. The nature of lead adsorption onto the surfaces of different corrosion products will be discussed. The desorption behaviour of lead from iron oxide surfaces after different treatment conditions will be used to propose a model for the transport and probable fate of lead in the secondary feedwater system. (author)

  5. Phase analysis of corrosion products of carbon steel in sea water

    International Nuclear Information System (INIS)

    Garcia R, J.; Yee M, H.; Maldonado M, H.; Nunez, L.; Reguera, E.

    1998-01-01

    Nowadays carbon steel continues being the most widely used metallic material in marine and coastal buildings. The economic losses, due to corrosion processes, of those countries with important industrial and social activities in coastal regions are highly significant. In this sense the evaluation of the corrosion process of carbon steel and other materials in seawater or in coastal zones is a primary task for protection methods or to predict the hfe of an specific installation. In this communication we present the phases analysis, using XRD and Moessbauer techniques, of corrosion products of a carbon steel (CT3, equivalent to AISI C1020) exposed in two natural corrosion stations in the Caribbean sea (Cuba). The exposition time run from days to 36 months and the evaluated rust are characteristic of samples totally immersed in seawater, from the splash zone and form coastal zones at different distance from the shoreline. Quantitative phase analysis shown presence of magnetite (Fe 3 O 4 ), maghemite (y-Fe 2 O 3 ), akaganeite (B-FeOOH), lepidocrocite (y-FeOOH) and goethite (a-FeOOH) as iron bearing phases, and CaCO 3 (Calcite and aragonite), these last ones mainly in the immersed samples. Quantitative phase analysis by XRD was implemented as a linear combination of the patterns characteristic of all the detected phases and an appropriate model for the background. The quantitative results were used in kinetic models to understand the phase transformation between the iron oxides and oxy hydroxides in the studied conditions. The XRD qualitative and quantitative results were corroborated by Moessbauer spectroscopy in the temperature range of 20 to 300 K. (Author)

  6. Rhenium Uptake as Analogue 96Tc by Steel Corrosion Products

    International Nuclear Information System (INIS)

    K.M. Krupka; C.F. Brown; H. Todd Schaef; S. M. Heald; M. M. Valenta; B. W. Arey

    2006-01-01

    Static batch experiments were used to examine the sorption of dissolved perrhenate [Re(VII)], as a surrogate for pertechnetate [Tc(VII)], on corrosion products of A-516 carbon steel coupons contacted with synthetic groundwater or dilute water. After 109 days of contact time, the concentration of dissolved Re(VII) in the synthetic groundwater matrix decreased by approximately 26%; the dilute water matrix experienced a 99% decrease in dissolved Re(VII) over the same time period. Bulk x-ray diffraction (XRD) results for the corroded steel coupons showed that the corrosion products consisted primarily of maghemite, lepidocrocite, and goethite. Analyses of the coupons by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) indicated that Re was present with the morphologically complex assemblages of Fe oxide/hydroxide corrosion products for samples spiked with the highest dissolved Re(VII) concentration (1.0 mmol/L) used for these experiments. Analyses of corroded steel coupons contacted with solutions containing 1.0 mmol/L Re(VII) by synchrotron-based methods confirmed the presence of Re sorbed with the corrosion product on the steel coupons. Analyses showed that the Re sorbed on these corroded coupons was in the +7 oxidation state, suggesting that the Re(VII) uptake mechanism did not involve reduction of Re to a lower oxidation state, such as +4. The results of our studies using Re(VII) as an analogue for 99 Tc(VII) suggest that 99 Tc(VII) would also be sorbed with steel corrosion products and that the inventory of 99 Tc(VII) released from breached waste packages would be lower than what is now conservatively estimated

  7. Removal of arsenite from water by synthetic siderite: Behaviors and mechanisms

    International Nuclear Information System (INIS)

    Guo Huaming; Li Yuan; Zhao Kai; Ren Yan; Wei Chao

    2011-01-01

    Synthetic siderite has been used as adsorbent for As(III) removal in this study. Effects of contact time, temperature, pH, co-existing anions on As(III) adsorption were intensively investigated. Adsorption mechanisms were also studied using the X-ray absorption technique. Results show that the maximum adsorption capacity is up to 9.98 mg g -1 at 25 deg, C at a siderite dosage of 2 g L -1 . Adsorption kinetics agrees with the Lagergren pseudo-second order model. Arsenic(III) adsorption can be better described by Langmuir isotherm model for As(III) adsorption at 55 deg. C, indicating that the coverage of the adsorption sites is in the form of monolayer, although Freundlich isotherm yields a better fit to the experimental data at 25, 35 and 45 deg. C. Thermodynamic study indicates that As(III) adsorption on the synthetic siderite is spontaneous and endothermic in nature. The adsorption capacity is enhanced with the increase in reaction temperature. The adsorption is independent on solution pH between 3.0 and 9.6. The presence of NO 3 - , SO 4 2- , PO 4 3- or SiO 3 2- with element concentrations less than 20 mg L -1 does not have adverse effect on As(III) adsorption. XANES spectra indicate that As mainly occurs as As(V) in the As adsorbed-materials, and the fraction of oxidized As(III) increases with the decrease in As(III) concentration. The formation of Fe hydroxide minerals (such as lepidocrocite and goethite) followed by As(III) oxidiation and adsorption is shown to be the main mechanism of As(III) removal by the synthetic siderite.

  8. Lead corrosion and transport in simulated secondary feedwater

    International Nuclear Information System (INIS)

    McGarvey, G.B.; Ross, K.J.; McDougall, T.E.; Turner, C.W.

    1998-01-01

    The ubiquitous presence of lead at trace levels in secondary feedwater is a concern to all operators of steam generators and has prompted laboratory studies of its interaction with Inconel 600, Inconel 690, Monel 400 and Incoloy 800. Acute exposures of steam generator alloys to high levels of,lead in the laboratory and in the field have accelerated the degradation of these alloys. There is some disagreement over the role of lead when the exposure is to chronic levels. It has been proposed that most of the present degradation of steam generator tubes is due to low levels of lead although few if any failures have been experimentally linked to lead when sub-parts per billion levels are present in the feedwater. One reason for the difficulty in assigning the role of the lead is related to its possible immobilization on the surfaces of corrosion products or iron oxide films in the feedwater system. We have measured lead adsorption profiles on the three principal corrosion products in the secondary feedwater; magnetite, lepidocrocite and hematite. In all cases, essentially complete adsorption of the lead is achieved at pH values less than that of the feedwater (9-10). If lead is maintained in this adsorbed state, it may be more chemically benign than lead that is free to dissolve in the feedwater and subsequently adsorb on steam generator tube surfaces. In this paper, we report on lead adsorption onto simulated corrosion products under simulated feedwater conditions and propose a physical model for the transport and fate of lead under operating conditions. The nature of lead adsorption onto the surfaces of different corrosion products will be discussed. The desorption behaviour of lead from iron oxide surfaces following different treatment conditions will be used to propose a model for tile transport and probable fate of lead in the secondary feedwater system. (author)

  9. Indoor atmospheric corrosion of historical ferrous alloys. System characterisation, mechanisms and modelling discussion

    International Nuclear Information System (INIS)

    Monnier, J.

    2008-12-01

    Understanding the mechanisms of indoor atmospheric corrosion in iron alloys is of primary importance in several fields, including for the conservation of Middle Ages monuments or the long term storage of nuclear waste. In this research, a double approach was developed, combining fine characterisation of corrosion systems and design of experiments to answers specific questions related to mechanisms understanding. Iron indoor atmospheric corrosion was investigated on samples coming from the reinforcing chain of the Amiens cathedral (15. century). In the first stage, the corrosion system has been extensively characterised from the macroscopic to the nano-metric scale. In particular, structural micro-analysis (μ-Raman, μ-XRD, μ-XAS) has been used to locate, identify and quantify the oxidised phases. Rust layers are composed of a matrix of nano-metric goethite, with low quantities of lepidocrocite and akaganeite mostly located in the extern part of the corrosion system. In addition, clear marblings are dispersed in the matrix, which are sometimes connected with the metal core. Although these may contain maghemite, these marblings are generally made of ferri-hydrite/feroxyhite phases. In the second stage, specific experiments have been carried out in an unsaturated marked medium to locate oxygen reduction sites in the rust layers. Several cases were evidenced, depending on the rust layer morphology. In addition, reduction processes of model phases have been studied in situ, using an electrochemical cell coupled with structural characterisation techniques. This combination highlighted the influence of reduction mode and pH on the type of reduced phase formed. From the obtained results, several mechanisms are proposed to explain the long term indoor atmospheric corrosion of iron, including rust layers morphology and phases properties. The different hypotheses have been integrated in a proposed method to diagnosis ancient ferrous systems stability. These hypotheses also

  10. The effect of surface chemistry on particulate fouling under flow-boiling conditions

    International Nuclear Information System (INIS)

    Turner, C.W.; Klimas, S.J.

    2001-01-01

    A model of particulate fouling has been developed that takes account of the influence of deposit consolidation on the kinetics of the fouling process. Fouling kinetics predicted by the model are linear, falling-rate or asymptotic, depending on the relative magnitudes of the rate constants for deposition, re-entrainment, and consolidation. One of the key predictions of the model is that the steady-state fouling rate is proportional to the ratio Kλ c /λ, where K, λ c and λ are the rate constants for deposition, consolidation, and removal, respectively. Tests conducted in a high-temperature recirculating-water loop have demonstrated that chemistry exerts a strong influence on the fouling kinetics of particulate corrosion product under flow-boiling conditions in alkaline water at 270 o C. For example, the fouling rates of lepidocrocite and hematite are 12 and 50 times greater, respectively, than the rate for magnetite. It is argued that the difference can be attributed to the sign of the surface charge that develops on the metal oxide surfaces in the high-temperature coolant, which, in turn, is a function of pH relative to the isoelectric point of the metal oxide. Chemical effects also influence fouling behaviour through the rate of consolidation. For example, when morpholine is used for the alkalizing agent the fouling rate is 3-5 times higher than the case when the pH is controlled using dimethylamine. The difference is attributed to the rate of deposit consolidation, which is 6-20 times greater than the rate of deposit removal for morpholine compared to 0.2-0.3 times the rate of removal for dimethylamine. The results of this investigation, together with the insights provided by the fouling model, are being used to guide the selection of the alkalizing amine to optimize its properties for both corrosion (pH) control and deposit control in the steam generator. (author)

  11. Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

    International Nuclear Information System (INIS)

    Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

    2005-01-01

    Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganeite, lepidocrocite and magnetite. Among these iron oxides, akaganeite in particular is the major component in the rust. Additionally, the amount of akaganeite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganeite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganeite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganeite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel. (author)

  12. Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.

    Science.gov (United States)

    Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi

    2015-01-01

    Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in

  13. Ceres Revealed in a Grain of Salt

    Science.gov (United States)

    Zolensky, M. E.; Bodnar, R. J.; Fries, M.; Chan, Q. H.-S.; Kebukawa, Y.; Mikouchi, T.; Hagiya, K.; Komatsu, M.; Ohsumi, K.; Steele, A.

    2016-01-01

    Introduction: Zag and Monahans (1998) are H chondrite regolith breccias containing 4.5 giga-year-old halite crystals which contain abundant inclusions of aqueous fluids, solids and organics. These all originated on a cryo-volcanically-active C class asteroid, probably 1 Ceres; the halite was transported to the regolith of the H chondrite parent asteroid, potentially 6 Hebe. Detailed analysis of these solids will thus potentially reveal the mineralogy of Ceres. Mineralogy of solids in the Monahans Halite Solid grains are present in the halites, which were entrained within the mother brines during eruption, including material from the interior and surface of the erupting body. The solids include abundant, widely variable organics that could not have been significantly heated (which would have resulted in the loss of fluids from the halite). Our analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction, UPLC-FD/QToF-MS, C-XANES and TEM reveal that these trapped grains include macromolecular carbon (MMC) similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99-59), high- and low-Ca pyroxene, feldspars, phyllosilicates, magnetite, sulfides, metal, lepidocrocite, carbonates, diamond, apatite and zeolites. Conclusions: The halite in Monahans and Zag derive from a water and carbon-rich object that was cryo-volcanically active in the early solar system, probably Ceres. The Dawn spacecraft found that Ceres includes C chondrite materials. Our samples include both protolith and aqueously-altered samples of the body, permitting understanding of alteration conditions. Whatever the halite parent body, it was rich in a wide variety of organics and warm, liquid water at the solar system's dawn.

  14. Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia.

    Science.gov (United States)

    Hiller, Edgar; Petrák, Marián; Tóth, Roman; Lalinská-Voleková, Bronislava; Jurkovič, L'ubomír; Kučerová, Gabriela; Radková, Anežka; Sottník, Peter; Vozár, Jaroslav

    2013-11-01

    mineral assemblage and their occurrence follows the order: chalcopyrite > pyrite > tetrahedrite>arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16-8.12) and the waters (pH 7.00-8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu>Sb>Hg>As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52-7.96) and low concentrations of dissolved metal(loid)s (tailings impoundment.

  15. A single-source solid-precursor method for making eco-friendly doped semiconductor nanoparticles emitting multi-color luminescence.

    Science.gov (United States)

    Manzoor, K; Aditya, V; Vadera, S R; Kumar, N; Kutty, T R N

    2007-02-01

    A novel synthesis method is presented for the preparation of eco-friendly, doped semiconductor nanocrystals encapsulated within oxide-shells, both formed sequentially from a single-source solid-precursor. Highly luminescent ZnS nanoparticles, in situ doped with Cu(+)-Al3+ pairs and encapsulated with ZnO shells are prepared by the thermal decomposition of a solid-precursor compound, zinc sulfato-thiourea-oxyhydroxide, showing layered crystal structure. The precursor compound is prepared by an aqueous wet-chemical reaction involving necessary chemical reagents required for the precipitation, doping and inorganic surface capping of the nanoparticles. The elemental analysis (C, H, N, S, O, Zn), quantitative estimation of different chemical groups (SO4(2-) and NH4(-)) and infrared studies suggested that the precursor compound is formed by the intercalation of thiourea, and/or its derivatives thiocarbamate (CSNH2(-)), dithiocarbamate (CS2NH2(-)), etc., and ammonia into the gallery space of zinc-sulfato-oxyhydroxide corbel where the Zn(II) ions are both in the octahedral as well as tetrahedral coordination in the ratio 3 : 2 and the dopant ions are incorporated within octahedral voids. The powder X-ray diffraction of precursor compound shows high intensity basal reflection corresponding to the large lattice-plane spacing of d = 11.23 angstroms and the Rietveld analysis suggested orthorhombic structure with a = 9.71 angstroms, b = 12.48 angstroms, c = 26.43 angstroms, and beta = 90 degrees. Transmission electron microscopy studies show the presence of micrometer sized acicular monocrystallites with prismatic platy morphology. Controlled thermolysis of the solid-precursor at 70-110 degrees C leads to the collapse of layered structure due to the hydrolysis of interlayer thiourea molecules or its derivatives and the S2- ions liberated thereby reacts with the tetrahedral Zn(II) atoms leading to the precipitation of ZnS nanoparticles at the gallery space. During this process

  16. Changes of porosity due to weathering in quartzites and slates of a Raña profile (Montes de Toledo, Central Spain

    Directory of Open Access Journals (Sweden)

    Molina Ballesteros, E.

    2013-12-01

    Full Text Available Rañas are alluvial fan deposits of Plio-Pleistocene age that form the piedmont platforms around the mountains in the interior of the Iberian Peninsula. They are composed of cobbles, pebbles and gravels of quartzite and some quartz, all embedded within a clayey matrix displaying striking changes in hues due to hydromorphism. Beneath these platforms, the Hercynian basement is consistently deeply weathered. In the profile of the Raña, the quartzite stones located into the clayey horizon have a weathering rind that is whitish to ochre in colour, in contrast to the dark reddish hue of those located within the leaching horizon, just below the land surface. These differences are related to changes in the physical properties (e.g., bulk density and porosity, mineralogy (presence of oxyhydroxides and weathering processes that have taken place in the profile. Such processes have led to the corrosion and replacement of the quartz grains by the iron oxyhydroxides. The main cause is the dramatic changes in the water regime occurring in the pores at the surfaces of the quartzite stones. Due to weathering the slates outcropping beneath the Raña have undergone important release of matter (ca. 30%, together with changes in the mineral association, with a progressive reduction in the component of the unweathered slates and an increase in new minerals (smectites, kaolinite and iron oxyhydroxides upwards.Las Rañas son depósitos de abanicos aluviales del Plio-Pleistoceno que forman plataformas de piedemonte alrededor de las montanas del interior de la Peninsula Iberica. Estan formadas de bloques, cantos y gravas de cuarcita dominantes y algún cuarzo engastados en una matriz arcillosa que muestra importantes contrastes de color causados por hidromorfismo. Bajo estas plataformas, el zocalo hercinico se encuentra profundamente alterado. En un perfil de Rana se distinguen dos tipos de horizontes: i el superior, de pocos decimetros de grosor, rico en cantos, gravas

  17. High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the NABIR Field-Research Center

    International Nuclear Information System (INIS)

    David R. Veblen; Chen Zhu; Lee Krumholz; Claudine Stirling; Emma-Kate Potter; Alex N. Halliday

    2004-01-01

    The effectiveness and feasibility of bioremediation at the field scale cannot be fully assessed until the mechanisms of immobilization and U speciation in the solid matrix are resolved. However, characterization of the immobilized U and its valence states is extremely difficult, because microbially mediated mineral precipitates are generally nanometer (nm)-sized, poorly crystalline, or amorphous. We are developing combined field emission gun--scanning electron microscopy (FEG-SEM, at Indiana University) and FEG transmission electron microscopy (TEM, at Hopkins) to detect and isolate uranium containing phases; (1) method developments for TEM sample preparations and parallel electron energy loss spectroscopy (EELS) determination of uranium valence; and (2) to determine the speciation, fate, reactivity, valence states of immobilized uranium, using the state-of-the-art 300-kV, FEG-TEM. We have obtained preliminary results on contaminated sediments from Area 3 at the Oak Ridge Field Research Center (FRC). TEM results show that the sediments contain numerous minerals, including quartz, mica/clay (muscovite and/or illite), rutile, ilmenite, zircon, and an Al-Sr-Ce-Ca phosphate mineral, none of which contain uranium above the EDS detection limit. Substantial U (up to ∼2 wt.%) is, however, clearly associated with two materials: (1) the Fe oxyhydroxide and (2) clots of a chemically complex material that is likely a mixture of several nm-scale phases. The Fe oxyhydroxide was identified as goethite from its polycrystalline SAED pattern and EDS analysis showing it to be very Fe-rich; the aggregate also displays one of several morphologies that are common for goethite. U is strongly sorbed to goethite in the FRC sediment, and the ubiquitous association with phosphorous suggests that complexes containing both U and P may play an important role in that sorption. Results from bulk analysis and SEM had previously demonstrated the association of U with Fe and thus suggested that U

  18. Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

    Science.gov (United States)

    Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

    2015-02-01

    ões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.

  19. Nutrient transport and transformation beneath an infiltration basin

    Science.gov (United States)

    Sumner, D.M.; Rolston, D.E.; Bradner, L.A.

    1998-01-01

    Field experiments were conducted to examine nutrient transport and transformation beneath an infiltration basin used for the disposal of treated wastewater. Removal of nitrogen from infiltrating water by denitrification was negligible beneath the basin, probably because of subsurface aeration as a result of daily interruptions in basin loading. Retention of organic nitrogen in the upper 4.6 m of the unsaturated zone (water table depth of approximately 11 m) during basin loading resulted in concentrations of nitrate as much as 10 times that of the applied treated wastewater, following basin 'rest' periods of several weeks, which allowed time for mineralization and nitrification. Approximately 90% of the phosphorus in treated wastewater was removed within the upper 4.6 m of the subsurface, primarily by adsorption reactions, with abundant iron and aluminum oxyhydroxides occurring as soil coatings. A reduction in the flow rate of infiltrating water arriving at the water table may explain the accumulation of relatively coarse (>0.45 ??m), organic forms of nitrogen and phosphorus slightly below the water table. Mineralization and nitrification reactions at this second location of organic nitrogen accumulation contributed to concentrations of nitrate as much as three times that of the applied treated wastewater. Phosphorus, which accumulated below the water table, was immobilized by adsorption or precipitation reactions during basin rest periods.Field experiments were conducted to examine nutrient transport and transformation beneath an infiltration basin used for the disposal of treated wastewater. Removal of nitrogen from infiltrating water by denitrification was negligible beneath the basin, probably because of subsurface aeration as a result of daily interruptions in basin loading. Retention of organic nitrogen in the upper 4.6 m of the unsaturated zone (water table depth of approximately 11 m) during basin loading resulted in concentrations of nitrate as much as 10

  20. Organic petrology, mineralogy and depositional environment of the Kipra lignite seam, Maritza-West basin, Bulgaria

    Energy Technology Data Exchange (ETDEWEB)

    Kostova, Irena [Department of Geology and Palaeontology, Sofia University ' ' St. Kliment Ohridski' ' , 1000, Sofia (Bulgaria); Zdravkov, Alexander [Department of Economic Geology, University of Mining and Geology ' ' St. Ivan Rilski' ' , 1700, Sofia (Bulgaria)

    2007-08-01

    concentrations. These minerals formed syngenetically and epigenetically. The syngenetic stage is characterized mainly by the formation of pyrite, carbonates, silicates and sulphates, whereas the Fe-oxyhydroxides, partially the carbonates and almost all silicates are of detrital origin. During the epigenetic stage, carbonates, sulphates, clay minerals, pyrite, and Fe-oxyhydroxides were formed. Alteration products like gypsum, jarosite, limonite, chlorite, kaolinite, illite, mica, and calcite were generated due to the transformation of detrital and authigenic minerals. (author)

  1. A kinetic model that explains the dependence of magnetic susceptibility of sediment on grain size and organic matter content in transitional marine environments. Testing case studies in estuarine-like environments of NW Iberia

    Science.gov (United States)

    Rey, D.; Mohamed, K. J.; Andrade, A.; Rubio, B.; Bernabeu, A. M.

    2017-12-01

    The wide use of magnetic proxies to study pollution, sedimentological processes, and environmental and paleoclimatic changes is currently limited by the lack of transference functions that closely correlate with the unmeasurable variables. Among them, magnetic susceptibility (MS) is the oldest and most popular, but have yet to live up to its expectations. This paper explores and quantifies how MS values of surficial sediments in transitional environments depends on grain size and on what can be said about the spatial distribution of hydrodynamic forces and the potential modulation of MS by sediment and organic matter provenances. The concentration of (oxyhydr)oxides in sands (d50 > 63 microns) is primarily controlled by their degree of dilution in the diamagnetic framework, which is larger for coarser grainsizes. In contrast, the concentration of (oxyhydr)oxides in muddy sediments is controlled by their dissolution rate during very early diagenesis, which is controlled by their content in organic matter (TOC), inversely dependent of grainsize. The balance between both components results in the study area in sands of d50 = 68 microns displaying the maximum MS values. The influence of organic matter on the dissolution of magnetite in surficial sediments can be quantified using a simple kinetic model. The model reveals the existence of a negative exponential relationship between magnetic susceptibility and grain size, that depends on the TOC of the fine-grained fraction. The model accurately predicts that a TOC increase of 0.35% results in a 50% reduction in the concentration of magnetite in the sediments of the Ría the Muros. We have also encountered this relationship not universal in this form, as its quantification is strongly modulated by coarse sediment mineralogy, TOC lability and by other factors such as wave climate, depth, and sediment oxygenation. Better understanding and quantification of the role that TOC, hydrodynamics, and changes in the geochemical

  2. Tellurium Stable Isotopes as a Paleoredox Proxy

    Science.gov (United States)

    Wasserman, N.; Johnson, T. M.

    2017-12-01

    Despite arguments for variably-oxygenated shallow waters and anoxic deep marine waters, which delayed animal development until the Neoproterozoic Oxidation Event, the magnitude of atmospheric oxygen during the Proterozoic is still uncertain [1]. The evidence for low pO2 (<0.1-1% PAL) is based on geochemical and isotopic proxies, which track the mobilization of Fe and Mn on the continents. For example, large chromium isotope shifts occur at the Neoproterozoic Oxidation Event due to the initiation of Cr redox cycling, but this proxy is insensitive to fluctuations in the lower-pO2 conditions at other times during the Proterozoic. Tellurium, a metalloid with a lower threshold to oxidation, may be sensitive to pO2 shifts in a lower range. In the reduced forms, Te(-II) and Te(0), the element is insoluble and immobile. However, in the more oxidized phases, Te(IV) and Te(VI), Te can form soluble oxyanions (though it tends to adsorb to Fe-oxyhydroxides and clays) [2]. Te stable isotopes have been shown to fractionate during abiotic or biologic reduction of Te(VI) or Te(IV) to elemental Te(0) [3, 4]. Utilizing hydride generation MC-ICP-MS, we are able to obtain high precision (2σ 0.04‰) measurements of δ128Te/125Te for natural samples containing < 10 ng of Te. A suite of Phanerozoic and Proterozoic ironstones show significant variation in δ128Te/125Te (<0.5‰), suggesting that the Te redox cycle was active during the Proterozoic. Future directions will include Te isotope measurements of Precambrian paleosols to determine natural isotope variation before the Great Oxidation Event and experiments to determine fractionation during adsorption to Fe-oxyhydroxides. [1] Planavsky et al. (2014) Science 346 (6209), pp. 635-638 [2] Qin et al. (2017) Environmental Science and Technology 51 (11), pp 6027-6035 [3] Baesman et al. (2007) Applied Environmental Microbiology 73 (7), pp 2135-2143 [4] Smithers and Krause (1968) Canadian Journal of Chemistry 46(4): pp 583-591

  3. Chemical processes for the extreme enrichment of tellurium into marine ferromanganese oxides

    Science.gov (United States)

    Kashiwabara, Teruhiko; Oishi, Yasuko; Sakaguchi, Aya; Sugiyama, Toshiki; Usui, Akira; Takahashi, Yoshio

    2014-04-01

    Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation. This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as

  4. Influence of boat material on the structure, stoichiometry and optical properties of gallium sulphide films prepared by thermal evaporation

    International Nuclear Information System (INIS)

    Rao, Pritty; Kumar, Sanjiv; Sahoo, N.K.

    2015-01-01

    The paper describes the deposition of thin films of gallium sulphide on soda-lime glass substrates by thermal evaporation of chemically synthesized powders consisting of gallium sulphide and gallium oxyhydroxide from a Mo or Ta boat and the evolution of their compositional, structural and optical properties on vacuum annealing. The films deposited from Mo or Ta boats possessed distinctly different properties. The Mo-boat evaporated pristine films were amorphous, transparent (α ∼ 10 3  cm −1 ) in visible region and had a direct band gap of about 3.2 eV. Vacuum annealing at 723 K brought about their crystallization predominantly into cubic γ-Ga 2 S 3 and a blue shift by about 0.2 eV. The Ta-boat evaporated pristine films were also amorphous but were absorbing (α ∼ 10 4  cm −1 ) and had a direct band gap of about 2.1 eV. These crystallized into hexagonal GaS and experienced a blue shift by more than 1.0 eV on vacuum annealing at 723 K. The dissimilar properties of the two kinds of films arose mainly from their different atomic compositions. The Mo-boat evaporated pristine films contained Ga and S in ∼1:1 atomic proportions while those prepared using Ta-boat were Ga rich which impaired their transmission characteristics. The former composition favoured the stabilization of S rich gallium sulphide (Ga 2 S 3 ) phase while the latter stabilised S deficient species, GaS. Besides inducing crystallization, vacuum annealing at 723 K also caused the diffusion of Ga in excess of atomic composition of the phase formed, into soda-lime glass which improved the optical transmission of the films. Gallium oxyhydroxide, an inevitable co-product of the chemical synthetic process, in the evaporant introduced oxygen and hydrogen impurities in the films which do not seem to significantly influence their optical properties. - Highlights: • Gallium sulphide films are prepared by thermal evaporation from a Mo or Ta boat. • Mo-boat prepared pristine film has Ga

  5. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    International Nuclear Information System (INIS)

    Kao, Yu-Hsuan; Wang, Sheng-Wei; Liu, Chen-Wuing; Wang, Pei-Ling; Wang, Chung-Ho; Maji, Sanjoy Kumar

    2011-01-01

    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ 34 S [SO 4 ] and δ 18 O [SO 4 ] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of 34 S [SO 4 ] and 18 O [SO 4 ] present in Type A, caused by microbial-mediated reduction of sulfate, and high 18 O enrichment factor (ε [SO 4 -H 2 O] ), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ 18 O [SO 4 ] and low δ 34 S [SO 4 ] values under mildly reducing conditions. Base on 18 O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O 2 , caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: → Seawater intrusion and elevated As are the main issues of groundwater in Taiwan. → Sulfur and oxygen isotopes of sulfate were analyzed to evaluate the As mobility. → Reductive dissolution of Fe minerals and

  6. Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release

    Energy Technology Data Exchange (ETDEWEB)

    Tabelin, Carlito Baltazar, E-mail: carlito@trans-er.eng.hokudai.ac.jp [Laboratory of Soil Environment Engineering, Faculty of Engineering, Hokkaido University, Sapporo (Japan); Hashimoto, Ayaka, E-mail: a.hashimoto@diaconsult.co.jp [DIA Consultants Co. Ltd., Sapporo (Japan); Igarashi, Toshifumi, E-mail: tosifumi@eng.hokudai.ac.jp [Laboratory of Groundwater and Mass Transport, Faculty of Engineering, Hokkaido University, Sapporo (Japan); Yoneda, Tetsuro, E-mail: yonet@eng.hokudai.ac.jp [Laboratory of Soil Environment Engineering, Faculty of Engineering, Hokkaido University, Sapporo (Japan)

    2014-03-01

    Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. - Highlights: • The bulk of

  7. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    Energy Technology Data Exchange (ETDEWEB)

    Kao, Yu-Hsuan [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Sheng-Wei [Agricultural Engineering Research Center, Chungli 320, Taiwan, ROC (China); Liu, Chen-Wuing, E-mail: lcw@gwater.agec.ntu.edu.tw [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Pei-Ling [Institute of Oceanography, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Chung-Ho [Institute of Earth Sciences, Academia Sinica, Taipei 115, Taiwan, ROC (China); Maji, Sanjoy Kumar [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China)

    2011-10-15

    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using {delta}{sup 34}S{sub [SO{sub 4]}} and {delta}{sup 18}O{sub [SO{sub 4]}} sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of {sup 34}S{sub [SO{sub 4]}} and {sup 18}O{sub [SO{sub 4]}} present in Type A, caused by microbial-mediated reduction of sulfate, and high {sup 18}O enrichment factor ({epsilon}{sub [SO{sub 4-H{sub 2O]}}}), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high {delta}{sup 18}O{sub [SO{sub 4]}} and low {delta}{sup 34}S{sub [SO{sub 4]}} values under mildly reducing conditions. Base on {sup 18}O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O{sub 2}, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: {yields} Seawater intrusion and elevated As are the main issues of groundwater in Taiwan

  8. Deconvolution of trace element (As, Cr, Mo, Th, U) sources and pathways to surface waters of a gold mining-influenced watershed.

    Science.gov (United States)

    Grosbois, C; Schäfer, J; Bril, H; Blanc, G; Bossy, A

    2009-03-01

    The Upper Isle River (SW France) drains the second most productive gold-mining district of France. A high resolution survey during one hydrological year of As, Cl(-), Cr, Fe, Mn, Mo, SO(4)(2-), Th and U dissolved concentrations in surface water aimed to better understand pathways of trace element export to the river system downstream from the mining district. Dissolved concentrations of As (up to 35000 ng/L) and Mo (up to 292 ng/L) were about 3-fold higher than the regional dissolved background and showed a negative logarithmic relation with discharge. Dissolved concentrations of Cr (up to 483 ng/L), Th (up to 48 ng/L) and U (up to 184 ng/L) increased with discharge. Geochemical relationships between molar ratios in surface water, geochemical background as well as rain- and groundwater data were combined. The contrasting behavior of distinct element groups was explained by a scenario involving three seasonal components: (i) The high flow component is poorly concentrated in As and Mo but highly concentrated in Cr, Th, U. This has been attributed to diffuse sources such as water-soil interactions, atmospheric inputs, bedrock and bed sediment weathering. Although this component probably also includes a contribution by weathering of sulfide veins, this signal is masked by dilution. (ii) One low flow component presents high SO(4)(2-), Fe, As and Mo and moderate Cr, Th and U concentrations. This component has been attributed to point sources such as mine gallery effluents, mining waste weathering and groundwater inputs from natural and/or mining-induced sulfide oxidation in the ore deposit. (iii) A second low flow component showing high As plus Mo concentrations associated with very low SO(4)(2-), Fe, Cr, Th and U concentrations, probably reflects trace element scavenging by ferric oxyhydroxide formation in the adjacent aquifer. This is supported by the decrease of Fe, Cr, Th and U in surface waters. Flux estimates suggest contrasting element-specific impacts on annual

  9. Acid drainage at the inactive Santa Lucia mine, western Cuba: Natural attenuation of arsenic, barium and lead, and geochemical behavior of rare earth elements

    Energy Technology Data Exchange (ETDEWEB)

    Romero, Francisco Martin, E-mail: fmrch@geologia.unam.mx [Instituto de Geologia, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Delegacion Coyoacan, 04510 Mexico D.F. (Mexico); Prol-Ledesma, Rosa Maria; Canet, Carles [Instituto de Geofisica, Universidad Nacional Autonoma de Mexico, Ciudad Universitaria, Delegacion Coyoacan, 04510 Mexico D.F. (Mexico); Alvares, Laura Nunez; Perez-Vazquez, Ramon [Facultad de Geologia y Mecanica, Universidad de Pinar del Rio (Cuba)

    2010-05-15

    A detailed geochemical study was conducted at the inactive Zn-Pb mine of Santa Lucia, in western Cuba. The studied mine-wastes are characterized by high total concentrations of potentially toxic elements (PTE), with average values of 17.4% Fe, 5.47% Ba, 2.27% Pb, 0.83% Zn, 1724 mg/kg As and 811 mg/kg Cu. Oxidation of sulfide minerals in mine-waste dumps and in the open pit produces acid mine effluents (pH = 2.5-2.6) enriched in dissolved SO{sub 4}{sup 2-} (up to 6754 mg/L), Fe (up to 4620 mg/L) and Zn (up to 2090 mg/L). Low pH values (2.5-2.8) and high dissolved concentrations of the same PTE were found in surface waters, up to 1500 m downstream from the mine. Nevertheless, concentrations of As, Ba and Pb in acid mine effluents and impacted surface waters are relatively low: 0.01-0.3 mg/L As, 0.002-0.03 mg/L Ba and 0.3-4.3 mg/L Pb. Analysis by X-ray diffraction and electron microscopy revealed the occurrence of lead-bearing barite and beudantite and the more common solid phases, reported elsewhere in similar environments including Fe-oxyhydroxides, jarosite, anglesite and plumbojarosite. Because the reported solubilities for barite and beudantite are very low under acidic conditions, these minerals may serve as the most important control in the mobility of As, Ba and Pb. In contrast, Fe-oxyhydroxides are relatively soluble under acidic conditions and, therefore, they may have a less significant role in PTE on-site immobilization. Mine-wastes and stream sediments show a light REE (LREE) and middle REE (MREE) enrichment relative to heavy REE (HREE). In contrast, acid mine effluents and surface waters are enriched in HREE relative to LREE. These results suggest that the LREE released during the oxidation of sulfides are captured by secondary (weathering) minerals, while the MREE are removed from the altered rocks. The low concentrations of LREE in acid stream water suggest that these elements can be retained in the sediments more strongly than HREE and MREE. One

  10. Sediment phosphorus speciation and mobility under dynamic redox conditions

    Science.gov (United States)

    Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

    2017-07-01

    Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the

  11. Origin and availability of organic matter leading to arsenic mobilisation in aquifers of the Red River Delta, Vietnam

    International Nuclear Information System (INIS)

    Eiche, Elisabeth; Berg, Michael; Hönig, Sarah-Madeleine; Neumann, Thomas; Lan, Vi Mai; Pham, Thi Kim Trang; Pham, Hung Viet

    2017-01-01

    Groundwater arsenic (As) concentrations in the Red River Delta (Vietnam) are often patchy and related to the microbially induced reduction of Fe oxy-hydroxides. In this study, we explored the influence of the origin, composition and availability of natural organic matter on the hydrochemical variability in the aquifers of Van Phuc. Carbon isotope signatures (δ"1"3C_o_r_g) and C/N ratios were assessed in combination with lithology, geochemistry, hydrochemistry, hydrology and the distribution of specific biomarkers. The elationship of C/N ratios and δ"1"3C_o_r_g distinguished four groups of sediment types that differ in their organic carbon sources. This includes organic carbon originating predominantly from vascular C_3 plants (C/N: 15.4–21.0, δ"1"3C_o_r_g: −28.6 to −26.7‰), C_4 plants (C/N: 10.6; δ"1"3C_o_r_g: −14.8‰), freshwater derived particulate organic carbon (C/N: ≤8; δ"1"3C_o_r_g:≤−24‰) as well as mixtures incorporating both sources. At the high As sites, we found particulate organic carbon (POC) being 1–2‰ less depleted in δ"1"3C_o_r_g than at low As sites. More importantly, however, our assessment shows that, the availability of organic matter has to be considered decisive with regard to groundwater As contamination. Fine-grained clayey sediments overlaying sands generally protect organic matter from substantial degradation and its leaching into an adjacent aquifer. However, at the sites that are high in dissolved As in Van Phuc, sediment layers rich in organic matter are hydraulically connected to the underlying aquifer. Here, soluble organic matter seeping into the aquifer can induce and/or enhance reducing conditions, thereby mobilising As from Fe oxy-hydroxides. Our study shows that both the clay content as well as the origin of organic matter are largely controlled by the depositional environment of the sediments. - Highlights: • Particulate organic carbon (POC) from C_3/C_4 plants and freshwater is a main source of

  12. Mineralogic variations in fluvial sediments contaminated by mine tailings as determined from AVIRIS data, Coeur D'Alene River Valley, Idaho

    Science.gov (United States)

    Farrand, W. H.; Harsanyi, Joseph C.

    1995-01-01

    The success of imaging spectrometry in mineralogic mapping of natural terrains indicates that the technology can also be used to assess the environmental impact of human activities in certain instances. Specifically, this paper describes an investigation into the use of data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mapping the spread of, and assessing changes in, the mineralogic character of tailings from a major silver and base metal mining district. The area under investigation is the Coeur d'Alene River Valley in northern Idaho. Mining has been going on in and around the towns of Kellogg and Wallace, Idaho since the 1880's. In the Kellogg-Smelterville Flats area, west of Kellogg, mine tailings were piled alongside the South Fork of the Coeur d'Alene River. Until the construction of tailings ponds in 1968 much of these waste materials were washed directly into the South Fork. The Kellogg-Smelterville area was declared an Environmental Protection Agency (EPA) Superfund site in 1983 and remediation efforts are currently underway. Recent studies have demonstrated that sediments in the Coeur d'Alene River and in the northern part of Lake Coeur d'Alene, into which the river flows, are highly enriched in Ag, Cu, Pb, Zn, Cd, Hg, As, and Sb. These trace metals have become aggregated in iron oxide and oxyhydroxide minerals and/or mineraloids. Reflectance spectra of iron-rich tailing materials are shown. Also shown are spectra of hematite and goethite. The broad bandwidth and long band center (near 1 micron) of the Fe(3+) crystal-field band of the iron-rich sediment samples combined with the lack of features on the Fe(3+) -O(2-) charge transfer absorption edge indicates that the ferric oxide and/or oxyhydroxide in these sediments is poorly crystalline to amorphous in character. Similar features are seen in poorly crystalline basaltic weathering products (e.g., palagonites). The problem of mapping and analyzing the downriver occurrences of iron

  13. Seasonal water quality variations in a river affected by acid mine drainage: the Odiel River (South West Spain)

    Energy Technology Data Exchange (ETDEWEB)

    Olias, M.; Nieto, J.M.; Sarmiento, A.M.; Ceron, J.C.; Canovas, C.R

    2004-10-15

    This paper intends to analyse seasonal variations of the quality of the water of the Odiel River. This river, together with the Tinto River, drains the Iberian Pyrite Belt (IPB), a region containing an abundance of massive sulphide deposits. Because of mining activity dating back to prehistoric times, these two rivers are heavily contaminated. The Odiel and Tinto Rivers drain into a shared estuary known as the Ria of Huelva. This work studies dissolved contaminant data in water of the Odiel River collected by various organisations, between October 1980 and October 2002, close to the rivers entry into the estuary. Flow data for this location were also obtained. The most abundant metals in the water, in order of abundance, are zinc (Zn), iron (Fe), manganese (Mn) and copper (Cu). Arsenic (As), cadmium (Cd) and lead (Pb) are also present but in much lower quantities. The quality of the river water is linked to precipitation; the maximum sulphate, Fe, Zn, Mn, Cd and Pb concentrations occur during the autumn rains, which dissolve the Fe hydroxysulphates that were precipitated during the summer months. In winter, the intense rains cause an increase in the river flow, producing a dilution of the contaminants and a slight increase in the pH. During spring and summer, the sulphate and metal concentration (except Fe) recover and once again increase. The Fe concentration pattern displays a low value during summer due to increased precipitation of ferric oxyhydroxides. The arsenic concentration displays a different evolution, with maximum values in winter, and minimum in spring and summer as they are strongly adsorbed and/or coprecipitated by the ferric oxyhydroxides. Mn and sulphates are the most conservative species in the water. Relative to sulphate, Mn, Zn and Cd, copper displays greater values in winter and lower ones in summer, probably due to its coprecipitation with hydroxysulphates during the spring and summer months. Cd and Zn also appear to be affected by the same

  14. Elevated arsenic and manganese in groundwaters of Murshidabad, West Bengal, India.

    Science.gov (United States)

    Sankar, M S; Vega, M A; Defoe, P P; Kibria, M G; Ford, S; Telfeyan, K; Neal, A; Mohajerin, T J; Hettiarachchi, G M; Barua, S; Hobson, C; Johannesson, K; Datta, S

    2014-08-01

    High levels of geogenic arsenic (As) and manganese (Mn) in drinking water has led to widespread health problems for the population of West Bengal, India. Here we delineate the extent of occurrences of As and Mn in Murshidabad, where the contaminated aquifers occur at shallow depths between 35 and 40 m and where access to safe drinking water is a critical issue for the local population. A total of 78 well-water samples were taken in 4 blocks on either s