Effects of iron-containing minerals on hydrothermal reactions of ketones

Science.gov (United States)

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2018-02-01

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

The graphite deposit at Borrowdale (UK): A catastrophic mineralizing event associated with Ordovician magmatism

Science.gov (United States)

Ortega, L.; Millward, D.; Luque, F. J.; Barrenechea, J. F.; Beyssac, O.; Huizenga, J.-M.; Rodas, M.; Clarke, S. M.

2010-04-01

The volcanic-hosted graphite deposit at Borrowdale in Cumbria, UK, was formed through precipitation from C-O-H fluids. The δ 13C data indicate that carbon was incorporated into the mineralizing fluids by assimilation of carbonaceous metapelites of the Skiddaw Group by andesite magmas of the Borrowdale Volcanic Group. The graphite mineralization occurred as the fluids migrated upwards through normal conjugate fractures forming the main subvertical pipe-like bodies. The mineralizing fluids evolved from CO 2-CH 4-H 2O mixtures (XCO 2 = 0.6-0.8) to CH 4-H 2O mixtures. Coevally with graphite deposition, the andesite and dioritic wall rocks adjacent to the veins were intensely hydrothermally altered to a propylitic assemblage. The initial graphite precipitation was probably triggered by the earliest hydration reactions in the volcanic host rocks. During the main mineralization stage, graphite precipitated along the pipe-like bodies due to CO 2 → C + O 2. This agrees with the isotopic data which indicate that the first graphite morphologies crystallizing from the fluid (cryptocrystalline aggregates) are isotopically lighter than those crystallizing later (flakes). Late chlorite-graphite veins were formed from CH 4-enriched fluids following the reaction CH 4 + O 2 → C + 2H 2O, producing the successive precipitation of isotopically lighter graphite morphologies. Thus, as mineralization proceeded, water-generating reactions were involved in graphite precipitation, further favouring the propylitic alteration. The structural features of the pipe-like mineralized bodies as well as the isotopic homogeneity of graphite suggest that the mineralization occurred in a very short period of time.

EMSP Project 70070: Reactivity of Primary Soil Minerals and Secondary Precipitates Beneath Leaking Hanford Waste Tanks - Final Report

International Nuclear Information System (INIS)

Nagy, Kathryn L.

2004-01-01

Since the late 1950s, leaks from 67 single-shell tanks at the Hanford Site have released about 1 million curies to the underlying sediments. The radioactive material was contained in water-based solutions generally characterized as having high pH values (basic solutions), high nitrate and nitrite concentrations, and high aluminum concentrations. The solutions were also hot, in some cases at or near boiling, as well as complex and highly variable in composition reflecting solutions obtained from multiple methods of reprocessing spent nuclear fuel. In order to understand the observed and probable distribution of radionuclides in the ground at Hanford, major reactions that likely occurred between the leaked fluids and the sediment minerals were investigated in laboratory experiments simulating environmental conditions. Reactions involving the dissolution of quartz and biotite and the simultaneous formation of new minerals were quantified at controlled pH values and temperature. Result s show that the dissolution of quartz and formation of new zeolite-like minerals could have altered the flow path of ground water and contaminant plumes and provided an uptake mechanism for positively-charged soluble radionuclides, such as cesium. The dissolution of biotite, a layered-iron-aluminum-silicate mineral, provided iron in a reduced form that could have reacted with negatively-charged soluble chromium, a toxic component of the wastes, to cause its reduction and precipitation as a new reduced-chromium mineral. The quantity of iron released in the experiments is sufficient to explain observations of reductions in dissolved chromium concentration in a plume beneath one Hanford tank. Fundamental data obtained in the project are the rates of the reactions at variable temperatures and pHs. Fundamental data were also obtained on aspects of the surface reactivity of clay or layered-silicate minerals, a small proportion of the total mass of the sediment minerals, but a large proportion

Geochemical modeling of the influence of silicate mineral alteration on alkalinity production and carbonate precipitation

Science.gov (United States)

Herda, Gerhard; Kraemer, Stephan M.; Gier, Susanne; Meister, Patrick

2016-04-01

as well as carbonates in porefluids under different pCO2 levels. In a second step, we will let the minerals react to a thermodynamically stable state and thereby observe the resulting alkalinity effect and the effect on carbonate precipitation. So far, modeling showed that saturation states of some of the most common clay minerals, including kaolinite, illite, montmorillonite and chlorite in a standard seawater solution strongly depend on silica and aluminum concentrations, but they show very little dependence on the pH. This is understandable since a congruent dissolution of clay minerals does not significantly increase or decrease the alkalinity. However, partial leaching of structural ions by incongruent dissolution/precipitation should have a strong effect on porewater alkalinity. Hence, substitution reactions will have to be simulated as part of this study. Calculated mineral alteration and rock-fluid interactions in deep sediments will contribute to a better understanding of carbonate diagenesis but also of long-term effects in subsurface CO2 storage reservoirs. Mavromatis et al. (2014) Chem. Geol. 385, 84-91. Parkhurst, D.L, and Appelo, C.A.J. (2013) U.S Geological Survey Techniques and Methods, book 6, chap. A43, 497 p. Wallmann et al. (2008) Geochim. Cosmochim. Acta 72, 3067-3090.

Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction.

Science.gov (United States)

Kang, Il-Mo; Roh, Ki-Min

2013-01-01

The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

Science.gov (United States)

Li, Wei; Livi, Kenneth J T; Xu, Wenqian; Siebecker, Matthew G; Wang, Yujun; Phillips, Brian L; Sparks, Donald L

2012-11-06

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Mineral-Surfactant Interactions for Minimum Reagents Precipitation and Adsorption for Improved Oil Recovery

Energy Technology Data Exchange (ETDEWEB)

P. Somasundaran

2008-09-20

Chemical EOR can be an effective method for increasing oil recovery and reducing the amount of produced water; however, reservoir fluids are chemically complex and may react adversely to the polymers and surfactants injected into the reservoir. While a major goal is to alter rock wettability and interfacial tension between oil and water, rock-fluid and fluid-fluid interactions must be understood and controlled to minimize reagent loss, maximize recovery and mitigate costly failures. The overall objective of this project was to elucidate the mechanisms of interactions between polymers/surfactants and the mineral surfaces responsible for determining the chemical loss due to adsorption and precipitation in EOR processes. The role of dissolved inorganic species that are dependent on the mineralogy is investigated with respect to their effects on adsorption. Adsorption, wettability and interfacial tension are studied with the aim to control chemical losses, the ultimate goal being to devise schemes to develop guidelines for surfactant and polymer selection in EOR. The adsorption behavior of mixed polymer/surfactant and surfactant/surfactant systems on typical reservoir minerals (quartz, alumina, calcite, dolomite, kaolinite, gypsum, pyrite, etc.) was correlated to their molecular structures, intermolecular interactions and the solution conditions such as pH and/or salinity. Predictive models as well as general guidelines for the use of polymer/surfactant surfactant/surfactant system in EOR have been developed The following tasks have been completed under the scope of the project: (1) Mineral characterization, in terms of SEM, BET, size, surface charge, and point zero charge. (2) Study of the interactions among typical reservoir minerals (quartz, alumina, calcite, dolomite, kaolinite, gypsum, pyrite, etc.) and surfactants and/or polymers in terms of adsorption properties that include both macroscopic (adsorption density, wettability) and microscopic (orientation

Extraction of rare earth elements from low-grade Bauxite via precipitation reaction

Science.gov (United States)

Kusrini, E.; Nurani, Y.; Bahari, ZJ

2018-03-01

The aim of this research was to determine the optimum hydrometallurgical parameters to extract the rare earth elements (REE) from low-grade bauxite through acid leaching and precipitation reaction. REE or lanthanide recovery by a precipitation method with sodium sulphate and sodium phosphate as precipitation agents is reported where the effect of pH and recovery of REE are described. The metal composition of REE in low-grade bauxite after treatment were analyzed by ICP-OES. The total recovery values of REE elements at the first precipitation reaction using sodium sulphate as the precipitation agent at pH 3.5 showed ~68.2% of lanthanum, ~18.9% cerium, and ~7.8% yttrium. Lanthanum was the rare-earth element present at the highest concentration in the low-grade bauxite after the series treatments. An optimum pH of 3.5 for precipitation of rare-earth elements using sodium sulphate was demonstrated where this method is recommended for the extraction of REE elements from low-grade bauxite.

Complex electrical monitoring of biopolymer and iron mineral precipitation for microbial enhanced hydrocarbon recovery

Science.gov (United States)

Wu, Y.; Hubbard, C. G.; Dong, W.; Hubbard, S. S.

2011-12-01

Microbially enhanced hydrocarbon recovery (MEHR) mechanisms are expected to be impacted by processes and properties that occur over a wide range of scales, ranging from surface interactions and microbial metabolism at the submicron scale to changes in wettability and pore geometry at the pore scale to geological heterogeneities at the petroleum reservoir scale. To eventually ensure successful, production-scale implementation of laboratory-developed MEHR procedures under field conditions, it is necessary to develop approaches that can remotely monitor and accurately predict the complex microbially-facilitated transformations that are expected to occur during MEHR treatments in reservoirs (such as the evolution of redox profiles, oil viscosity or matrix porosity/permeability modifications). Our initial studies are focused on laboratory experiments to assess the geophysical signatures of MEHR-induced biogeochemical transformations, with an ultimate goal of using these approaches to monitor field treatments. Here, we explore the electrical signatures of two MEHR processes that are designed to produce end-products that will plug high permeability zones in reservoirs and thus enhance sweep efficiency. The MEHR experiments to induce biopolymers (in this case dextran) and iron mineral precipitates were conducted using flow-through columns. Leuconostoc mesenteroides, a facultative anaerobe, known to produce dextran from sucrose was used in the biopolymer experiments. Paused injection of sucrose, following inoculation and initial microbial attachment, was carried out on daily basis, allowing enough time for dextran production to occur based on batch experiment observations. Electrical data were collected on daily basis and fluid samples were extracted from the column for characterization. Changes in electrical signal were not observed during initial microbial inoculation. Increase of electrical resistivity and decrease of electrical phase response were observed during the

Impact of elevated CO_2 concentrations on carbonate mineral precipitation ability of sulfate-reducing bacteria and implications for CO_2 sequestration

International Nuclear Information System (INIS)

Paul, Varun G.; Wronkiewicz, David J.; Mormile, Melanie R.

2017-01-01

Interest in anthropogenic CO_2 release and associated global climatic change has prompted numerous laboratory-scale and commercial efforts focused on capturing, sequestering or utilizing CO_2 in the subsurface. Known carbonate mineral precipitating microorganisms, such as the anaerobic sulfate-reducing bacteria (SRB), could enhance the rate of conversion of CO_2 into solid minerals and thereby improve long-term storage of captured gasses. The ability of SRB to induce carbonate mineral precipitation, when exposed to atmospheric and elevated pCO_2, was investigated in laboratory scale tests with bacteria from organic-rich sediments collected from hypersaline Lake Estancia, New Mexico. The enriched SRB culture was inoculated in continuous gas flow and batch reactors under variable headspace pCO_2 (0.0059 psi to 20 psi). Solution pH, redox conditions, sulfide, calcium and magnesium concentrations were monitored in the reactors. Those reactors containing SRB that were exposed to pCO_2 of 14.7 psi or less showed Mg-calcite precipitation. Reactors exposed to 20 psi pCO_2 did not exhibit any carbonate mineralization, likely due to the inhibition of bacterial metabolism caused by the high levels of CO_2. Hydrogen, lactate and formate served as suitable electron donors for the SRB metabolism and related carbonate mineralization. Carbon isotopic studies confirmed that ∼53% of carbon in the precipitated carbonate minerals was derived from the CO_2 headspace, with the remaining carbon being derived from the organic electron donors, and the bicarbonate ions available in the liquid medium. The ability of halotolerant SRB to induce the precipitation of carbonate minerals can potentially be applied to the long-term storage of anthropogenic CO_2 in saline aquifers and other ideal subsurface rock units by converting the gas into solid immobile phases. - Highlights: • SRB under study are capable of precipitating calcite up to 14.7 psi pCO_2. • At 20 psi pCO_2, bacterial activity

Investigating Interactions between the Silica and Carbon Cycles during Precipitation and Early Diagenesis of Authigenic Clay/Carbonate-Mineral Associations in the Carbonate Rock Record

Science.gov (United States)

McKenzie, J. A.; Francisca Martinez Ruiz, F.; Sanchez-Roman, M.; Anjos, S.; Bontognali, T. R. R.; Nascimento, G. S.; Vasconcelos, C.

2017-12-01

The study of authigenic clay/carbonate-mineral associations within carbonate sequences has important implications for the interpretation of scientific problems related with rock reservoir properties, such as alteration of potential porosity and permeability. More specifically, when clay minerals are randomly distributed within the carbonate matrix, it becomes difficult to predict reservoir characteristics. In order to understand this mineral association in the geological record, we have undertaken a comparative study of specially designed laboratory experiments with modern environments, where clay minerals have been shown to precipitate together with a range of carbonate minerals, including calcite, Mg-calcite and dolomite. Two modern dolomite-forming environments, the Coorong lakes, South Australia and Brejo do Espinho Rio de Janeiro, Brazil, were selected for this investigation. For comparative evaluation, enrichment microbial culture experiments, using natural pore water from Brejo do Espinho as the growth medium to promote mineral precipitation, were performed under both aerobic and anaerobic conditions. To establish the environmental parameters and biological processes facilitating the dual mineral association, the experimental samples have been compared with the natural minerals using HRTEM measurements. The results demonstrate that the clay and carbonate minerals apparently do not co-precipitate, but the precipitation of the different minerals in the same sample has probably occurred under different environmental conditions with variable chemistries, e.g., hypersalinity versus normal salinity resulting from the changing ratio of evaporation versus precipitation. Thus, the investigated mineral association is not a product of diagenetic processes but of sequential in situ precipitation processes related to changes in the silica and carbon availability. Implications for ancient carbonate formations will be presented and discussed in the context of a specific

Precipitation reactions in a beryllium-bearing stainless steel

International Nuclear Information System (INIS)

Carr, M.J.; Heiple, C.R.

1980-01-01

Precipitation reactions in a beryllium-bearing stainless steel alloy have been studied by TEM and electron diffraction for ageing temperatures between 400 0 and 900 0 C. The nominal composition of the alloy was 38% Ni - 21% Cr - 1% Mn - 0.5% Be - Bal Fe. Specimens were solutionized for one hour at 1150 0 C and water quenched. The ageing reaction was studied by hardness measurements for times between 0.5 and 16 hours. The TEM specimens dicussed herein were made from samples aged one hour

Dynamics of mineral crystallization at inclusion-garnet interface from precipitated slab-derived fluid phase: first in-situ synchrotron x-ray measurements

Science.gov (United States)

Malaspina, Nadia; Alvaro, Matteo; Campione, Marcello; Nestola, Fabrizio

2015-04-01

Remnants of the fluid phase at ultrahigh pressure (UHP) in subduction environments may be preserved as primary multiphase inclusions in UHP minerals. These inclusions are frequently hosted by minerals stable at mantle depths, such as garnet, and show the same textural features as fluid inclusions. The mineral infillings of the solid multiphase inclusions are generally assumed to have crystallized by precipitation from the solute load of dense supercritical fluids equilibrating with the host rock. Notwithstanding the validity of this assumption, the mode of crystallization of daughter minerals during precipitation within the inclusion and/or the mechanism of interaction between the fluid at supercritical conditions and the host mineral are still poorly understood from a crystallographic point of view. A case study is represented by garnet orthopyroxenites from the Maowu Ultramafic Complex (China) deriving from harzburgite precursors metasomatised at ~ 4 GPa, 750 °C by a silica- and incompatible trace element-rich fluid phase. This metasomatism produced poikilitic orthopyroxene and inclusion-rich garnet porphyroblasts. Solid multiphase primary inclusions in garnet display a size within a few tens of micrometers and negative crystal shapes. Infilling minerals (spinel: 10-20 vol.%; amphibole, chlorite, talc, mica: 80- 90 vol.%) occur with constant volume ratios and derive from trapped solute-rich aqueous fluids. To constrain the possible mode of precipitation of daughter minerals, we performed for the first time a single-crystal X-ray diffraction experiment by means of Synchrotron Radiation at DLS-Diamond Light Source. In combination with electron probe microanalyses, this measurement allowed the unique identification of each mineral phase and their reciprocal orientations. We demonstrated the epitaxial relationship between spinel and garnet and between some hydrous minerals. Epitaxy drives a first-stage nucleation of spinel under near-to-equilibrium conditions

Cintichem modified process - {sup 99}Mo precipitation step: application of statistical analysis tools over the reaction parameters

Energy Technology Data Exchange (ETDEWEB)

Teodoro, Rodrigo; Dias, Carla R.B.R.; Osso Junior, Joao A., E-mail: jaosso@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Fernandez Nunez, Eutimio Gustavo [Universidade de Sao Paulo (EP/USP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Quimica

2011-07-01

Precipitation of {sup 99}Mo by {alpha}-benzoin oxime ({alpha}-Bz) is a standard precipitation method for molybdenum due the high selectivity of this agent. Nowadays, statistical analysis tools have been employed in analytical systems to prove its efficiency and feasibility. IPEN has a project aiming the production of {sup 99}Mo by the fission of {sup 235}U route. The processing uses as the first step the precipitation of {sup 99}Mo with {alpha}-Bz. This precipitation step involves many key reaction parameters. The aim of this work is based on the development of the already known acidic route to produce {sup 99}Mo as well as the optimization of the reactional parameters applying statistical tools. In order to simulate {sup 99}Mo precipitation, the study was conducted in acidic media using HNO{sub 3}, {alpha}Bz as precipitant agent and NaOH /1%H{sub 2}O{sub 2} as dissolver solution. Then, a Mo carrier, KMnO{sub 4} solutions and {sup 99}Mo tracer were added to the reaction flask. The reactional parameters ({alpha}-Bz/Mo ratio, Mo carrier, reaction time and temperature, and cooling reaction time before filtration) were evaluated under a fractional factorial design of resolution V. The best values of each reactional parameter were determined by a response surface statistical planning. The precipitation and recovery yields of {sup 99}Mo were measured using HPGe detector. Statistical analysis from experimental data suggested that the reactional parameters {alpha}-Bz/Mo ratio, reaction time and temperature have a significant impact on {sup 99}Mo precipitation. Optimization statistical planning showed that higher {alpha}Bz/Mo ratios, room temperature, and lower reaction time lead to higher {sup 99}Mo yields. (author)

A generic transport-reactive model for simulating microbially influenced mineral precipitation in porous medium

NARCIS (Netherlands)

Zhou, J.; Van Turnhout, A.G.; Heimovaara, T.J.; Afanasyev, M.

2015-01-01

The spatial and temporal distribution of precipitated minerals is one of the key factors governing various processes in the sub-surface environment, including microbially influenced corrosion (MIC) (Huang, 2002), bio-cementation (van Paassen et al., 2010) and sediment diagenesis (Paraska et al.,

Coprecipitation of {sup 14}C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways

Energy Technology Data Exchange (ETDEWEB)

Hodkin, David J. [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Stewart, Douglas I. [School of Civil Engineering, University of Leeds (United Kingdom); Graham, James T. [National Nuclear Laboratory, Sellafield, Cumbria (United Kingdom); Burke, Ian T., E-mail: I.T.Burke@leeds.ac.uk [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom)

2016-08-15

This study investigated the simultaneous removal of Sr{sup 2+} and {sup 14}CO{sub 3}{sup 2−} from pH > 12 Ca(OH){sub 2} solution by the precipitation of calcium carbonate. Initial Ca{sup 2+}:CO{sub 3}{sup 2−} ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of {sup 14}C and Sr{sup 2+} both occurred in the system containing 10 mM Ca{sup 2+} and 1 mM CO{sub 3}{sup 2−} (99.7% and 98.6% removal respectively). A kinetic model is provided that describes {sup 14}C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of {sup 14}C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated > 46% of the {sup 14}C back to solution. Sr{sup 2+} removal occurred as Ca{sup 2+} became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for {sup 90}Sr and {sup 14}C in radioactively contaminated waters (<$0.25 reagent cost per m{sup 3} treated). - Highlights: • 99.7% of {sup 14}C and 98.6% of Sr removed from aqueous solution by CaCO{sub 3} precipitation. • Remobilization of {sup 14}C observed during calcium carbonate recrystallization. • Sr displayed variable distribution coefficient (possibly affected by Ca:Sr ratio). • Reagent cost of $0.22/m{sup 3} of treated groundwater.

Dynamics of mineral crystallization from precipitated slab-derived fluid phase: first in situ synchrotron X-ray measurements

Science.gov (United States)

Malaspina, Nadia; Alvaro, Matteo; Campione, Marcello; Wilhelm, Heribert; Nestola, Fabrizio

2015-03-01

Remnants of the fluid phase at ultrahigh pressure (UHP) in subduction environments may be preserved as primary multiphase inclusions in UHP minerals. The mode of crystallization of daughter minerals during precipitation within the inclusion and/or the mechanism of interaction between the fluid at supercritical conditions and the host mineral are still poorly understood from a crystallographic point of view. A case study is represented by garnet-orthopyroxenites from the Maowu Ultramafic Complex (China) deriving from harzburgite precursors metasomatized at ~4 GPa, 750 °C by a silica- and incompatible trace element-rich fluid phase. This metasomatism produced poikilitic orthopyroxene and inclusion-rich garnet porphyroblasts. Solid multiphase primary inclusions in garnet display a size within a few tens of micrometres and negative crystal shapes. Infilling minerals (spinel: 10-20 vol%; amphibole, chlorite, talc, mica: 80-90 vol%) occur with constant volume proportions and derive from trapped solute-rich aqueous fluids. To constrain the possible mode of precipitation of daughter minerals, we performed for the first time a single-crystal X-ray diffraction experiment by synchrotron radiation at Diamond Light Source. In combination with electron probe microanalyses, this measurement allowed the unique identification of each mineral phase and reciprocal orientations. We demonstrated the epitaxial relationship between spinel and garnet and between some hydrous minerals. Such information is discussed in relation to the physico-chemical aspects of nucleation and growth, shedding light on the mode of mineral crystallization from a fluid phase trapped at supercritical conditions.

Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

Directory of Open Access Journals (Sweden)

Y. Liu

2010-11-01

Full Text Available The heterogeneous reactions of carbonyl sulfide (OCS on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al₂O₃, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe₂O₃ and ZnO, respectively, whereas no apparent uptake of OCS by SiO₂ and TiO₂ was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H₂S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γ_BET of mineral dust was estimated to be in the range of 3.84×10⁻⁷–2.86×10⁻⁸. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr⁻¹, which is comparable to the annual flux of OCS for its reaction with ·OH.

Validation of a plant-wide phosphorus modelling approach with minerals precipitation in a full-scale WWTP

DEFF Research Database (Denmark)

Mbamba, Christian Kazadi; Flores Alsina, Xavier; Batstone, Damien John

2016-01-01

approach describing ion speciation and ion pairing with kinetic multiple minerals precipitation. Model performance is evaluated against data sets from a full-scale wastewater treatment plant, assessing capability to describe water and sludge lines across the treatment process under steady-state operation...... plant. Dynamic influent profiles were generated using a calibrated influent generator and were used to study the effect of long-term influent dynamics on plant performance. Model-based analysis shows that minerals precipitation strongly influences composition in the anaerobic digesters, but also impacts......The focus of modelling in wastewater treatment is shifting from single unit to plant-wide scale. Plant wide modelling approaches provide opportunities to study the dynamics and interactions of different transformations in water and sludge streams. Towards developing more general and robust...

Effect of the mineral precipitation-dissolution at tunnel walls during the operational and post-operational phases

Energy Technology Data Exchange (ETDEWEB)

Domenech, Cristina; Arcos, David; Duro, Lara; Grandia, Fidel [Enviros Consul ting, Valldoreix, Barcelona (Spain)

2007-11-15

The extent of reversibility of the geochemical conditions disturbed during the construction and operational phases is of importance in order to assess the chemical evolution of the repository system. In this regard, it is essential to have a deep understanding of the chemical status of the repository system at closure in order to describe its immediate geochemical evolution beyond this point. This project assesses the dissolution and precipitation of minerals due to the interaction with groundwater in the deposition tunnel wall-rock during the operational phase (prior to tunnel backfilling) and during the saturation phase, also considering the effect on the backfill material. We have performed a 2D model in which a fracture intersecting the main tunnel has been considered. The project has been developed in two consecutive stages. The first stage simulates the precipitation and dissolution of minerals in the tunnel wall rock during the operational phase (100 years after excavation) when the tunnel is empty and filled with air. During this stage, water flows through fractures into the tunnel. The results of the model suggest that the interaction between groundwater, fracture-filling minerals, and atmospheric O{sub 2}(g) and CO{sub 2}(g) present in the tunnel leads to the precipitation of secondary minerals (calcite and iron(III) oxy-hydroxide) that do not significantly affect the porosity of the area surrounding the tunnel. The second stage starts after the operational phase, once the tunnel is backfilled, and simulates the interaction of groundwater with fracture-filling minerals and the backfill material. The model implemented assumes that the backfill is already water saturated and that water flows following the regional head gradient. Moreover, it also assumes that O2(g) is still present in the tunnel wall, as a result of the operational phase disturbances. The results show that oxygen will oxidise pyrite in the backfill and promote the precipitation of Fe

Mineral formation and organo-mineral controls on the bioavailability of carbon at the terrestrial-aquatic interface

Science.gov (United States)

Rod, K. A.; Smith, A. P.; Renslow, R.

2016-12-01

Recent evidence highlights the importance of organo-mineral interactions in regulating the source or sink capacity of soil. High surface area soils, such as allophane-rich or clay-rich soils, retain organic matter (OM) via sorption to mineral surfaces which can also contribute physical isolation in interlayer spaces. Despite the direct correlation between mineral surfaces and OM accumulation, the pedogenic processes controlling the abundance of reactive surface areas and their distribution in the mineral matrix remains unclear. As global soil temperatures rise, the dissolution of primary minerals and formation of new secondary minerals may be thermodynamically favored as part of soil weathering process. Newly formed minerals can supply surfaces for organo-metallic bonding and may, therefore, stabilize OM by surface bonding and physical exclusion. This is especially relevant in environments that intersect terrestrial and aquatic systems, such as the capillary fringe zone in riparian ecosystems. To test the mechanisms of mineral surface area protection of OM, we facilitated secondary precipitation of alumino-silicates in the presence of OM held at two different temperatures in natural Nisqually River sediments (Mt Rainier, WA). This was a three month reaction intended to simulate early pedogenesis. To tease out the influence of mineral surface area increase during pedogenesis, we incubated the sediments at two different soil moisture contents to induce biodegradation. We measured OM desorption, biodegradation, and the molecular composition of mineral-associated OM both prior to and following the temperature manipulation. To simulate the saturation of capillary fringe sediment and associated transport and reaction of OM, column experiments were conducted using the reacted sediments. More co-precipitation was observed in the 20°C solution compared to the 4°C reacted solution suggesting that warming trends alter mineral development and may remove more OM from solution

Mineral dissolution and precipitation in carbonate dominated terranes assessed using Mg isotopes

Science.gov (United States)

Tipper, E.; Calmels, D.; Gaillardet, J.; Galy, A.

2013-12-01

Carbonate weathering by carbonic acid consumes atmospheric CO2 during mineral dissolution, fixing it as aqueous bicarbonate over millennial time-scales. Ocean acidification has increased the solubility of CO2 in seawater by changing the balance of pH to alkalinity (the oceanic reservoir of carbon). This has lengthened the time-scale for CO2 sequestration by carbonate weathering to tens of thousands of years. At a global scale, the net consumption of CO2 is at least equal to that from silicate weathering, but there is far less work on carbonate weathering compared to silicate weathering because it has generally been assumed to be CO2 neutral on geological time-scales. Carbonate rocks are more readily dissolved than silicate rocks, meaning that their dissolution will likely respond much more rapidly to global environmental change when compared with the dissolution of silicate minerals. Although far less concentrated than Ca in many carbonates, Mg substitutes for Ca and is more concentrated than any other metal ion. Tracing the behavior of Mg in river waters, using Mg stable isotopes (26Mg/24Mg ratio expressed as delta26Mg in per mil units) is therefore a novel way to understand the complex series of dissolution/precipitation reactions that govern solute concentrations of Ca and Mg, and hence CO2 transfer by carbonate weathering. We present new Mg isotope data on a series of river and spring waters from the Jura mountains in North-East France. The stratigraphic column is relatively uniform throughout the Jura mountains and is dominated by limestones. As the limestone of the Jura Mountains were deposited in high-energy shallow water environments (shore line, lagoon and coral reefs), they are usually clay and organic poor. The delta26Mg of the local rocks is very constant at circa -4permil. The delta26Mg of the river waters is also fairly constant, but offset from the rock at -2.5permil. This is an intriguing observation because the dissolution of limestones is expected

Mineral transformation and biomass accumulation associated with uranium bioremediation at Rifle, Colorado.

Science.gov (United States)

Li, Li; Steefel, Carl I; Williams, Kenneth H; Wilkins, Michael J; Hubbard, Susan S

2009-07-15

Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates. The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can bean effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.

Aqueous complexation, precipitation, and adsorption reactions of cadmium in the geologic environment

International Nuclear Information System (INIS)

Zachara, J.M.; Rai, D.; Felmy, A.R.; Cowan, C.E.; Smith, S.C.; Moore, D.A.; Resch, C.T.

1992-06-01

This report contains new laboratory data and equilibrium constants for important solubility and adsorption reactions of Cd that occur in soil and groundwater and attenuate Cd migration. In addition, extensive interaction experiments with Cd and soils from electric utility sites are described. These experiments show the importance of precipitation and adsorption reactions in soil and demonstrate how such reactions can be modeled to predict Cd attenuation near utility sites

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

Science.gov (United States)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Post-precipitation bias in band-tailed pigeon surveys conducted at mineral sites

Science.gov (United States)

Overton, C.T.; Schmitz, R.A.; Casazza, Michael L.

2005-01-01

Many animal surveys to estimate populations or index trends include protocol prohibiting counts during rain but fail to address effects of rainfall preceding the count. Prior research on Pacific Coast band-tailed pigeons (Patagioenas fasciata monilis) documented declines in use of mineral sites during rainfall. We hypothesized that prior precipitation was associated with a short-term increase in use of mineral sites following rain. We conducted weekly counts of band-tailed pigeons at 19 Pacific Northwest mineral sites in 2001 and 20 sites in 2002. Results from regression analysis indicated higher counts ???2 days after rain (11.31??5.00% [x????SE]) compared to ???3 days. Individual index counts conducted ???2 days after rain were biased high, resulting in reduced ability to accurately estimate population trends. Models of band-tailed pigeon visitation rates throughout the summer showed increased mineral-site counts during both June and August migration periods, relative to the July breeding period. Our research supported previous studies recommending that mineral-site counts used to index the band-tailed pigeon population be conducted during July. We further recommend conducting counts >3 days after rain to avoid weather-related bias in index estimation. The design of other population sampling strategies that rely on annual counts should consider the influence of aberrant weather not only coincident with but also preceding surveys if weather patterns are thought to influence behavior or detection probability of target species.

Impact of dissolution and carbonate precipitation on carbon storage in basalt

Science.gov (United States)

Wells, R. K.; Xiong, W.; Tadeoye, J.; Menefee, A.; Ellis, B. R.; Skemer, P. A.; Giammar, D.

2016-12-01

The spatial evolution of silicate mineral dissolution, carbonate precipitation, and the transport of fluids influence the viability of carbon storage in basalt reservoirs. Dissolution of natural basalt and subsequent carbonate precipitation in systems with different transport processes operating were characterized using static and flow-through (5 mL/hr) experiments at 50, 100, and 150 °C, and 100 bar CO2. Intact samples and cores with milled pathways that simulate fractures were tested. Spatial and mineralogical patterns in dissolution and precipitation were analyzed using optical and electron microscopy, microCT scanning, and surface roughness data. Precipitates and fluid chemistry were analyzed using Raman spectroscopy, SEM-EDS, and ICP-MS. Analysis of the bulk solution and surface topography suggests dissolution of olivine and pyroxene grains begins within hours of the start of the experiments. In flow-through experiments, total effluent cation concentrations reach a peak concentration within a few hours then drop towards a steady state within a few days. In static experiments, the initial rate of cation release is faster than it is after several weeks. In both cases Ca2+, Mg2+, and Fe2+ are the dominant cations in solution in the initial stages of reaction. Lower concentrations of Na2+, K+, and Al3+, and the preservation of feldspar and matrix grains after several weeks of reaction indicate the slow reactivity of these minerals. As the reaction progresses, the surface roughness increases steadily with cavities developing at the sites of olivine and pyroxene grains. Post-reaction analysis of basalt samples reacted at static conditions with milled pathways reveals that both siderite and amorphous silica precipitated within diffusion-limited zones as early as 4-6 weeks. Siderite abundance varies with distance along the pathway with the highest concentration of carbonates 1-2 cm below the fracture opening. Siderite precipitates are large enough to fill fracture

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Yoo, J.H.; Kim, E.H.

1998-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, the photochemical decomposition mechanism of oxalates in the presence of nitric acid was elucidated by experimental work. The decomposition of oxalates was proved to be dominated by the reaction with hydroxyl radical generated from the nitric acid, rather than with nitrite ion also formed from nitrate ion. The decomposition rate of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was found to be 0.003 M/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Investigating the early stages of mineral precipitation by potentiometric titration and analytical ultracentrifugation.

Science.gov (United States)

Kellermeier, Matthias; Cölfen, Helmut; Gebauer, Denis

2013-01-01

Despite the importance of crystallization for various areas of research, our understanding of the early stages of the mineral precipitation from solution and of the actual mechanism of nucleation is still rather limited. Indeed, detailed insights into the processes underlying nucleation may enable a systematic development of novel strategies for controlling mineralization, which is highly relevant for fields ranging from materials chemistry to medicine. In this work, we describe experimental aspects of a quantitative assay, which relies on pH titrations combined with in situ metal ion potentiometry and conductivity measurements. The assay has originally been designed to study the crystallization of calcium carbonate, one of the most abundant biominerals. However, the developed procedures can also be readily applied to any compound containing cations for which ion-selective electrodes are available. Besides the possibility to quantitatively assess ion association prior to nucleation and to directly determine thermodynamic solubility products of precipitated phases, the main advantage of the crystallization assay is the unambiguous identification of the different stages of precipitation (i.e., prenucleation, nucleation, and early postnucleation) and the characterization of the multiple effects of additives. Furthermore, the experiments permit targeted access to distinct precursor species and intermediate stages, which thus can be analyzed by additional methods such as cryo-electron microscopy or analytical ultracentrifugation (AUC). Regarding ion association in solution, AUC detects entities significantly larger than simple ion pairs, so-called prenucleation clusters. Sedimentation coefficient values and distributions obtained for the calcium carbonate system are discussed in light of recent insights into the structural nature of prenucleation clusters. © 2013 Elsevier Inc. All rights reserved.

A non-classical view of the modulation of mineral precipitation by organic additives

Science.gov (United States)

Ruiz-Agudo, Encarnacion; Ruiz-Agudo, Cristina; Burgos-Cara, Alejandro; Putnis, Christine; Rodriguez-Navarro, Carlos; Putnis, Andrew

2016-04-01

Questions persist on the mechanisms of crystallization of sparingly soluble minerals such as calcium carbonate, calcium oxalate or barium sulphate. Compared to CaCO3, the mechanisms of nucleation and growth in the CaC2O4-H2O or BaSO4-H2O systems have received less attention. These phases are important due to their relevance as biominerals and/or unwanted mineral deposits in technological applications. Growing evidence suggests that sparingly soluble salts form by non-classical nucleation and growth pathways, where pre-nucleation ion associates and amorphous (solid or liquid) precursor phase(s) play a critical role (e.g. Rodríguez-Navarro et al. (2015), Ruiz-Agudo et al. (2015)). Indeed the identification of pre-nucleation species in these systems and their strong interactions with organic compounds (Verch et al. 2011) raises the possibility that the control of organics on biomineralization may begin even earlier than previously thought. A sound knowledge of the physical mechanisms by which acidic macromolecules affect nucleation and early growth may offer general insights concerning the molecular control of biomineralization, as well as being critical for improving strategies to control unwanted mineral deposition or for the synthesis of biomimetic materials. Here we present investigations on the initial stages of the precipitation of these relevant minerals in organic-free solutions to identify the precipitation pathway and to look for any potential precursor phase(s) to the final, crystalline polymorph. As well, we explore the effects that several acidic organic compounds have on the different precipitation stages identified. We find that organic additives such as citric acid, polyacrilic acid or a commercial copolymer of maleic acid/allyl sulfonic acid with phosphonate groups can be active at modifying pre-nucleation stages (destabilizing of pre-nucleation species or hampering the aggregation and growth of pre-nucleation associates) and subsequently strongly

Effect of Mineral Dissolution/Precipitation and CO2 Exsolution on CO2 transport in Geological Carbon Storage.

Science.gov (United States)

Xu, Ruina; Li, Rong; Ma, Jin; He, Di; Jiang, Peixue

2017-09-19

Geological carbon sequestration (GCS) in deep saline aquifers is an effective means for storing carbon dioxide to address global climate change. As the time after injection increases, the safety of storage increases as the CO 2 transforms from a separate phase to CO 2 (aq) and HCO 3 - by dissolution and then to carbonates by mineral dissolution. However, subsequent depressurization could lead to dissolved CO 2 (aq) escaping from the formation water and creating a new separate phase which may reduce the GCS system safety. The mineral dissolution and the CO 2 exsolution and mineral precipitation during depressurization change the morphology, porosity, and permeability of the porous rock medium, which then affects the two-phase flow of the CO 2 and formation water. A better understanding of these effects on the CO 2 -water two-phase flow will improve predictions of the long-term CO 2 storage reliability, especially the impact of depressurization on the long-term stability. In this Account, we summarize our recent work on the effect of CO 2 exsolution and mineral dissolution/precipitation on CO 2 transport in GCS reservoirs. We place emphasis on understanding the behavior and transformation of the carbon components in the reservoir, including CO 2 (sc/g), CO 2 (aq), HCO 3 - , and carbonate minerals (calcite and dolomite), highlight their transport and mobility by coupled geochemical and two-phase flow processes, and consider the implications of these transport mechanisms on estimates of the long-term safety of GCS. We describe experimental and numerical pore- and core-scale methods used in our lab in conjunction with industrial and international partners to investigate these effects. Experimental results show how mineral dissolution affects permeability, capillary pressure, and relative permeability, which are important phenomena affecting the input parameters for reservoir flow modeling. The porosity and the absolute permeability increase when CO 2 dissolved water is

Mineral Replacement Reactions as a Precursor to Strain Localisation: an (HR-)EBSD approach

Science.gov (United States)

Gardner, J.; Wheeler, J.; Wallis, D.; Hansen, L. N.; Mariani, E.

2017-12-01

Much remains to be learned about the links between metamorphism and deformation. Our work investigates the behaviour of fluid-mediated mineral replacement reaction products when exposed to subsequent shear stresses. We focus on albite from a metagabbro that has experienced metamorphism and subsequent deformation at greenschist facies, resulting in a reduction in grain size and associated strain localisation. EBSD maps show that prior to grain size reduction, product grains are highly distorted, yet they formed, and subsequently deformed, at temperatures at which extensive dislocation creep is unlikely. The Weighted Burgers Vector can be used to quantitatively describe the types of Burgers vectors present in geometrically necessary dislocation (GND) populations derived from 2-D EBSD map data. Application of this technique to the distorted product grains reveals the prominence of, among others, dislocations with apparent [010] Burgers vectors. This supports (with some caveats) the idea that dislocation creep is not responsible for the observed lattice distortion, as there are no known slip systems in plagioclase with a [010] Burgers vector. Distortion in a replacement microstructure has also been attributed to the presence of nanoscale product grains, which share very similar, but not identical, orientations due to topotactic nucleation from adjacent sites on the same substrate. As a precipitate, the product grains should be expected to be largely free of elastic strain. However, high angular resolution EBSD results demonstrate that product grains contain both elastic strains (> 10-3) and residual stresses (several hundred MPa), as well as GND densities on the order of 1014-1015 m-2. Thus we suggest the observed distortion (elastic strain plus rotations) in the lattice is produced during the mineral replacement reaction by a lattice mismatch and volume change between parent and product. Stored strain energy then provides a driving force for recovery and

Biosedimentary and geochemical constraints on the precipitation of mineral crusts in shallow sulphate lakes

Science.gov (United States)

Cabestrero, Óscar; del Buey, Pablo; Sanz-Montero, M. Esther

2018-04-01

Seasonal desiccation of Mg2+-(Na+)-(Ca2+)-SO42--(Cl-) saline lakes in La Mancha (Central Spain) that host microbial mats led to the precipitation of hydrated Na-Mg sulphates and gypsum. Sulphates precipitated in the submerged conditions form extensive biolaminites, whilst in marginal areas they produce thin crusts. Sedimentological, mineralogical, petrographic and high resolution textural studies reveal that the crusts were formed within the benthic microbial mats that thrive at salinities ranging from 160 to 340 g·L-1. The minerals of the crusts are primary bloedite (Na2Mg(SO4)2·4H2O), epsomite (MgSO4·7H2O), gypsum (CaSO4·2H2O) and mirabilite (Na2SO4·10H2O), as well as secondary hexahydrite (MgSO4·6H2O) and thenardite (Na2SO4). Primary bloedite crystals, which form the framework of surficial and submerged crusts are seen to nucleate subaqueously and grow incorporatively within the matgrounds. Displacive and incorporative epsomite grows on previous bloedite crystals and also on the ground. Mirabilite is precipitated rapidly at the brine-air interface over bloedite and epsomite. Hexahydrite and thenardite are formed due to dehydration of epsomite and mirabilite, respectively. Hydrochemical modeling with PHREEQC indicated that evaporitic biolaminites are forming from brines undersaturated with respect to bloedite, epsomite and mirabilite, which suggests that the microorganisms contribute to the heterogeneous nucleation of the sulphates in the microbial mats. Unlike carbonates, the influence of microbes on the growth and morphology of complicated double salts such as bloedite has not been documented previously and provides a new perspective on the formation of hydrated sulphate minerals that are common on Earth as well as other planets.

Evolution of permeability in siliceous rocks induced by mineral dissolution and precipitation

International Nuclear Information System (INIS)

Yasuhara, Hideaki; Kinoshita, Naoki; Kurikami, Hiroshi; Nakashima, Shinichiro; Kishida, Kiyoshi

2007-01-01

A conceptual model is presented to follow the evolution of permeability in siliceous rocks mediated by pressure solution. Specifically, the main minerals of siliceous rocks that are quartz, cristobalite, and amorphous silica, are focused to examine differences of the permeability evolutions among them at effective pressures of 1, 5, and 10 MPa, and temperatures of 20 and 90degC. The rates and magnitudes of permeability reduction increase with increases of the pressures and temperatures applied. Ultimate permeabilities reduced by the order of 90 % at the completion of dissolution-mediated compaction at 10 MPa and 90degC. Precipitation may augment more degradation of flow transport in time. (author)

Coupled multiphase reactive flow and mineral dissolution-precipitation kinetics: Examples of long-term CO2 sequestration in Utsira Sand, Norway and Mt. Simon Formation, Midwest USA

Science.gov (United States)

Zhang, Y.; Zhang, G.; Lu, P.; Hu, B.; Zhu, C.

2017-12-01

The extent of CO2 mineralization after CO2 injection into deep saline aquifers is a result of the complex coupling of multiphase fluid flow, mass transport, and brine-mineral reactions. The effects of dissolution rate laws and groundwater flow on the long-term fate of CO2 have been seriously overlooked. To investigate these effects, we conducted multiphase (CO2 and brine) coupled reactive transport modeling of CO2 storage in two sandy formations (Utsira Sand, Norway1,2 and Mt. Simon formation, USA 3) using ToughReact and simulated a series of scenarios. The results indicated that: (1) Different dissolution rate laws for feldspars can significantly affect the amount of CO2 mineralization. Increased feldspar dissolution will promote CO2 mineral trapping through the coupling between feldspar dissolution and carbonate mineral precipitation at raised pH. The predicted amount of CO2 mineral trapping when using the principle of detailed balancing-based rate law for feldspar dissolution is about twice as much as that when using sigmoidal rate laws in the literature. (2) Mineral trapping is twice as much when regional groundwater flow is taken into consideration in long-term simulations (e.g., 10,000 years) whereas most modeling studies neglected the regional groundwater flow back and effectively simulated a batch reactor process. Under the influence of regional groundwater flow, the fresh brine from upstream continuously dissolves CO2 at the tail of CO2 plume, generating a large acidified area where large amount of CO2 mineralization takes place. The upstream replenishment of groundwater results in ˜22% mineral trapping at year 10,000, compared to ˜4% when this effect is ignored. Refs: 1Zhang, G., Lu, P., Wei, X., Zhu, C. (2016). Impacts of Mineral Reaction Kinetics and Regional Groundwater Flow on Long-Term CO2 Fate at Sleipner. Energy & Fuels, 30(5), 4159-4180. 2Zhu, C., Zhang, G., Lu, P., Meng, L., Ji, X. (2015). Benchmark modeling of the Sleipner CO2 plume

Distribution of Clay Minerals in Light Coal Fractions and the Thermal Reaction Products of These Clay Minerals during Combustion in a Drop Tube Furnace

Directory of Open Access Journals (Sweden)

Sida Tian

2016-06-01

Full Text Available To estimate the contribution of clay minerals in light coal fractions to ash deposition in furnaces, we investigated their distribution and thermal reaction products. The light fractions of two Chinese coals were prepared using a 1.5 g·cm−3 ZnCl2 solution as a density separation medium and were burned in a drop-tube furnace (DTF. The mineral matter in each of the light coal fractions was compared to that of the relevant raw coal. The DTF ash from light coal fractions was analysed using hydrochloric acid separation. The acid-soluble aluminium fractions of DTF ash samples were used to determine changes in the amorphous aluminosilicate products with increasing combustion temperature. The results show that the clay mineral contents in the mineral matter of both light coal fractions were higher than those in the respective raw coals. For the coal with a high ash melting point, clay minerals in the light coal fraction thermally transformed more dehydroxylation products compared with those in the raw coal, possibly contributing to solid-state reactions of ash particles. For the coal with a low ash melting point, clay minerals in the light coal fraction produced more easily-slagging material compared with those in the raw coal, playing an important role in the occurrence of slagging. Additionally, ferrous oxide often produces low-melting substances in coal ash. Due to the similarities of zinc oxide and ferrous oxide in silicate reactions, we also investigated the interactions of clay minerals in light coal fractions with zinc oxide introduced by a zinc chloride solution. The extraneous zinc oxide could react, to a small extent, with clay minerals in the coal during DTF combustion.

Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

Energy Technology Data Exchange (ETDEWEB)

Penner, Larry R.; O' Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

2004-01-01

Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

International Nuclear Information System (INIS)

Penner, Larry R.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

2004-01-01

Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism

Experiment and simulation study on the effects of cement minerals on the water-rock-CO2 interaction during CO2 geological storage

Science.gov (United States)

Liu, N.; Cheng, J.

2016-12-01

The CO2 geological storage is one of the most promising technology to mitigate CO2 emission. The fate of CO2 underground is dramatically affected by the CO2-water-rock interaction, which are mainly dependent on the initial aquifer mineralogy and brine components. The cement minerals are common materials in sandstone reservoir but few attention has been paid for its effects on CO2-water-rock interaction. Five batch reactions, in which 5% cement minerals were assigned to be quartz, calcite, dolomite, chlorite and Ca-montmorillonite, respectively, were conducted to understanding the cement minerals behaviors and its corresponding effects on the matrix minerals alterations during CO2 geological storage. Pure mineral powders were selected to mix and assemble the 'sandstone rock' with different cement components meanwhile keeping the matrix minerals same for each group as 70% quartz, 20% K-feldspar and 5% albite. These `rock' reacted with 750ml deionized water and CO2 under 180° and 18MPa for 15 days, during which the water chemistry evolution and minerals surface micromorphology changes has been monitored. The minerals saturation indexes calculation and phase diagram as well as the kinetic models were made by PHREEQC to uncover the minerals reaction paths. The experiment results indicated that the quartz got less eroded, on the contrary, K-feldspar and albite continuously dissolved to favor the gibbsite and kaolinite precipitations. The carbonates cement minerals quickly dissolved to reach equilibrium with the pH buffered and in turn suppressed the alkali feldspar dissolutions. No carbonates minerals precipitations occurred until the end of reactions for all groups. The simulation results were basically consistent with the experiment record but failed to simulate the non-stoichiometric reactions and the minerals kinetic rates seemed underestimated at the early stage of reactions. The cement minerals significantly dominated the reaction paths during CO2 geological

Continuous precipitation of mineral products: influence of mixing conditions on the co-precipitation of cerium-zirconium mixed oxides

International Nuclear Information System (INIS)

Di Patrizio, Nicolas

2015-01-01

An automated experimental set-up with rapid mixers is used to study the influence of mixing conditions on the co-precipitation of cerium-zirconium mixed oxides. The intensity of mixing is controlled by the inlet flow rates of the reacting solutions. An engulfment model is used to estimate a mixing time from the measurement of a segregation index by the Villermaux-Dushman reaction system. Three geometries of Hartridge Roughton mixers are compared. Mixing performance is better when a separate mixing chamber upstream of a narrower outlet pipe is present. A better mixing decreases the maximal reducibility temperature of the material and increases the crystal strains of the particles calcined at 1100 C. This is probably due to a better homogenization of the particles content. The important incorporation of nitrates in the particle at the outlet of the mixers shows precipitation occurs while the mixing process is not finished. This experimental result was confirmed by numerical simulation and an estimation of sur-saturations during the mixing process. (author)

Heterogeneous Reactions between Toluene and NO2 on Mineral Particles under Simulated Atmospheric Conditions.

Science.gov (United States)

Niu, Hejingying; Li, Kezhi; Chu, Biwu; Su, Wenkang; Li, Junhua

2017-09-05

Heterogeneous reactions between organic and inorganic gases with aerosols are important for the study of smog occurrence and development. In this study, heterogeneous reactions between toluene and NO 2 with three atmospheric mineral particles in the presence or absence of UV light were investigated. The three mineral particles were SiO 2 , α-Fe 2 O 3 , and BS (butlerite and szmolnokite). In a dark environment, benzaldehyde was produced on α-Fe 2 O 3 . For BS, nitrotoluene and benzaldehyde were obtained. No aromatic products were produced in the absence of NO 2 in the system. In the presence of UV irradiation, benzaldehyde was detected on the SiO 2 surface. Identical products were produced in the presence and absence of UV light over α-Fe 2 O 3 and BS. UV light promoted nitrite to nitrate on mineral particles surface. On the basisi of the X-ray photoelectron spectroscopy (XPS) results, a portion of BS was reduced from Fe 3+ to Fe 2+ with the adsorption of toluene or the reaction with toluene and NO 2 . Sulfate may play a key role in the generation of nitrotoluene on BS particles. From this research, the heterogeneous reactions between organic and inorganic gases with aerosols that occur during smog events will be better understood.

Geochemical models of metasomatism in ultramafic systems: Serpentinization, rodingitization, and sea floor carbonate chimney precipitation

Science.gov (United States)

Palandri, J.L.; Reed, M.H.

2004-01-01

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300??C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25??C and w/r less than ???32, conditions are sufficiently reducing to yield H2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH- production by olivine and pyroxene dissolution in the absence of counterbalancing OH- consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg2+ and Ca2+ to accumulate in the aqueous phase in exchange for H+. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300??C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg??. In serpentinization by seawater at 300??C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300??C yields rodingite-type mineral assemblages, including

Nitrate-cancrinite precipitation on quartz sand in simulated Hanford tank solutions.

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Bickmore, B R; Nagy, K L; Young, J S; Drexler, J W

2001-11-15

Caustic NaNO3 solutions containing dissolved Al were reacted with quartz sand at 89 degrees C to simulate possible reactions between leaked nuclear waste and primary subsurface minerals at the U.S. Department of Energy's Hanford site in Washington. Nitrate-cancrinite began to precipitate onto the quartz after 2-10 days, cementing the grains together. Estimates of the equilibrium constant for the precipitation reaction differ for solutions with 0.1 or 1.0 m OH- (log Keq = 30.4 +/- 0.8 and 36.2 +/- 0.6, respectively). The difference in solubility may be attributable to more perfect crystallinity (i.e., fewer stacking faults) in the higher-pH cancrinite structure. This is supported by electron micrographs of crystal morphology and measured rates of Na volatilization under an electron beam. Precipitate crystallinity may affect radionuclide mobility, because stacking faults in the cancrinite structure can diminish its zeolitic cation exchange properties. The precipitation rate near the onset of nucleation depends on the total Al and Si concentrations in solution. The evolution of experimental Si concentrations was modeled by considering the dependence of quartz dissolution rate on AI(OH)4- activity, cancrinite precipitation, and the reduction of reactive surface area of quartz due to coverage by cancrinite.

Process for the reduction of competitive oxidant consuming reactions in the solution mining of a mineral

International Nuclear Information System (INIS)

Stover, D.E.

1980-01-01

The present invention relates to an improved method for the solution mining of a mineral from a subterranean formation. More specifically, the invention relates to an improved method which enhances significantly the recovery of the mineral from a subterranean formation via solution mining by reducing the oxidant consuming reactions which compete with the mineral for the oxidant injected therein

Precipitation kinetics of Mg-carbonates, influence of organic ligands and consequences for CO2 mineral sequestration

International Nuclear Information System (INIS)

Gautier, Q.

2012-01-01

Forming magnesium carbonate minerals through carbonation of magnesium silicates has been proposed as a safe and durable way to store carbon dioxide, with a possibly high potential to offset anthropogenic CO 2 emissions. To date however, chemical reactions involved in this process are facing strong kinetic limitations, which originate in the low reactivity of both Mg-silicates and Mg-carbonates. Numerous studies have focused on the dissolution of Mg-silicates, under the questionable hypothesis that this step limits the whole process. This thesis work focuses instead on the mechanisms and rates of formation of magnesium carbonates, which are the final products of carbonation reactions. The first part of the work is dedicated to studying the influence on magnesite precipitation kinetics of three organic ligands known to accelerate Mg-silicates dissolution rates: oxalate, citrate and EDTA. With help of mixed-flow reactor experiments performed between 100 and 150 C, we show that these ligands significantly reduce magnesite growth rates, through two combined mechanisms: (1) complexation of Mg 2+ cations in aqueous solution, which was rigorously estimated from a thermodynamic database established through a critical review of the literature, and (2) adsorption of ligands to a limited number of surface sites, leading to a decrease of the precipitation rate constant. The observed growth inhibition is maximal with citrate. We then used hydrothermal atomic force microscopy to probe the origin of the documented growth inhibition. Our observations show that citrate and oxalate interact with the crystal growth process on magnesite surface, modifying the shape of growth hillocks as well as the step generation frequency through spiral growth. We also show that the ligands adsorb preferentially on different kink-sites, which is probably related to their different structures and chemical properties. We propose that the stronger magnesite growth inhibition caused by citrate is related

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

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Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system

Kinetics of Heterogeneous Reaction of Sulfur Dioxide on Authentic Mineral Dust: Effects of Relative Humidity and Hydrogen Peroxide.

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Huang, Liubin; Zhao, Yue; Li, Huan; Chen, Zhongming

2015-09-15

Heterogeneous reaction of SO2 on mineral dust seems to be an important sink for SO2. However, kinetic data about this reaction on authentic mineral dust are scarce and are mainly limited to low relative humidity (RH) conditions. In addition, little is known about the role of hydrogen peroxide (H2O2) in this reaction. Here, we investigated the uptake kinetics of SO2 on three authentic mineral dusts (i.e., Asian mineral dust (AMD), Tengger desert dust (TDD), and Arizona test dust (ATD)) in the absence and presence of H2O2 at different RHs using a filter-based flow reactor, and applied a parameter (effectiveness factor) to the estimation of the effective surface area of particles for the calculation of the corrected uptake coefficient (γc). We found that with increasing RH, the γc decreases on AMD particles, but increases on ATD and TDD particles. This discrepancy is probably due to the different mineralogy compositions and aging extents of these dust samples. Furthermore, the presence of H2O2 can promote the uptake of SO2 on mineral dust at different RHs. The probable explanations are that H2O2 rapidly reacts with SO2 on mineral dust in the presence of adsorbed water, and OH radicals, which can be produced from the heterogeneous decomposition of H2O2 on the mineral dust, immediately react with adsorbed SO2 as well. Our results suggest that the removal of SO2 via the heterogeneous reaction on mineral dust is an important sink for SO2 and has the potential to alter the physicochemical properties (e.g., ice nucleation ability) of mineral dust particles in the atmosphere.

Fault geometry and fluid-rock reaction: Combined controls on mineralization in the Xinli gold deposit, Jiaodong Peninsula, China

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Yang, Lin; Zhao, Rui; Wang, Qingfei; Liu, Xuefei; Carranza, Emmanuel John M.

2018-06-01

The structures and fluid-rock reaction in the Xinli gold deposit, Jiaodong Peninsula, were investigated to further understand their combined controls on the development of permeability associated with ore-forming fluid migration. Orebodies in this deposit are hosted by the moderately SE-to S-dipping Sanshandao-Cangshang fault (SCF). Variations in both dip direction and dip angle along the SCF plane produced fault bends, which controlled the fluid accumulation and ore-shoot formation. Gold mineralizations occurred in early gold-quartz-pyrite and late gold-quartz-polymetallic sulphide stages following pervasive sericitization and silicification alterations. Theoretical calculation indicates that sericitization caused 8-57% volume decrease resulting in the development/enlargement of voids, further increase of grain-scale permeability, and resultant precipitation of the early gold-quartz-pyrite pods, which destroyed permeability. The rock softening produced by alterations promoted activities of SCF secondary faults and formation of new fractures, which rebuilt the permeability and controlled the late gold-quartz-polymetallic sulfide veins. Quantitative studies on permeability distributions show that the southwestern and northeastern bend areas with similar alteration and mineralization have persistent and anti-persistent permeability networks, respectively. These were likely caused by different processes of rebuilding permeability due to different stress states resulting from changes in fault geometry.

Effect of Hydrochemistry on Mineral Precipitation and Textural Diversity in Serpentinization-driven Alkaline Environments; Insights from Thermal Springs in the Oman Ophiolite.

Science.gov (United States)

Bach, W.; Giampouras, M.; Garcia-Ruiz, J. M.; Garrido, C. J.; Los, C.; Fussmann, D.; Monien, P.

2017-12-01

Interactions between meteoric water and ultramafic rocks within Oman ophiolite give rise to the formation of thermal spring waters of variable composition and temperature. Discharge of two different types of water forms complex hydrological networks of streams and ponds, in which the waters mix, undergo evaporation, and take up atmospheric CO2. We conducted a pond-by-pond sampling of waters and precipitates in two spring sites within the Wadi Tayin massif, Nasif and Khafifah, and examined how hydrochemistry and associated mineral saturation states affect the variations in mineral phases and textures. Three distinctive types of waters were identified in the system: a) Mg-type (7.9 11.6); Ca-OH-rich waters, and c) Mix-type (9.6 < pH < 11.5); waters arising upon mixing of Mg-type and Ca-type. PHREEQC was used to evaluate the role of mixing in aqueous speciation and the evolution of the saturation index value of different mineral phases. Mineral and textural characterization by X-ray diffraction, Raman spectroscopy and scanning electron microscopy were combined with these hydrogeochemical constraints to determine the factors controlling mineralogical and textural diversity in the system. In Ca-type waters, uptake of CO2 during the exposure of the fluids to the atmosphere is the predominant precipitation mechanism of CaCO3. High Mg:Ca ratios and high supersaturation rate of CaCO3 favor the growth of aragonite over calcite in mixed fluids. Changes in morphology and texture of aragonite crystals and crystal aggregates indicate the variations in the values of supersaturation and supersaturation rate of CaCO3 in the different water types. Brucite precipitation is common and driven by fluid mixing, while interaction with air-derived CO2 causes its alteration to hydromagnesite. The proximity of gabbroic lithologies appears to affect the presence of Al-bearing layered double hydroxides (LDHs). Furthermore, transformation of nesquehonite to dypingite in Mg-type waters record a

Seasonal factors controlling mineral precipitation in the acid mine drainage at Donghae coal mine, Korea

International Nuclear Information System (INIS)

Kim, J.J.; Kim, S.J.

2004-01-01

Monitoring over a 12 month period in the Sanae creek flow in acid mine drainage, Donghae coal mine area, demonstrates that the concentrations of dissolved metals and sulphate are highest during autumn when water flow in the creek is at its lowest. The highest pH values of the stream were measured in April and May, whereas the lowest pH was recorded in October. The Fe concentration of stream water rapidly decreased downstream due to the precipitation of Fe oxyhydroxide and/or oxyhydroxysulfate phases in the stream. Mineral precipitates in the creek in the Donghae mine area show various colours such as brownish yellow (Munsell colour 9.5 YR hues), reddish brown (Munsell colour 3.5 YR hues) and white depending on seasons and distance from the pollution source in the creek. Such phenomena are attributed to the variation in pH and chemical composition of stream water caused by seasonal factors. The measured pH ranges in stream water of the brownish yellow, white and reddish brown precipitates are pH 3.2-4.5, 4.5-6.0 and 5.3-6.9, respectively

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

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Fulvio Di Lorenzo

2018-05-01

Full Text Available One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS. Here, we studied the different steps of wollastonite (CaSiO3 carbonation (silicate dissolution → carbonate precipitation as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA, a natural enzyme that catalyzes the reversible hydration of CO2(aq, and biomimetic metal-organic frameworks (MOFs. Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl-specific. CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.

The Transformation of Coal-Mining Waste Minerals in the Pozzolanic Reactions of Cements

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Rosario Giménez-García

2016-06-01

Full Text Available The cement industry has the potential to become a major consumer of recycled waste materials that are transformed and recycled in various forms as aggregates and pozzolanic materials. These recycled waste materials would otherwise have been dumped in landfill sites, leaving hazardous elements to break down and contaminate the environment. There are several approaches for the reuse of these waste products, especially in relation to clay minerals that can induce pozzolanic reactions of special interest in the cement industry. In the present paper, scientific aspects are discussed in relation to several inert coal-mining wastes and their recycling as alternative sources of future eco-efficient pozzolans, based on activated phyllosilicates. The presence of kaolinite in this waste indicates that thermal treatment at 600 °C for 2 h transformed these minerals into a highly reactive metakaolinite over the first seven days of the pozzolanic reaction. Moreover, high contents of metakaolinite, together with silica and alumina sheet structures, assisted the appearance of layered double hydroxides through metastable phases, forming stratlingite throughout the main phase of the pozzolanic reaction after 28 days (as recommended by the European Standard as the reaction proceeded.

Anhydrite precipitation in seafloor hydrothermal systems

Science.gov (United States)

Theissen-Krah, Sonja; Rüpke, Lars H.

2016-04-01

The composition and metal concentration of hydrothermal fluids venting at the seafloor is strongly temperature-dependent and fluids above 300°C are required to transport metals to the seafloor (Hannington et al. 2010). Ore-forming hydrothermal systems and high temperature vents in general are often associated with faults and fracture zones, i.e. zones of enhanced permeabilities that act as channels for the uprising hydrothermal fluid (Heinrich & Candela, 2014). Previous numerical models (Jupp and Schultz, 2000; Andersen et al. 2015) however have shown that high permeabilities tend to decrease fluid flow temperatures due to mixing with cold seawater and the resulting high fluid fluxes that lead to short residence times of the fluid near the heat source. A possible mechanism to reduce the permeability and thereby to focus high temperature fluid flow are mineral precipitation reactions that clog the pore space. Anhydrite for example precipitates from seawater if it is heated to temperatures above ~150°C or due to mixing of seawater with hydrothermal fluids that usually have high Calcium concentrations. We have implemented anhydrite reactions (precipitation and dissolution) in our finite element numerical models of hydrothermal circulation. The initial results show that the precipitation of anhydrite efficiently alters the permeability field, which affects the hydrothermal flow field as well as the resulting vent temperatures. C. Andersen et al. (2015), Fault geometry and permeability contrast control vent temperatures at the Logatchev 1 hydrothermal field, Mid-Atlantic Ridge, Geology, 43(1), 51-54. M. D. Hannington et al. (2010), Modern Sea-Floor Massive Sulfides and Base Metal Resources: Toward an Estimate of Global Sea-Floor Massive Sulfide Potential, in The Challenge of Finding New Mineral Resources: Global Metallogeny, Innovative Exploration, and New Discoveries, edited by R. J. Goldfarb, E. E. Marsh and T. Monecke, pp. 317-338, Society of Economic Geologists

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.

Interactions in the Geo-Biosphere: Processes of Carbonate Precipitation in Microbial Mats

Science.gov (United States)

Dupraz, C.; Visscher, P. T.

2009-12-01

Microbial communities are situated at the interface between the biosphere, the lithosphere and the hydrosphere. These microbes are key players in the global carbon cycle, where they influence the balance between the organic and inorganic carbon reservoirs. Microbial populations can be organized in microbial mats, which can be defined as organosedimentary biofilms that are dominated by cyanobacteria, and exhibit tight coupling of element cycles. Complex interactions between mat microbes and their surrounding environment can result in the precipitation of carbonate minerals. This process refers as ‘organomineralization sensu lato' (Dupraz et al. in press), which differs from ‘biomineralization’ (e.g., in shells and bones) by lacking genetic control on the mineral product. Organomineralization can be: (1) active, when microbial metabolic reactions are responsible for the precipitation (“biologically-induced” mineralization) or (2) passive, when mineralization within a microbial organic matrix is environmentally driven (e.g., through degassing or desiccation) (“biologically-influenced” mineralization). Studying microbe-mineral interactions is essential to many emerging fields of the biogeoscience, such as the study of life in extreme environments (e.g, deep biosphere), the origin of life, the search for traces of extraterrestrial life or the seek of new carbon sink. This research approach combines sedimentology, biogeochemistry and microbiology. Two tightly coupled components that control carbonate organomineralization s.l.: (1) the alkalinity engine and (2) the extracellular organic matter (EOM), which is ultimately the location of mineral nucleation. Carbonate alkalinity can be altered both by microbial metabolism and environmental factors. In microbial mats, the net accumulation of carbonate minerals often reflect the balance between metabolic activities that consume/produce CO2 and/or organic acids. For example, photosynthesis and sulfate reduction

FLUID EVOLUTION AND MINERAL REACTIONS DURING SHEAR ZONE FORMATION AT NUSFJORD, LOFOTEN, NORWAY (Invited)

Science.gov (United States)

Kullerud, K.

2009-12-01

At Nusfjord in Lofoten, Norway, three 0.3 - 3 m thick shear zones occur in a gabbro-anorthosite. During deformation, the shear zones were infiltrated by a hydrous fluid enriched in Cl. In the central parts of the shear zones, fluid-rock interaction resulted in complete break-down of the primary mafic silicates. Complete hydration of these minerals to Cl-free amphibole and biotite suggests that the hydrous fluid was present in excess during deformation in these parts of the shear zones. Along the margins of the shear zones, however, the igneous mafic silicates (Cpx, Bt, Opx) were only partly overgrown by hydrous minerals. Here, Cl-enriched minerals (Amph, Bt, Scp, Ap) can be observed. Amphibole shows compositions covering the range 0.1 - 4.0 wt % Cl within single thin sections. Mineral textures and extreme compositional variations of the Cl-bearing minerals indicate large chemical gradients of the fluid phase. Relics of primary mafic silicates and compositionally zoned reaction coronas around primary mafic silicates suggest that the free fluid was totally consumed before the alteration of the primary phases were completed. The extreme variations in the Cl-content of amphibole are inferred to monitor a gradual desiccation of the Cl-bearing grain-boundary fluid during fluid-mineral reactions accordingly: 1) The first amphibole that formed during the reactions principally extracted water from the fluid, resulting in a slight increase in the Cl content of the fluid. 2) Continued amphibole-forming reactions resulted in gradual consumption of the free fluid phase, principally by extracting water from the fluid, resulting in an increase in its Cl-content. Higher Cl-content of the fluid resulted in higher Cl-content of the equilibrium amphibole. 3) The most Cl-enriched amphibole (4 wt % Cl) formed in equilibrium with the last volumes of the grain-boundary fluid, which had evolved to a highly saline solution. Mineral reactions within a 1-2 thick zone of the host rock along

Investigation of microbial-mineral interactions by Moessbauer spectroscopy

International Nuclear Information System (INIS)

Sawicki, J.A.; Brown, D.A.

1998-01-01

Moessbauer spectroscopy was used to investigate the reactions of microbes with iron minerals in aqueous solutions and as components of rocks in banded iron formations and granite. A microbial biofilm that formed on a wall of an excavated granite vault in a deep underground laboratory initiated this research. At the aerobic face of the biofilm, iron was found in a form of ferrihydrite; in the anaerobic face against the rock, iron was found as very small siderite particles. Laboratory incubations of the biofilm microbial consortium showed different mineral species could be formed. When the microbial consortium from the biofilm was incubated with magnetite grains, up to about 10% of the iron was altered in three weeks to hematite. The ability of the consortium to precipitate iron both as Fe 2+ and Fe 3+ in close proximity may have a bearing on the deposition of banded iron formations. These reactions could also be important in microbially induced corrosion

Sorption and redox reactions of As(III) and As(V) within secondary mineral coatings on aquifer sediment grains.

Science.gov (United States)

Singer, David M; Fox, Patricia M; Guo, Hua; Marcus, Matthew A; Davis, James A

2013-10-15

Important reactive phenomena that affect the transport and fate of many elements occur at the mineral-water interface (MWI), including sorption and redox reactions. Fundamental knowledge of these phenomena are often based on observations of ideal mineral-water systems, for example, studies of molecular scale reactions on single crystal faces or the surfaces of pure mineral powders. Much less is understood about MWI in natural environments, which typically have nanometer to micrometer scale secondary mineral coatings on the surfaces of primary mineral grains. We examined sediment grain coatings from a well-characterized field site to determine the causes of rate limitations for arsenic (As) sorption and redox processes within the coatings. Sediments were obtained from the USGS field research site on Cape Cod, MA, and exposed to synthetic contaminated groundwater solutions. Uptake of As(III) and As(V) into the coatings was studied with a combination of electron microscopy and synchrotron techniques to assess concentration gradients and reactive processes, including electron transfer reactions. Transmission electron microscopy (TEM) and X-ray microprobe (XMP) analyses indicated that As was primarily associated with micrometer- to submicrometer aggregates of Mn-bearing nanoparticulate goethite. As(III) oxidation by this phase was observed but limited by the extent of exposed surface area of the goethite grains to the exterior of the mineral coatings. Secondary mineral coatings are potentially both sinks and sources of contaminants depending on the history of a contaminated site, and may need to be included explicitly in reactive transport models.

Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone, New Hampshire, USA

Science.gov (United States)

McAleer, Ryan J.; Bish, David L.; Kunk, Michael J.; Sicard, Karri R.; Valley, Peter M.; Walsh, Gregory J.; Wathen, Bryan A.; Wintsch, R.P.

2016-01-01

We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na-poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric-forming Na-rich muscovite is also progressively replaced by fabric-forming Na-poor muscovite. The mineralogy of the new phyllonitic fault-rock produced is dominated by Na-poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric-forming Na-rich muscovite is selectively replaced at high-strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high-grade porphyroblasts by weaker Na-poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na-rich muscovite-defined foliation destroys not only the metastable high-grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.

Periodic precipitation a microcomputer analysis of transport and reaction processes in diffusion media, with software development

CERN Document Server

Henisch, H K

1991-01-01

Containing illustrations, worked examples, graphs and tables, this book deals with periodic precipitation (also known as Liesegang Ring formation) in terms of mathematical models and their logical consequences, and is entirely concerned with microcomputer analysis and software development. Three distinctive periodic precipitation mechanisms are included: binary diffusion-reaction; solubility modulation, and competitive particle growth. The book provides didactic illustrations of a valuable investigational procedure, in the form of hypothetical experimentation by microcomputer. The development

FIA-FAAS method for tannin determination based on a precipitation reaction with hemoglobin

Directory of Open Access Journals (Sweden)

Ferreira Edilene C.

2003-01-01

Full Text Available A flow system, coupled with flame atomic absorption spectrometry (FIA-FAAS, was developed for tannin determination in pigeon pea samples, exploring the precipitation reaction between tannins and proteins. Sample extracts obtained by sonication with a 50% (v/v methanol solution were introduced into the system and induced to react with a hemoglobin solution. The precipitate produced was retained on a filter located in the analytical flow. A reversed flow of 1% (w/v sodium dodecyl sulfate solution was used for solubilization of the precipitate from the filter and to conduct the tannin-hemoglobin complex to the FAAS, to quantify the iron ions present in the hemoglobin structure. A tannic acid solution was used to prepare the analytical curve. The proposed method allowed determination of 30 samples per hour, a standard deviation of 9.7% (n=10, and a quantification limit of 0.27 mg L-1 for tannic acid.

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals

International Nuclear Information System (INIS)

Feng Xionghan; Zhai Limei; Tan Wenfeng; Liu Fan; He Jizheng

2007-01-01

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite ≥ cryptomelane > todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb 2+ , Cu 2+ , Co 2+ , Cd 2+ and Zn 2+ , while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb 2+ among the tested heavy metals. Hydration tendency (pK 1 ) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn 2+ varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0) > cryptomelane (422.6) > todorokite (59.7) > hausmannite (36.6). - The characteristics of heavy metal adsorption and Cr(III) oxidation on Mn oxide minerals are determined by their structure, composition, surface property and crystallinity

Mineral CO2 sequestration by steel slag carbonation

International Nuclear Information System (INIS)

Huijgen, W.J.J.; Comans, R.N.J.; Witkamp, G.J.

2005-12-01

Mineral CO2 sequestration, i.e., carbonation of alkaline silicate Ca/Mg minerals, analogous to natural weathering processes, is a possible technology for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline Ca-rich industrial residues are presented as a possible feedstock for mineral CO2 sequestration. These materials are cheap, available near large point sources of CO2, and tend to react relatively rapidly with CO2 due to their chemical instability. Ground steel slag was carbonated in aqueous suspensions to study its reaction mechanisms. Process variables, such as particle size, temperature, carbon dioxide pressure, and reaction time, were systematically varied, and their influence on the carbonation rate was investigated. The maximum carbonation degree reached was 74% of the Ca content in 30 min at 19 bar pressure, 100C, and a particle size of <38 μm. The two must important factors determining the reaction rare are particle size (<2 mm to <38 μm) and reaction temperature (25-225C). The carbonation reaction was found to occur in two steps: (1) leaching of calcium from the steel slag particles into the solution; (2) precipitation of calcite on the surface of these particles. The first step and, more in particular, the diffusion of calcium through the solid matrix toward the surface appeared to be the rate-determining reaction step, The Ca diffusion was found to be hindered by the formation of a CaCO3-coating and a Ca-depleted silicate zona during the carbonation process. Research on further enhancement of the reaction rate, which would contribute to the development of a cost-effective CO2-sequestration process, should focus particularly on this mechanism

Microbially mediated mineral carbonation

Science.gov (United States)

Power, I. M.; Wilson, S. A.; Dipple, G. M.; Southam, G.

2010-12-01

Mineral carbonation involves silicate dissolution and carbonate precipitation, which are both natural processes that microorganisms are able to mediate in near surface environments (Ferris et al., 1994; Eq. 1). (Ca,Mg)SiO3 + 2H2CO3 + H2O → (Ca,Mg)CO3 + H2O + H4SiO4 + O2 (1) Cyanobacteria are photoautotrophs with cell surface characteristics and metabolic processes involving inorganic carbon that can induce carbonate precipitation. This occurs partly by concentrating cations within their net-negative cell envelope and through the alkalinization of their microenvironment (Thompson & Ferris, 1990). Regions with mafic and ultramafic bedrock, such as near Atlin, British Columbia, Canada, represent the best potential sources of feedstocks for mineral carbonation. The hydromagnesite playas near Atlin are a natural biogeochemical model for the carbonation of magnesium silicate minerals (Power et al., 2009). Field-based studies at Atlin and corroborating laboratory experiments demonstrate the ability of a microbial consortium dominated by filamentous cyanobacteria to induce the precipitation of carbonate minerals. Phototrophic microbes, such as cyanobacteria, have been proposed as a means for producing biodiesel and other value added products because of their efficiency as solar collectors and low requirement for valuable, cultivable land in comparison to crops (Dismukes et al., 2008). Carbonate precipitation and biomass production could be facilitated using specifically designed ponds to collect waters rich in dissolved cations (e.g., Mg2+ and Ca2+), which would allow for evapoconcentration and provide an appropriate environment for growth of cyanobacteria. Microbially mediated carbonate precipitation does not require large quantities of energy or chemicals needed for industrial systems that have been proposed for rapid carbon capture and storage via mineral carbonation (e.g., Lackner et al., 1995). Therefore, this biogeochemical approach may represent a readily

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid.

Science.gov (United States)

Lederer, Madeline R; Staniec, Allison R; Coates Fuentes, Zoe L; Van Ry, Daryl A; Hinrichs, Ryan Z

2016-12-08

Biogenic volatile organic compounds (BVOCs), including the monoterpene limonene, are a major source of secondary organic aerosol (SOA). While gas-phase oxidation initiates the dominant pathway for BVOC conversion to SOA, recent studies have demonstrated that biogenic hydrocarbons can also directly react with acidic droplets. To investigate whether mineral dust may facilitate similar reactive uptake of biogenic hydrocarbons, we studied the heterogeneous reaction of limonene with mineral substrates using condensed-phase infrared spectroscopy and identified the formation of irreversibly adsorbed organic products. For kaolinite, Arizona Test Dust, and silica at 30% relative humidity, GC-MS identified limonene-1,2-diol as the dominant product with total organic surface concentrations on the order of (3-5) × 10 18 molecules m -2 . Experiments with 18 O-labeled water support a mechanism initiated by oxidation of limonene by surface redox sites forming limonene oxide followed by water addition to the epoxide to form limonenediol. Limonene uptake on α-alumina, γ-alumina, and montmorillonite formed additional products in high yield, including carveol, carvone, limonene oxide, and α-terpineol. To model tropospheric processing of mineral aerosol, we also exposed each mineral substrate to gaseous nitric acid prior to limonene uptake and identified similar surface adsorbed products that were formed at rates 2 to 5 times faster than without nitrate coatings. The initial rate of reaction was linearly dependent on gaseous limonene concentration between 5 × 10 12 and 5 × 10 14 molecules cm -3 (0.22-20.5 ppm) consistent with an Eley-Rideal-type mechanism in which gaseous limonene reacts directly with reactive surface sites. Increasing relative humidity decreased the amount of surface adsorbed products indicating competitive adsorption of surface adsorbed water. Using a laminar flow tube reactor we measured the uptake coefficient for limonene on kaolinite at 25% RH to range from

An Analysis of Undergraduate General Chemistry Students' Misconceptions of the Submicroscopic Level of Precipitation Reactions

Science.gov (United States)

Kelly, Resa M.; Barrera, Juliet H.; Mohamed, Saheed C.

2010-01-01

This study examined how 21 college-level general chemistry students, who had received instruction that emphasized the symbolic level of ionic equations, explained their submicroscopic-level understanding of precipitation reactions. Students' explanations expressed through drawings and semistructured interviews revealed the nature of the…

Application of stereolithographic custom models for studying the impact of biofilms and mineral precipitation on fluid flow.

Science.gov (United States)

Stoner, D L; Watson, S M; Stedtfeld, R D; Meakin, P; Griffel, L K; Tyler, T L; Pegram, L M; Barnes, J M; Deason, V A

2005-12-01

Here we introduce the use of transparent experimental models fabricated by stereolithography for studying the impacts of biomass accumulation, minerals precipitation, and physical configuration of flow paths on liquid flow in fracture apertures. The internal configuration of the models ranged in complexity from simple geometric shapes to those that incorporate replicated surfaces of natural fractures and computationally derived fracture surfaces. High-resolution digital time-lapse imaging was employed to qualitatively observe the migration of colloidal and soluble dyes through the flow models. In this study, a Sphingomonas sp. and Sporosarcina (Bacillus) pasteurii influenced the fluid dynamics by physically altering flow paths. Microbial colonization and calcite deposition enhanced the stagnant regions adjacent to solid boundaries. Microbial growth and calcite precipitation occurred to a greater extent in areas behind the fabricated obstacles and less in high-velocity orifices.

A coupled hydrodynamic-hydrochemical modeling for predicting mineral transport in a natural acid drainage system.

Science.gov (United States)

Zegers Risopatron, G., Sr.; Navarro, L.; Montserrat, S., Sr.; McPhee, J. P.; Niño, Y.

2017-12-01

The geochemistry of water and sediments, coupled with hydrodynamic transport in mountainous channels, is of particular interest in central Chilean Andes due to natural occurrence of acid waters. In this paper, we present a coupled transport and geochemical model to estimate and understand transport processes and fate of minerals at the Yerba Loca Basin, located near Santiago, Chile. In the upper zone, water presentes low pH ( 3) and high concentrations of iron, aluminum, copper, manganese and zinc. Acidity and minerals are the consequence of water-rock interactions in hydrothermal alteration zones, rich in sulphides and sulphates, covered by seasonal snow and glaciers. Downstream, as a consequence of neutral to alkaline lateral water contributions (pH >7) along the river, pH increases and concentration of solutes decreases. The mineral transport model has three components: (i) a hydrodynamic model, where we use HEC-RAS to solve 1D Saint-Venant equations, (ii) a sediment transport model to estimate erosion and sedimentation rates, which quantify minerals transference between water and riverbed and (iii) a solute transport model, based on the 1D OTIS model which takes into account the temporal delay in solutes transport that typically is observed in natural channels (transient storage). Hydrochemistry is solved using PHREEQC, a software for speciation and batch reaction. Our results show that correlation between mineral precipitation and dissolution according to pH values changes along the river. Based on pH measurements (and according to literature) we inferred that main minerals in the water system are brochantite, ferrihydrite, hydrobasaluminite and schwertmannite. Results show that our model can predict the transport and fate of minerals and metals in the Yerba Loca Basin. Mineral dissolution and precipitation process occur for limited ranges of pH values. When pH values are increased, iron minerals (schwertmannite) are the first to precipitate ( 2.5

Effects of belowground litter addition, increased precipitation and clipping on soil carbon and nitrogen mineralization in a temperate steppe

OpenAIRE

Ma, L.; Guo, C.; Xin, X.; Yuan, S.; Wang, R.

2013-01-01

Soil carbon (C) and nitrogen (N) cycling are sensitive to changes in environmental factors and play critical roles in the responses of terrestrial ecosystems to natural and anthropogenic perturbations. This study was conducted to quantify the effects of belowground particulate litter (BPL) addition, increased precipitation and their interactions on soil C and N mineralization in two adjacent sites where belowground photosynthate allocation was manipulated through vegetation ...

Relative flotation response of zinc sulfide: Mineral and precipitate

Energy Technology Data Exchange (ETDEWEB)

Rao, S.R.; Finch, J.A. [McGill Univ., Montreal, Quebec (Canada). Dept. of Mining and Metallurgical Engineering; Zhou, Z.; Xu, Z. [Univ. of Alberta, Edmonton, Alberta (Canada). Dept. of Chemical and Materials Engineering

1998-04-01

Flotation continues to extend to nonmineral applications, including recycling of materials, soil remediation, and effluent treatment. A study has been conducted to compare the floatability of fine zinc sulfide (ZnS) precipitates and sphalerite particles. The floatability of the precipitates was significantly poorer compared to sphalerite particles when xanthate was used as the collector. The floatability was improved by using dodecylamine as the collector, and the difference in floatability between the precipitates was further improved significantly by incorporating a hydrodynamic cavitation tube in a conventional (mechanical) flotation cell. The improved kinetics was attributed to in-situ gas nucleation on the precipitates.

The impact of mineral fertilization and atmospheric precipitation on yield of field crops on family farms

Directory of Open Access Journals (Sweden)

Munćan Mihajlo

2016-01-01

Full Text Available The field crop production, as the most important branch of plant production of the Republic of Serbia, in the period 2002-2011, was carried out on an average of over 2.7 million hectares, 82.7% of which took place on the individual farms/family holdings. Hence, the subject of research in this paper covers yields of major field crops realized on family farms in the region of Vojvodina in the period 1972-2011. The main objective of the research is to study the interdependence of utilization of mineral fertilizers and atmospheric precipitation during the vegetation period and realized yields of major field crops on family farms in the observed period. The regression analysis was applied in order to verify dependencies and determine the form of dependence of achieved yields from examined variables. The results showed that the main limiting factors for obtaining high and stable yields of field crops is inadequate use of fertilizers and the lack of precipitation during the vegetation period.

Activation of magnesium rich minerals as carbonation feedstock materials for CO2 sequestration

International Nuclear Information System (INIS)

Maroto-Valer, M.M.; Kuchta, M.E.; Zhang, Y.; Andresen, J.M.; Fauth, D.J.

2005-01-01

Mineral carbonation, the reaction of magnesium-rich minerals such as olivine and serpentine with CO 2 to form stable mineral carbonates, is a novel and promising approach to carbon sequestration. However, the preparation of the minerals prior to carbonation can be energy intensive, where some current studies have been exploring extensive pulverization of the minerals below 37 μm, heat treatment of minerals up to 650 o C, prior separation of CO 2 from flue gases, and carbonation at high pressures, temperatures and long reaction times of up to 125 atm, 185 o C and 6 h, respectively. Thus, the objective of the mineral activation concept is to promote and accelerate carbonation reaction rates and efficiencies through surface activation to the extent that such rigorous reaction conditions were not required. The physical activations were performed with air and steam, while chemical activations were performed with a suite of acids and bases. The parent serpentine, activated serpentines, and carbonation products were characterized to determine their surface properties and assess their potential as carbonation minerals. The results indicate that the surface area of the raw serpentine, which is approximately 8 m 2 /g, can be increased through physical and chemical activation methods to over 330 m 2 /g. The chemical activations were more effective than the physical activations at increasing the surface area, with the 650 o C steam activated serpentine presenting a surface area of only 17 m 2 /g. Sulfuric acid was the most effective acid used during the chemical activations, resulting in surface areas greater than 330 m 2 /g. Several of the samples produced underwent varying degrees of carbonation. The steam activated serpentine underwent a 60% conversion to magnesite at 155 o C and 126 atm in 1 h, while the parent sample only exhibited a 7% conversion. The most promising results came from the carbonation of the extracted Mg(OH) 2 solution, where, based on the amount of

Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds

Energy Technology Data Exchange (ETDEWEB)

Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

1995-07-01

Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

Instability of an infiltration-driven dissolution-precipitation front with a nonmonotonic porosity profile

Science.gov (United States)

Kondratiuk, Paweł; Dutka, Filip; Szymczak, Piotr

2016-04-01

Infiltration of a rock by an external fluid very often drives it out of chemical equilibrium. As a result, alteration of the rock mineral composition occurs. It does not however proceed uniformly in the entire rock volume. Instead, one or more reaction fronts are formed, which are zones of increased chemical activity, separating the altered (product) rock from the yet unaltered (primary) one. The reaction fronts propagate with velocities which are usually much smaller than those of the infiltrating fluid. One of the simplest examples of such alteration is the dissolution of some of the minerals building the primary rock. For instance, calcium carbonate minerals in the rock matrix can be dissolved by infiltrating acidic fluids. In such a case the product rock has higher porosity and permeability than the primary one. Due to positive feedbacks between the reactant transport, fluid flow, and porosity generation, the reaction fronts in porosity-generating replacement systems are inherently unstable. An arbitrarily small protrusion of the front gets magnified and develops into a highly porous finger-like or funnel-like structure. This feature of dissolution fronts, dubbed the "reactive-infiltration instability" [1], is responsible for the formation of a number of geological patterns, such as solution pipes or various karst forms. It is also of practical importance, since spontaneous front breakup and development of localized highly porous flow paths (a.k.a. "wormholes") is favourable by petroleum engineers, who apply acidization to oil-bearing reservoirs in order to increase their permeability. However, more complex chemical reactions might occur during infiltration of a rock by a fluid. In principle, the products of dissolution might react with other species present either in the fluid or in the rock and reprecipitate [2]. The dissolution and precipitation fronts develop and and begin to propagate with equal velocities, forming a single dissolution-precipitation front

Studying of Nano SiO2 Preparation from Rice Husk Ash by Using High Gravity Reaction Precipitation Technology

International Nuclear Information System (INIS)

Nguyen Thanh Chung; Tran Ngoc Ha; Hoang Van Duc

2013-01-01

A novel method (High-gravity reactive precipitation - HGRP) was developed to prepare nano-SiO 2 from rice husk ash using gas-liquid reaction system. The precipitated silica produced by our proposed method had average size of 20 nm with narrow size distribution and purity of SiO 2 was approximately 99.2%. The principles of the method as well as experimental conditions were also described. (author)

Mineral matter reactions in cokes

Energy Technology Data Exchange (ETDEWEB)

D. French; R. Sakurovs; M. Grigore [CSIRO Energy Technology (Australia)

2009-07-15

Some cokes appear to be particularly susceptible to weakening in the blast furnace. A mechanism which has been postulated to explain this is silica reduction by coke. Thus this project was initiated to ascertain the behaviour of quartz and silicates in coke with an emphasis on the role of the clay minerals. It is now possible to obtain quantitative mineralogical data and, the case of coal, to also obtain quantitative data on mineral grain size, shape and association through the use of automated electron beam image analysis techniques. This new ability can allow relationships between the amount of minerals in a coke and its reactivity to be established for the first time. Samples of five Australian coking coals were selected based upon quartz and clay mineral contents, mineral grain size and association. Samples were also provided by BlueScope Steel of coal, feed coke, and tuyere coke samples from the bosh, deadman and raceway regions of the blast furnace. The analytical work program conducted was as follows: Preparation of cokes by CSIRO; Petrography of starting coals and cokes; QEMSCAN of coals; LTA and XRD of starting coals and cokes; Coke reactivity tests (NSC and small scale); Petrography, LTA and XRD of reacted cokes; Petrographic and XRD examination of heat treated cokes. This study indicates that the NSC reactivity test does not adequately reflect the behaviour of coke in the lower part of the blast furnace. Further investigation of the behaviour of coke in the lower part of the blast furnace is required.

EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

Energy Technology Data Exchange (ETDEWEB)

Lindquist, W. Brent; Jones, Keith W.; Um, Wooyong; Rockhold, mark; Peters, Catherine A.; Celia, Michael A.

2013-02-15

This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site - specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE’s legacy waste problems. We established three key issues of reactive flow upscaling, and organized this project in three corresponding thrust areas. 1) Reactive flow experiments. The combination of mineral dissolution and precipitation alters pore network structure and the subsequent flow velocities, thereby creating a complex interaction between reaction and transport. To examine this phenomenon, we conducted controlled laboratory experimentation using reactive flow-through columns. Results and Key Findings: Four reactive column experiments (S1, S3, S4, S5) have been completed in which simulated tank waste leachage (STWL) was reacted with pure quartz sand, with and without Aluminum. The STWL is a caustic solution that dissolves quartz. Because Al is a necessary element in the formation of

ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN; A

International Nuclear Information System (INIS)

M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

2001-01-01

Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO(sub 2) emissions can be overcome. Permanent and safe methods for CO(sub 2) capture and disposal/storage need to be developed. Mineralization of stationary-source CO(sub 2) emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH)(sub 2) was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (i) its structural and chemical simplicity, (ii) interest in Mg(OH)(sub 2) gas-solid carbonation as a potentially cost-effective CO(sub 2) mineral sequestration process component, and (iii) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO(sub 2) sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This report covers the third year progress of this grant, as well as providing an integrated overview of the progress in years 1-3, as we have been granted a one-year no-cost extension to wrap up a few studies and publications to optimize project impact

In-situ nanoscale imaging of clay minerals with atomic force microscopy

International Nuclear Information System (INIS)

Bosbach, D.

2010-01-01

Document available in extended abstract form only. Clay minerals play a key role in many concepts for high-level nuclear waste repository systems in deep geological formations. Various aspects related to the long-term safety of nuclear disposal are linked to their fundamental physical-chemical properties, in particular with respect to their reactivity in aqueous environments. Atomic Force Microscopy (AFM) allows high resolution imaging of clay minerals in-situ while they are exposed to an aqueous solution. The presentation is intended to provide an overview of examples of AFM studies on clay minerals: 1. AFM is an ideal tool to visualize the shape of individual clay particles down to molecular scales including a quantitative description of for example their aspect ratio. Furthermore, the particle size can be easily extracted from AFM data for individual particles as well as particle size distribution. 2. Surface area of clay minerals is a key issue when discussing heterogeneous reactions such as dissolution, adsorption or (surface) precipitation - total surface area, BET surface area, reactive surface area need to be distinguished. In particular reactive surface area is linked to specific reactive surface sites. AFM is of course able to identify such sites and consequently AFM data allow to characterize and to quantify reactive surface area. 3. The reactivity of clay mineral surfaces in aqueous environments controls the behaviour of clay minerals under repository conditions and also affects the migration/retention of radionuclides. It could be shown that the dissolution of smectite particles under acidic conditions at room temperature primarily occurs at (hk0) particle edges, whereas the reactivity of the (001) basal surfaces is very limited. The heterogeneous (surface) precipitation of secondary iron (hydr)oxides phase could be unraveled by AFM observations. Surface precipitation occurs preferentially at (hk0) edges surfaces. Ignoring the surface site specific

Formation mechanism of uranium minerals at sandstone-type uranium deposits

International Nuclear Information System (INIS)

Li Shengfu; Zhang Yun

2004-01-01

By analyzing the behavior and existence form of uranium in different geochemical environments, existence form of uranium and uranium minerals species, this paper expounds the formation mechanism of main commercial uranium mineral--pitchblende: (1) uranium is a valence-changeable element. It is reactivated and migrates in oxidized environment, and is reduced and precipitated in reducing environment; (2) [UO 2 (CO 3 ) 3 ] 4- , [UO 2 (CO 3 ) 2 ] 2- coming from oxidized environment react with reductants such as organic matter, sulfide and low-valence iron at the redox front to form simple uranium oxide--pitchblende; (3)the adsorption of uranium by organic matter and clay minerals accelerates the reduction and the concentration of uranium. Therefore, it is considered, that the reduction of SO 4 2- by organic matter to form H 2 S, and the reduction of UO 2 2+ by H 2 S are the main reasons for the formation of pitchblende. This reaction is extensively and universally available in neutral and weakly alkaline carbonate solution. The existense of reductants such as H 2 S is the basic factor leading to the decrease of Eh in environments and the oversaturation of UO 2 2+ at the redox front in groundwater, thus accelerating the adsorption and the precipitation of uranium

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

Science.gov (United States)

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

An overview of hydrodynamic studies of mineralization

Directory of Open Access Journals (Sweden)

Guoxiang Chi

2011-07-01

Full Text Available Fluid flow is an integral part of hydrothermal mineralization, and its analysis and characterization constitute an important part of a mineralization model. The hydrodynamic study of mineralization deals with analyzing the driving forces, fluid pressure regimes, fluid flow rate and direction, and their relationships with localization of mineralization. This paper reviews the principles and methods of hydrodynamic studies of mineralization, and discusses their significance and limitations for ore deposit studies and mineral exploration. The driving forces of fluid flow may be related to fluid overpressure, topographic relief, tectonic deformation, and fluid density change due to heating or salinity variation, depending on specific geologic environments and mineralization processes. The study methods may be classified into three types, megascopic (field observations, microscopic analyses, and numerical modeling. Megascopic features indicative of significantly overpressured (especially lithostatic or supralithostatic fluid systems include horizontal veins, sand injection dikes, and hydraulic breccias. Microscopic studies, especially microthermometry of fluid inclusions and combined stress analysis and microthermometry of fluid inclusion planes (FIPs can provide important information about fluid temperature, pressure, and fluid-structural relationships, thus constraining fluid flow models. Numerical modeling can be carried out to solve partial differential equations governing fluid flow, heat transfer, rock deformation and chemical reactions, in order to simulate the distribution of fluid pressure, temperature, fluid flow rate and direction, and mineral precipitation or dissolution in 2D or 3D space and through time. The results of hydrodynamic studies of mineralization can enhance our understanding of the formation processes of hydrothermal deposits, and can be used directly or indirectly in mineral exploration.

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

International Nuclear Information System (INIS)

Xu Tianfu; Apps, John A.; Pruess, Karsten

2004-01-01

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO 2 disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO 2 injection, the authors have analyzed the impact of CO 2 immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO 2 at high pressure were performed. The modeling considered the following important factors affecting CO 2 sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO 2 solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO 2 injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO 2 sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO 2 that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO 2 dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters

Analysis of mineral trapping for CO{sub 2} disposal in deep aquifers

Energy Technology Data Exchange (ETDEWEB)

Xu, Tianfu; Apps, John A.; Pruess, Karsten

2001-07-20

CO{sub 2} disposal into deep aquifers has been suggested as a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO{sub 2} disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO{sub 2} injection, we have analyzed the impact of CO{sub 2} immobilization through carbonate precipitation. A survey of all major classes of rock-forming minerals, whose alteration would lead to carbonate precipitation, indicated that very few minerals are present in sufficient quantities in aquifer host rocks to permit significant sequestration of CO{sub 2}. We performed batch reaction modeling of the geochemical evolution of three different aquifer mineralogies in the presence of CO{sub 2} at high pressure. Our modeling considered (1) redox processes that could be important in deep subsurface environments, (2) the presence of organic matter, (3) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, and (4) CO{sub 2} solubility dependence on pressure, temperature and salinity of the system. The geochemical evolution under both natural background and CO{sub 2} injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO{sub 2} sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO{sub 2} that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO{sub 2} dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of ferric mineral precursors such as glauconite, which in turn is dependent on the reactivity of associated organic material. The accumulation of carbonates in

Soil Organic Matter Stabilization via Mineral Interactions in Forest Soils with Varying Saturation Frequency

Science.gov (United States)

Possinger, A. R.; Inagaki, T.; Bailey, S. W.; Kogel-Knabner, I.; Lehmann, J.

2017-12-01

Soil carbon (C) interaction with minerals and metals through surface adsorption and co-precipitation processes is important for soil organic C (SOC) stabilization. Co-precipitation (i.e., the incorporation of C as an "impurity" in metal precipitates as they form) may increase the potential quantity of mineral-associated C per unit mineral surface compared to surface adsorption: a potentially important and as yet unaccounted for mechanism of C stabilization in soil. However, chemical, physical, and biological characterization of co-precipitated SOM as such in natural soils is limited, and the relative persistence of co-precipitated C is unknown, particularly under dynamic environmental conditions. To better understand the relationships between SOM stabilization via organometallic co-precipitation and environmental variables, this study compares mineral-SOM characteristics across a forest soil (Spodosol) hydrological gradient with expected differences in co-precipitation of SOM with iron (Fe) and aluminum (Al) due to variable saturation frequency. Soils were collected from a steep, well-drained forest soil transect with low, medium, and high frequency of water table intrusion into surface soils (Hubbard Brook Experimental Forest, Woodstock, NH). Lower saturation frequency soils generally had higher C content, C/Fe, C/Al, and other indicators of co-precipitation interactions resulting from SOM complexation, transport, and precipitation, an important process of Spodosol formation. Preliminary Fe X-ray Absorption Spectroscopic (XAS) characterization of SOM and metal chemistry in low frequency profiles suggest co-precipitation of SOM in the fine fraction (soils showed greater SOC mineralization per unit soil C for low saturation frequency (i.e., higher co-precipitation) soils; however, increased mineralization may be attributed to non-mineral associated fractions of SOM. Further work to identify the component of SOM contributing to rapid mineralization using 13C

CO2 Absorption and Magnesium Carbonate Precipitation in MgCl2–NH3–NH4Cl Solutions: Implications for Carbon Capture and Storage

Directory of Open Access Journals (Sweden)

Chen Zhu

2017-09-01

Full Text Available CO2 absorption and carbonate precipitation are the two core processes controlling the reaction rate and path of CO2 mineral sequestration. Whereas previous studies have focused on testing reactive crystallization and precipitation kinetics, much less attention has been paid to absorption, the key process determining the removal efficiency of CO2. In this study, adopting a novel wetted wall column reactor, we systematically explore the rates and mechanisms of carbon transformation from CO2 gas to carbonates in MgCl2–NH3–NH4Cl solutions. We find that reactive diffusion in liquid film of the wetted wall column is the rate-limiting step of CO2 absorption when proceeding chiefly through interactions between CO2(aq and NH3(aq. We further quantified the reaction kinetic constant of the CO2–NH3 reaction. Our results indicate that higher initial concentration of NH4Cl ( ≥ 2 mol · L − 1 leads to the precipitation of roguinite [ ( NH 4 2 Mg ( CO 3 2 · 4 H 2 O ], while nesquehonite appears to be the dominant Mg-carbonate without NH4Cl addition. We also noticed dypingite formation via phase transformation in hot water. This study provides new insight into the reaction kinetics of CO2 mineral carbonation that indicates the potential of this technique for future application to industrial-scale CO2 sequestration.

In situ mid-infrared spectroscopic titration of forsterite with water in supercritical CO2: Dependence of mineral carbonation on quantitative water speciation

Science.gov (United States)

Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Martin, P.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2011-12-01

Geologic sequestration of carbon dioxide holds promise for helping mitigate CO2 emissions generated from the burning of fossil fuels. Supercritical CO2 (scCO2) plumes containing variable water concentrations (wet scCO2) will displace aqueous solution and dominate the pore space adjacent to caprocks. It is important to understand possible mineral reactions with wet scCO2 to better predict long-term caprock integrity. We introduce novel in situ instrumentation that enables quantitative titrations of reactant minerals with water in scCO2 at temperatures and pressures relevant to target geologic reservoirs. The system includes both transmission and attenuated total reflection mid-infrared optics. Transmission infrared spectroscopy is used to measure concentrations of water dissolved in the scCO2, adsorbed on mineral surfaces, and incorporated into precipitated carbonates. Single-reflection attenuated total reflection infrared spectroscopy is used to monitor water adsorption, mineral dissolution, and carbonate precipitation reactions. Results are presented for the infrared spectroscopic titration of forsterite (Mg2SiO4), a model divalent metal silicate, with water in scCO2 at 100 bar and at both 50 and 75°C. The spectral data demonstrate that the quantitative speciation of water as either dissolved or adsorbed is important for understanding the types, growth rates, and amounts of carbonate precipitates formed. Relationships between dissolved/adsorbed water, water concentrations, and the role of liquid-like adsorbed water are discussed. Our results unify previous in situ studies from our laboratory based on infrared spectroscopy, nuclear magnetic resonance spectroscopy and X-ray diffraction.

Physical heterogeneity control on effective mineral dissolution rates

Science.gov (United States)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher

Growth dynamics and composition of tubular structures in a reaction-precipitation system

Science.gov (United States)

Pagano, Jason John

Self-organization in reaction precipitation systems occurs in many physical, chemical, biological, and geological systems. In particular, chemical reactions provide a wealth of examples for this intriguing process. Permanent tubular structures arise from the interplay of chemical and transport phenomena such as diffusion and fluid flow. These astonishing tubular structures are prevalent throughout nature. Examples include black smokers at hydrothermal vents, silica tubes in setting cement, soda-straw stalactites in caves, and biological structures such as the outer skeleton of certain algae. In this work, the aim is to establish and understand a laboratory scale model by examining the, seemingly simple, precipitation reaction between sodium silicate and copper sulfate as well as zinc sulfate. The tubular precipitation structures in so-called silica gardens are known to many scientists and non-scientists alike. However, little is known regarding their growth dynamics and chemical composition. We devised an injection technique which provides control over parameters that are not accessible in the classic silica garden system. For the example of cupric sulfate injection into waterglass solution, we identify three distinct growth regimes (jetting, popping, and budding) and study their concentration dependent transitions. Here we describe the composition and morphology of the tube material using techniques such as electron microscopy and vibrational spectroscopy. Specifically, we find that the tube wall consists of metal hydroxide that is stabilized by a thin, exterior silica layer. After synthesis the tubes can be further modified by using chemical and/or physical means. A second study aims to understand tubule formation under "reverse" conditions. More specifically, waterglass is being injected into lighter cupric sulfate solution. In these experiments, single, downward growing precipitation tubes are created. Four distinct growth regimes are observed and their

A coupled reaction and transport model for assessing the injection, migration and fate of waste fluids

International Nuclear Information System (INIS)

Liu, X.; Ortoleva, P.

1996-01-01

The use of reaction-transport modeling for reservoir assessment and management in the context of deep well waste injection is evaluated. The study is based on CIRF.A (Chemical Interaction of Rock and Fluid), a fully coupled multiphase flow, contaminant transport, and fluid and mineral reaction model. Although SWIFT (Sandia Waste-Isolation Flow and Transport Model) is often the numerical model of choice, it can not account for chemical reactions involving rock, wastes, and formation fluids and their effects on contaminant transport, rock permeability and porosity, and the integrity of the reservoir and confining units. CIRF.A can simulate all these processes. Two field cases of waste injection were simulated by CIRF.A. Both observation data and simulation results show mineral precipitation in one case and rock dissolution in another case. Precipitation and dissolution change rock porosity and permeability, and hence the pattern of fluid migration. The model is shown to be invaluable in analyzing near borehole and reservoir-scale effects during waste injection and predicting the 10,000 year fate of the waste plume. The benefits of using underpressured compartments as waste repositories were also demonstrated by CIRF.A simulations

Note: CO₂-mineral dissolution experiments using a rocking autoclave and a novel titanium reaction cell.

Science.gov (United States)

Purser, Gemma; Rochelle, Christopher A; Wallis, Humphrey C; Rosenqvist, Jörgen; Kilpatrick, Andrew D; Yardley, Bruce W D

2014-08-01

A novel titanium reaction cell has been constructed for the study of water-rock-CO2 reactions. The reaction cell has been used within a direct-sampling rocking autoclave and offers certain advantages over traditional "flexible gold/titanium cell" approaches. The main advantage is robustness, as flexible cells are prone to rupture on depressurisation during gas-rich experiments. The reaction cell was tested in experiments during an inter-laboratory comparison study, in which mineral kinetic data were determined. The cell performed well during experiments up to 130 °C and 300 bars pressure. The data obtained were similar to those of other laboratories participating in the study, and also to previously published data.

Characterization of cement minerals, cements and their reaction products at the atomic and nano scale

DEFF Research Database (Denmark)

Skibsted, Jørgen; Hall, Christopher

2008-01-01

Recent advances and highlights in characterization methods are reviewed for cement minerals, cements and their reaction products. The emphasis is on X-ray and neutron diffraction, and on nuclear magnetic resonance methods, although X-ray absorption and Raman spectroscopies are discussed briefly...

Characterization of cement minerals, cements and their reaction products at the atomic and nano scale

International Nuclear Information System (INIS)

Skibsted, Jorgen; Hall, Christopher

2008-01-01

Recent advances and highlights in characterization methods are reviewed for cement minerals, cements and their reaction products. The emphasis is on X-ray and neutron diffraction, and on nuclear magnetic resonance methods, although X-ray absorption and Raman spectroscopies are discussed briefly

Calcium Carbonate Precipitation for CO2 Storage and Utilization: A Review of the Carbonate Crystallization and Polymorphism

Directory of Open Access Journals (Sweden)

Ribooga Chang

2017-07-01

Full Text Available The transformation of CO2 into a precipitated mineral carbonate through an ex situ mineral carbonation route is considered a promising option for carbon capture and storage (CCS since (i the captured CO2 can be stored permanently and (ii industrial wastes (i.e., coal fly ash, steel and stainless-steel slags, and cement and lime kiln dusts can be recycled and converted into value-added carbonate materials by controlling polymorphs and properties of the mineral carbonates. The final products produced by the ex situ mineral carbonation route can be divided into two categories—low-end high-volume and high-end low-volume mineral carbonates—in terms of their market needs as well as their properties (i.e., purity. Therefore, it is expected that this can partially offset the total cost of the CCS processes. Polymorphs and physicochemical properties of CaCO3 strongly rely on the synthesis variables such as temperature, pH of the solution, reaction time, ion concentration and ratio, stirring, and the concentration of additives. Various efforts to control and fabricate polymorphs of CaCO3 have been made to date. In this review, we present a summary of current knowledge and recent investigations entailing mechanistic studies on the formation of the precipitated CaCO3 and the influences of the synthesis factors on the polymorphs.

Microscale Biosignatures and Abiotic Mineral Authigenesis in Little Hot Creek, California

Directory of Open Access Journals (Sweden)

Emily A. Kraus

2018-05-01

Full Text Available Hot spring environments can create physical and chemical gradients favorable for unique microbial life. They can also include authigenic mineral precipitates that may preserve signs of biological activity on Earth and possibly other planets. The abiogenic or biogenic origins of such precipitates can be difficult to discern, therefore a better understanding of mineral formation processes is critical for the accurate interpretation of biosignatures from hot springs. Little Hot Creek (LHC is a hot spring complex located in the Long Valley Caldera, California, that contains mineral precipitates composed of a carbonate base (largely submerged topped by amorphous silica (largely emergent. The precipitates occur in close association with microbial mats and biofilms. Geological, geochemical, and microbiological data are consistent with mineral formation via degassing and evaporation rather than direct microbial involvement. However, the microfabric of the silica portion is stromatolitic in nature (i.e., wavy and finely laminated, suggesting that abiogenic mineralization has the potential to preserve textural biosignatures. Although geochemical and petrographic evidence suggests the calcite base was precipitated via abiogenic processes, endolithic microbial communities modified the structure of the calcite crystals, producing a textural biosignature. Our results reveal that even when mineral precipitation is largely abiogenic, the potential to preserve biosignatures in hot spring settings is high. The features found in the LHC structures may provide insight into the biogenicity of ancient Earth and extraterrestrial rocks.

Analysis of mineral trapping for CO(sub 2) disposal in deep aquifers; TOPICAL

International Nuclear Information System (INIS)

Xu, Tianfu; Apps, John A.; Pruess, Karsten

2001-01-01

CO(sub 2) disposal into deep aquifers has been suggested as a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO(sub 2) disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO(sub 2) injection, we have analyzed the impact of CO(sub 2) immobilization through carbonate precipitation. A survey of all major classes of rock-forming minerals, whose alteration would lead to carbonate precipitation, indicated that very few minerals are present in sufficient quantities in aquifer host rocks to permit significant sequestration of CO(sub 2). We performed batch reaction modeling of the geochemical evolution of three different aquifer mineralogies in the presence of CO(sub 2) at high pressure. Our modeling considered (1) redox processes that could be important in deep subsurface environments, (2) the presence of organic matter, (3) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, and (4) CO(sub 2) solubility dependence on pressure, temperature and salinity of the system. The geochemical evolution under both natural background and CO(sub 2) injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO(sub 2) sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO(sub 2) that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO(sub 2) dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of ferric mineral precursors such as glauconite, which in turn is dependent on the reactivity of associated organic material. The accumulation of carbonates in

The role of amino acids in hydroxyapatite mineralization

Science.gov (United States)

2016-01-01

Polar and charged amino acids (AAs) are heavily expressed in non-collagenous proteins (NCPs), and are involved in hydroxyapatite (HA) mineralization in bone. Here, we review what is known on the effect of single AAs on HA precipitation. Negatively charged AAs, such as aspartic acid, glutamic acid (Glu) and phosphoserine are largely expressed in NCPs and play a critical role in controlling HA nucleation and growth. Positively charged ones such as arginine (Arg) or lysine (Lys) are heavily involved in HA nucleation within extracellular matrix proteins such as collagen. Glu, Arg and Lys intake can also increase bone mineral density by stimulating growth hormone production. In vitro studies suggest that the role of AAs in controlling HA precipitation is affected by their mobility. While dissolved AAs are able to inhibit HA precipitation and growth by chelating Ca2+ and PO43− ions or binding to nuclei of calcium phosphate and preventing their further growth, AAs bound to surfaces can promote HA precipitation by attracting Ca2+ and PO43− ions and increasing the local supersaturation. Overall, the effect of AAs on HA precipitation is worth being investigated more, especially under conditions closer to the physiological ones, where the presence of other factors such as collagen, mineralization inhibitors, and cells heavily influences HA precipitation. A deeper understanding of the role of AAs in HA mineralization will increase our fundamental knowledge related to bone formation, and could lead to new therapies to improve bone regeneration in damaged tissues or cure pathological diseases caused by excessive mineralization in tissues such as cartilage, blood vessels and cardiac valves. PMID:27707904

Calcium Carbonate Precipitation for CO{sub 2} Storage and Utilization: A Review of the Carbonate Crystallization and Polymorphism

Energy Technology Data Exchange (ETDEWEB)

Chang, Ribooga; Kim, Semin; Lee, Seungin; Choi, Soyoung; Kim, Minhee; Park, Youngjune, E-mail: young@gist.ac.kr [Carbon and Energy Systems, School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju (Korea, Republic of)

2017-07-10

The transformation of CO{sub 2} into a precipitated mineral carbonate through an ex situ mineral carbonation route is considered a promising option for carbon capture and storage (CCS) since (i) the captured CO{sub 2} can be stored permanently and (ii) industrial wastes (i.e., coal fly ash, steel and stainless-steel slags, and cement and lime kiln dusts) can be recycled and converted into value-added carbonate materials by controlling polymorphs and properties of the mineral carbonates. The final products produced by the ex situ mineral carbonation route can be divided into two categories—low-end high-volume and high-end low-volume mineral carbonates—in terms of their market needs as well as their properties (i.e., purity). Therefore, it is expected that this can partially offset the total cost of the CCS processes. Polymorphs and physicochemical properties of CaCO{sub 3} strongly rely on the synthesis variables such as temperature, pH of the solution, reaction time, ion concentration and ratio, stirring, and the concentration of additives. Various efforts to control and fabricate polymorphs of CaCO{sub 3} have been made to date. In this review, we present a summary of current knowledge and recent investigations entailing mechanistic studies on the formation of the precipitated CaCO{sub 3} and the influences of the synthesis factors on the polymorphs.

Modelling of water-gas-rock geo-chemical interactions. Application to mineral diagenesis in geological reservoirs

International Nuclear Information System (INIS)

Bildstein, Olivier

1998-01-01

Mineral diagenesis in tanks results from interactions between minerals, water, and possibly gases, over geological periods of time. The associated phenomena may have a crucial importance for reservoir characterization because of their impact on petrophysical properties. The objective of this research thesis is thus to develop a model which integrates geochemical functions necessary to simulate diagenetic reactions, and which is numerically efficient enough to perform the coupling with a transport model. After a recall of thermodynamic and kinetic backgrounds, the author discusses how the nature of available analytic and experimental data influenced choices made for the formalization of physical-chemical phenomena and for behaviour laws to be considered. Numerical and computational aspects are presented in the second part. The model is validated by using simple examples. The different possible steps during the kinetic competition between two mineral are highlighted, as well the competition between mineral reaction kinetics and water flow rate across the rock. Redox reactions are also considered. In the third part, the author reports the application of new model functions, and highlights the contribution of the modelling to the understanding of some complex geochemical phenomena and to the prediction of reservoir quality. The model is applied to several diagenetic transformations: cementation of dolomitic limestone by anhydride, illite precipitation, and thermal reduction of sulphates [fr

Thermal analysis of precipitation reactions in a Ti-25Nb-3Mo-3Zr-2Sn alloy

International Nuclear Information System (INIS)

Kent, Damon; Wang, Gui; Dargusch, Matthew S.; Pas, Steven; Zhu, Suming

2012-01-01

A study was undertaken on a Ti-25Nb-3Mo-3Zr-2Sn alloy using differential scanning calorimetry (DSC) in order to improve understanding of the precipitation reactions occurring during aging heat treatments. The investigation showed that isothermal ω phase can be formed in the cast and solution treated alloy at low aging temperatures. An exothermic peak in the temperature range of 300 to 400 C was detected for precipitation of the ω phase, with approximate activation energy of 176 kJ/mol. The ω phase begins to dissolve at temperatures around 400 C and precipitation of the α phase is favoured at higher temperatures between 400 C and 600 C. An exothermic peak with activation energy of 197 kJ/mol was measured for precipitation of the α phase. Deformation resulting in the formation of the stress induced α'' phase altered the DSC heating profile for the solution treated alloy. The exothermic peak associated with precipitation of the ω phase was not detected during heating of the deformed material and increased endothermic heating associated with recovery and recrystallisation was observed. (orig.)

Kerogen-mineral reactions at raised temperatures in the presence of water

Energy Technology Data Exchange (ETDEWEB)

Eglinton, T I; Rowland, S J; Curtis, C D; Douglas, A G

1986-01-01

Kerogen has been artificially matured under hydrous pyrolysis conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330/sup 0/C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry. In the 280/sup 0/C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330/sup 0/C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (approx. 40% wt/wt). Biomarker epimerization reactions have also proceeded further in the 330/sup 0/C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.

Continuing Studies on Direct Aqueous Mineral Carbonation of CO{sub 2} Sequestration

Energy Technology Data Exchange (ETDEWEB)

O' Connor, W.K.; Dahlin, D.C.; Nilsen, D.N.; Gerdemann, S.J.; Rush, G.E.; Penner, L.R.; Walters, R.P.; Turner, P.C.

2002-03-04

Direct aqueous mineral carbonation has been investigated as a process to convert gaseous CO{sub 2} into a geologically stable, solid final form. The process utilizes a solution of sodium bicarbonate (NaHCO{sub 3}), sodium chloride (NaCl), and water, mixed with a mineral reactant, such as olivine (Mg{sub 2}SiO{sub 4}) or serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}]. Carbon dioxide is dissolved into this slurry, by diffusion through the surface and gas dispersion within the aqueous phase. The process includes dissolution of the mineral and precipitation of the magnesium carbonate mineral magnesite (MgCO{sub 3}) in a single unit operation. Activation of the silicate minerals has been achieved by thermal and mechanical means, resulting in up to 80% stoichiometric conversion of the silicate to the carbonate within 30 minutes. Heat treatment of the serpentine, or attrition grinding of the olivine and/or serpentine, appear to activate the minerals by the generation of a non-crystalline phase. Successful conversion to the carbonate has been demonstrated at ambient temperature and relatively low (10 atm) partial pressure of CO{sub 2} (P{sub CO2}). However, optimum results have been achieved using the bicarbonate-bearing solution, and high P{sub CO2}. Specific conditions include: 185 C; P{sub CO2}=150 atm; 30% solids. Studies suggest that the mineral dissolution rate is not solely surface controlled, while the carbonate precipitation rate is primarily dependent on the bicarbonate concentration of the slurry. Current and future activities include further examination of the reaction pathways and pretreatment options, the development of a continuous flow reactor, and an evaluation of the economic feasibility of the process.

Magnesite dissolution and precipitation rates at hydrothermal conditions

International Nuclear Information System (INIS)

Saldi, Giuseppe

2009-01-01

complexation model originally developed at 25 deg. C. The decrease of dissolution rates observed from 150 to 200 deg. C can be explained by the increasing carbonation and hydrolysis of the rate controlling >MgOH 2 + sites. As a result of the decreasing rates of dissolution, the achievement of alkaline conditions and temperatures higher than 100 deg. C by CO 2 -rich fluids represents a favorable condition for CO 2 sequestration as dissolved alkalinity in deep aquifers where carbonate minerals are major constituting phases. The use of a hydrogen electrode concentration cell (HECC) corroborates the kinetic data obtained at close to equilibrium conditions by the precise determination of magnesite solubility product as a function of temperature (50-200 deg. C). These measurements allowed generating the thermodynamic properties of this phase and comparing them with those obtained from calorimetric measurements and phase equilibria experiments. The results of this study significantly improve our understanding of the kinetic behaviour of carbonate minerals in hydrothermal systems and provide an essential database for the future study of dissolution/precipitation reactions of carbonate minerals in complex systems. This work also provides important kinetic constraints for the geochemical modeling of CO 2 sequestration processes and will help the evaluation of impact and risks connected to a long-term storage. (author) [fr

Mineral catalysis of oil producing reactions in coal liquefaction

Energy Technology Data Exchange (ETDEWEB)

Shridharani, K.G.

1983-01-01

This work was concerned primarily with the development of a relatively inexpensive, readily available, high activity catalyst that can be used as a disposable catalyst in coal liquefaction processes. For a fair evaluation of the developmental mineral catalyst (presulfided iron oxide), it was necessary to determine at different stages of this work, whether catalyst inhibition, deactivation or activity was the limiting factor in coal liquefaction catalysis. First, different routes were explored to prepare a high hydrogenation activity, iron-based catalyst. Naphthalene hydrogenation was used as a model reaction to rate the hydrogenation activities of different additives. Presulfiding of iron oxide with H/sub 2/S, under controlled conditions, rendered the highest hydrogenation activity mineral catalyst, which had a hydrogenation activity even greater than that of commercial CoMo/Al/sub 2/O/sub 3/ catalyst sulfided with creosote oil and hydrogen. Sulfiding of CoMo/Al/sub 2/O/sub 3/ catalyst with H/sub 2/S remarkably improved its initial hydrogenation activity. Second, the catalyst inhibition and deactivation during liquefaction were studied. Liquefaction-process solvents contain a number of compounds that can either deactivate or inhibit the hydrogenation activity of a catalyst. Finally, the hydrocracking activity of the presulfided iron oxide catalyst was compared with that of commercial catalysts, CoMo/Al/sub 2/O/sub 3/ and low alumina FCC catalyst.

Biogrout, ground improvement by microbial induced carbonate precipitation

NARCIS (Netherlands)

Van Paassen, L.A.

2009-01-01

Biogrout is a new ground improvement method based on microbially induced precipitation of calcium carbonate (MICP). When supplied with suitable substrates, micro-organisms can catalyze biochemical conversions in the subsurface resulting in precipitation of inorganic minerals, which change the

Precipitation of aluminum and magnesium secondary minerals from uranium mill raffinate (pH 1.0–10.5) and their controls on aqueous contaminants

International Nuclear Information System (INIS)

Robertson, Jared; Hendry, M. Jim; Essilfie-Dughan, J.; Chen, J.

2016-01-01

Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)_3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)_3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)_3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations. - Highlights: • Simulated a U mill neutralization process to identify Al–Mg secondary mineralogy. • Identified AlOHSO_4, Al–Fe(OH)_3, Al(OH)_3, and Mg–Al hydrotalcite as precipitates. • Aqueous As, Ni, Mo, and Se concentrations controlled by Al–Mg minerals. • Experimental hydrotalcite uptake of As, Mo, and Se was comparable to ferrihydrite. • Updates the current model of aqueous contaminant

TUCS/phosphate mineralization of actinides

Energy Technology Data Exchange (ETDEWEB)

Nash, K.L. [Argonne National Lab., IL (United States)

1997-10-01

This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

Coupling diffusion and high-pH precipitation/dissolution in the near field of a HLW repository in clay by means of reactive solute transport models

Science.gov (United States)

Samper, J.; Font, I.; Yang, C.; Montenegro, L.

2004-12-01

The reference concept for a HLW repository in clay in Spain includes a 75 cm thick bentonite buffer which surrounds canisters. A concrete sustainment 20 cm thick is foreseen between the bentonite buffer and the clay formation. The long term geochemical evolution of the near field is affected by a high-pH hyperalkaline plume induced by concrete. Numerical models of multicomponent reactive transport have been developped in order to quantify the evolution of the system over 1 Ma. Water flow is negligible once the bentonite buffer is saturated after about 20 years. Therefore, solute transport occurs mainly by diffusion. Models account for aqueous complexation, acid-base and redox reactions, cation exchange, and mineral dissolution precipitation in the bentonite, the concrete and the clay formation. Numerical results obtained witth CORE2D indicate that the high-pH plume causes significant changes in porewater chemistry both in the bentonite buffer and the clay formation. Porosity changes caused by mineral dissolution/precipitation are extremely important. Therefore, coupled modes of diffusion and reactive transport accounting for changes in porosity caused by mineral precipitation are required in order to obtain realistic predictions.

Permeability changes due to mineral diagenesis in fractured crust: implications for hydrothermal circulation at mid-ocean ridges

Science.gov (United States)

Fontaine, Fabrice Jh.; Rabinowicz, Michel; Boulègue, Jacques

2001-01-01

The hydrothermal processes at ridge crests have been extensively studied during the last two decades. Nevertheless, the reasons why hydrothermal fields are only occasionally found along some ridge segments remain a matter of debate. In the present study we relate this observation to the mineral precipitation induced by hydrothermal circulation. Our study is based on numerical models of convection inside a porous slot 1.5 km high, 2.25 km long and 120 m wide, where seawater is free to enter and exit at its top while the bottom is held at a constant temperature of 420°C. Since the fluid circulation is slow and the fissures in which seawater circulates are narrow, the reactions between seawater and the crust achieve local equilibrium. The rate of mineral precipitation or dissolution is proportional to the total derivative of the temperature with respect to time. Precipitation of minerals reduces the width of the fissures and thus percolation. Using conventional permeability versus porosity laws, we evaluate the evolution of the permeability field during the hydrothermal circulation. Our computations begin with a uniform permeability and a conductive thermal profile. After imposing a small random perturbation on the initial thermal field, the circulation adopts a finger-like structure, typical of convection in vertical porous slots thermally influenced by surrounding walls. Due to the strong temperature dependence of the fluid viscosity and thermal expansion, the hot rising fingers are strongly buoyant and collide with the top cold stagnant water layer. At the interface of the cold and hot layers, a horizontal boundary layer develops causing massive precipitation. This precipitation front produces a barrier to the hydrothermal flow. Consequently, the flow becomes layered on both sides of the front. The fluid temperature at the top of the layer remains quite low: it never exceeds a temperature of 80°C, well below the exit temperature of hot vent sites observed at

A review on the kinetics of microbially induced calcium carbonate precipitation by urea hydrolysis

Science.gov (United States)

van Paassen, L. A.

2017-12-01

In this study the kinetics of calcium carbonate precipitation induced by the ureolytic bacteria are reviewed based on experiments and mathematical modelling. The study shows how urea hydrolysis rate depends on the amount of bacteria and the conditions during growth, storage, hydrolysis and precipitation. The dynamics of Microbially Induced Carbonate Precipitation has been monitored in non-seeded liquid batch experiments. Results show that particulary for a fast hydrolysis of urea (>1 M-urea day-1) in a highly concentrated equimolar solution with calcium chloride (>0.25 M) the solubility product of CaCO3 is exceeded within a short period (less than 30 minutes), the supersaturation remains high for an exended period, resulting in prolonged periods of nucleation and crystal growth and extended growth of metastable precursor mineral phases. The pH, being a result of the speciation, quickly rises until critical supersaturation is reached and precipitation is initiated. Then pH drops (sometimes showing oscillating behaviour) to about neutral where it stays until all substrates are depleted. Higher hydrolysis rates lead to higher supersaturation and pH and relatively many small crystals, whereas higher concentrations of urea and calcium chloride mainly lead to lower pH values. The conversion can be reasonably monitored by electrical conductivity and reasonably predicted, using a simplified model based on a single reaction as long as the urea hydrolysis rate is known. Complex geochemical models, which include chemical speciciation through acid-base equilibria and kinetic equations to describe mineral precipitation, do not show significant difference from the simplified model regarding the bulk chemistry and the total amount of precipitates. However, experiments show that ureolytic MICP can result in a highly variable crystal morphologies with large variation in the affected hydraulic properties when applied in a porous medium. In order to calculate the number, size and

Simulations of reactive transport and precipitation with smoothed particle hydrodynamics

Science.gov (United States)

Tartakovsky, Alexandre M.; Meakin, Paul; Scheibe, Timothy D.; Eichler West, Rogene M.

2007-03-01

A numerical model based on smoothed particle hydrodynamics (SPH) was developed for reactive transport and mineral precipitation in fractured and porous materials. Because of its Lagrangian particle nature, SPH has several advantages for modeling Navier-Stokes flow and reactive transport including: (1) in a Lagrangian framework there is no non-linear term in the momentum conservation equation, so that accurate solutions can be obtained for momentum dominated flows and; (2) complicated physical and chemical processes such as surface growth due to precipitation/dissolution and chemical reactions are easy to implement. In addition, SPH simulations explicitly conserve mass and linear momentum. The SPH solution of the diffusion equation with fixed and moving reactive solid-fluid boundaries was compared with analytical solutions, Lattice Boltzmann [Q. Kang, D. Zhang, P. Lichtner, I. Tsimpanogiannis, Lattice Boltzmann model for crystal growth from supersaturated solution, Geophysical Research Letters, 31 (2004) L21604] simulations and diffusion limited aggregation (DLA) [P. Meakin, Fractals, scaling and far from equilibrium. Cambridge University Press, Cambridge, UK, 1998] model simulations. To illustrate the capabilities of the model, coupled three-dimensional flow, reactive transport and precipitation in a fracture aperture with a complex geometry were simulated.

Effects of physical and geochemical heterogeneities on mineral transformation and biomass accumulation during biostimulation experiments at Rifle, Colorado.

Science.gov (United States)

Li, Li; Steefel, Carl I; Kowalsky, Michael B; Englert, Andreas; Hubbard, Susan S

2010-03-01

Electron donor amendment for bioremediation often results in precipitation of secondary minerals and the growth of biomass, both of which can potentially change flow paths and the efficacy of bioremediation. Quantitative estimation of precipitate and biomass distribution has remained challenging, partly due to the intrinsic heterogeneities of natural porous media and the scarcity of field data. In this work, we examine the effects of physical and geochemical heterogeneities on the spatial distributions of mineral precipitates and biomass accumulated during a biostimulation field experiment near Rifle, Colorado. Field bromide breakthrough data were used to infer a heterogeneous distribution of hydraulic conductivity through inverse transport modeling, while the solid phase Fe(III) content was determined by assuming a negative correlation with hydraulic conductivity. Validated by field aqueous geochemical data, reactive transport modeling was used to explicitly keep track of the growth of the biomass and to estimate the spatial distribution of precipitates and biomass. The results show that the maximum mineral precipitation and biomass accumulation occurs in the vicinity of the injection wells, occupying up to 5.4vol.% of the pore space, and is dominated by reaction products of sulfate reduction. Accumulation near the injection wells is not strongly affected by heterogeneities present in the system due to the ubiquitous presence of sulfate in the groundwater. However, accumulation in the down-gradient regions is dominated by the iron-reducing reaction products, whose spatial patterns are strongly controlled by both physical and geochemical heterogeneities. Heterogeneities can lead to localized large accumulation of mineral precipitates and biomass, increasing the possibility of pore clogging. Although ignoring the heterogeneities of the system can lead to adequate prediction of the average behavior of sulfate-reducing related products, it can also lead to an

Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms

Science.gov (United States)

Marlot, Caroline; Barraud, Elodie; Le Gallet, Sophie; Eichhorn, Marc; Bernard, Frédéric

2012-07-01

YAG nanopowders with an average grain size of 30 nm have been successfully synthesized by the co-precipitation method using nitrates with precipitant of ammonium hydrogen carbonate. The influence of precipitation conditions such as pH, aging time and calcination temperature on the formation of secondary phases has been studied. The accurate control of pH value at every stage of precipitation process is crucial to avoid the presence of YAM (Yttrium Aluminium Monoclinic, Y4Al2O9) and yttrium oxide (Y2O3) after calcination. The reaction mechanisms have been investigated using different techniques such as infrared spectroscopy, x-ray diffraction and thermal analyses. The YAG phase is formed around 1050 °C passing through an intermediate phase called YAP (Yttrium Aluminium Perovskite, YAlO3). Local chemical heterogeneities are responsible for the deviation of the Y:Al ratio and the formation of YAP during heat treatment.

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

Energy Technology Data Exchange (ETDEWEB)

Chen Zhu

2006-08-31

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

Heavy metal immobilization via microbially induced carbonate precipitation and co-precipitation

Science.gov (United States)

Lauchnor, E. G.; Stoick, E.

2017-12-01

Microbially induced CaCO3 precipitation (MICP) has been successfully used in applications such as porous media consolidation and sealing of leakage pathways in the subsurface, and it has the potential to be used for remediation of metal and radionuclide contaminants in surface and groundwater. In this work, MICP is investigated for removal of dissolved heavy metals from contaminated mine discharge water via co-precipitation in CaCO3 or formation of other metal carbonates. The bacterially catalyzed hydrolysis of urea produces inorganic carbon and ammonium and increases pH and the saturation index of carbonate minerals to promote precipitation of CaCO3. Other heavy metal cations can be co-precipitated in CaCO3 as impurities or by replacing Ca2+ in the crystal lattice. We performed laboratory batch experiments of MICP in alkaline mine drainage sampled from an abandoned mine site in Montana and containing a mixture of heavy metals at near neutral pH. Both a model bacterium, Sporosarcina pasteurii, and a ureolytic bacterium isolated from sediments on the mine site were used to promote MICP. Removal of dissolved metals from the aqueous phase was determined via inductively coupled plasma mass spectrometry and resulting precipitates were analyzed via electron microscopy and energy dispersive x-ray spectroscopy (EDX). Both S. pasteurii and the native ureolytic isolate demonstrated ureolysis, increased the pH and promoted precipitation of CaCO3 in batch tests. MICP by the native bacterium reduced concentrations of the heavy metals zinc, copper, cadmium, nickel and manganese in the water. S. pasteurii was also able to promote MICP, but with less removal of dissolved metals. Analysis of precipitates revealed calcium carbonate and phosphate minerals were likely present. The native isolate is undergoing identification via 16S DNA sequencing. Ongoing work will evaluate biofilm formation and MICP by the isolate in continuous flow, gravel-filled laboratory columns. This research

Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals and industrial wastes as a Novel Carbon Capture and Storage Technology

Science.gov (United States)

Park, A. H. A.

2014-12-01

Increasing concentration of CO2 in the atmosphere is attributed to rising consumption of fossil fuels around the world. The development of solutions to reduce CO2 emissions to the atmosphere is one of the most urgent needs of today's society. One of the most stable and long-term solutions for storing CO2 is via carbon mineralization, where minerals containing metal oxides of Ca or Mg are reacted with CO2 to produce thermodynamically stable Ca- and Mg-carbonates that are insoluble in water. Carbon mineralization can be carried out in-situ or ex-situ. In the case of in-situ mineralization, the degree of carbonation is thought to be limited by both mineral dissolution and carbonate precipitation reaction kinetics, and must be well understood to predict the ultimate fate of CO2 within geological reservoirs. While the kinetics of in-situ mineral trapping via carbonation is naturally slow, it can be enhanced at high temperature and high partial pressure of CO2. The addition of weak organic acids produced from food waste has also been shown to enhance mineral weathering kinetics. In the case of the ex-situ carbon mineralization, the role of these ligand-bearing organic acids can be further amplified for silicate mineral dissolution. Unfortunately, high mineral dissolution rates often lead to the formation of a silica-rich passivation layer on the surface of silicate minerals. Thus, the use of novel solvent mixture that allows chemically catalyzed removal of this passivation layer during enhanced Mg-leaching surface reaction has been proposed and demonstrated. Furthermore, an engineered biological catalyst, carbonic anhydrase, has been developed and evaluated to accelerate the hydration of CO2, which is another potentially rate-limiting step of the carbonation reaction. The development of these novel catalytic reaction schemes has significantly improved the overall efficiency and sustainability of in-situ and ex-situ mineral carbonation technologies and allowed direct

[The adaptation reactions in hormonal systems to the internal use of mineral waters].

Science.gov (United States)

Polushina, N D

1991-01-01

A single intake of mineral water Essentuki 17 by male Wistar rats (n-130, b. w. 180-250 g) leads to stress reactions. It is evident from elevated levels of ACTH, hydrocortisone, leuenkephaline, glucagon and gastrin. Course intake of the water brings about a rise in most of the hormones levels studied. However, single doses of Essentuki 17 inhibit production of hormones in the adrenals, hypophysis, hypothalamus, the system of endogenic opiates. The enhancement of relevant levels are noted in the gastroenteropancreatic system.

A review of United States yellow cake precipitation practice

International Nuclear Information System (INIS)

Litz, J.E.; Coleman, R.B.

1980-01-01

The various process flowsheets used to produce concentrated uranium solutions are reviewed. The choices of flowsheets are affected by ore alkalinity, uranium mineralization, and the impurities solubilized during leaching. The techniques used to precipitate yellow cake from concentrated uranium solutions are reviewed. Consideration is given to precipitation chemistry, reagent requirements, and process equipment and costs for precipitation, dewatering, drying and calcining. (author)

Values of Deploying a Compact Polarimetric Radar to Monitor Extreme Precipitation in a Mountainous Area: Mineral County, Colorado

Science.gov (United States)

Cheong, B. L.; Kirstetter, P. E.; Yu, T. Y.; Busto, J.; Speeze, T.; Dennis, J.

2015-12-01

Precipitation in mountainous regions can trigger flash floods and landslides especially in areas affected by wildfire. Because of the small space-time scales required for observation, they remain poorly observed. A light-weighted X-band polarimetric radar can rapidly respond to the situation and provide continuous rainfall information with high resolution for flood forecast and emergency management. A preliminary assessment of added values to the operational practice in Mineral county, Colorado was performed in Fall 2014 and Summer 2015 with a transportable polarimetric radar deployed at the Lobo Overlook. This region is one of the numerous areas in the Rocky Mountains where the WSR-88D network does not provide sufficient weather coverage due to blockages, and the limitations have impeded forecasters and local emergency managers from making accurate predictions and issuing weather warnings. High resolution observations were collected to document the precipitation characteristics and demonstrate the added values of deploying a small weather radar in such context. The analysis of the detailed vertical structure of precipitation explain the decreased signal sampled by the operational radars. The specific microphysics analyzed though polarimetry suggest that the operational Z-R relationships may not be appropriate to monitor severe weather over this wildfire affected region. Collaboration with the local emergency managers and the National Weather Service shows the critical value of deploying mobile, polarimetric and unmanned radars in complex terrain. Several selected cases are provided in this paper for illustration.

On the complex conductivity signatures of calcite precipitation

Energy Technology Data Exchange (ETDEWEB)

Wu, Yuxin; Hubbard, Susan; Williams, Kenneth Hurst; Ajo-Franklin, Jonathan

2009-11-01

Calcite is a mineral phase that frequently precipitates during subsurface remediation or geotechnical engineering processes. This precipitation can lead to changes in the overall behavior of the system, such as flow alternation and soil strengthening. Because induced calcite precipitation is typically quite variable in space and time, monitoring its distribution in the subsurface is a challenge. In this research, we conducted a laboratory column experiment to investigate the potential of complex conductivity as a mean to remotely monitor calcite precipitation. Calcite precipitation was induced in a glass bead (3 mm) packed column through abiotic mixing of CaCl{sub 2} and Na{sub 2}CO{sub 3} solutions. The experiment continued for 12 days with a constant precipitation rate of {approx}0.6 milimole/d. Visual observations and scanning electron microscopy imaging revealed two distinct phases of precipitation: an earlier phase dominated by well distributed, discrete precipitates and a later phase characterized by localized precipitate aggregation and associated pore clogging. Complex conductivity measurements exhibited polarization signals that were characteristic of both phases of calcite precipitation, with the precipitation volume and crystal size controlling the overall polarization magnitude and relaxation time constant. We attribute the observed responses to polarization at the electrical double layer surrounding calcite crystals. Our experiment illustrates the potential of electrical methods for characterizing the distribution and aggregation state of nonconductive minerals like calcite. Advancing our ability to quantify geochemical transformations using such noninvasive methods is expected to facilitate our understanding of complex processes associated with natural subsurface systems as well as processes induced through engineered treatments (such as environmental remediation and carbon sequestration).

Up-scaling mineral-aqueous interfacial processes that govern isotope and trace element partitioning during calcite growth

Science.gov (United States)

Lammers, L. N.

2014-12-01

The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can

Obtaining new composite biomaterials by means of mineralization of methacrylate hydrogels using the reaction–diffusion method

Energy Technology Data Exchange (ETDEWEB)

Ramadan, Yousof [Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of Madrid, 28040 Madrid (Spain); González-Sánchez, M. Isabel [Department of Physical Chemistry, School of Industrial Engineering, Castilla-La Mancha University, 02071 Albacete (Spain); Hawkins, Karl [Centre of Nanohealth, Institute of Life Sciences, College of Medicine, Swansea University, Singleton Park, Swansea SA2 8PP, Wales (United Kingdom); Rubio-Retama, Jorge [Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of Madrid, 28040 Madrid (Spain); Valero, Edelmira [Department of Physical Chemistry, School of Industrial Engineering, Castilla-La Mancha University, 02071 Albacete (Spain); Perni, Stefano [School of Pharmacy and Pharmaceutical Sciences, Cardiff University, Cardiff CF103NB (United Kingdom); Department of Biological Engineering, MA Institute of Technology, Cambridge (United States); Prokopovich, Polina [School of Pharmacy and Pharmaceutical Sciences, Cardiff University, Cardiff CF103NB (United Kingdom); Institute of Medical Engineering and Medical Physics, School of Engineering, Cardiff University, Cardiff (United Kingdom); Department of Biological Engineering, MA Institute of Technology, Cambridge (United States); López-Cabarcos, Enrique, E-mail: cabarcos@farm.ucm.es [Department of Physical Chemistry II, Faculty of Pharmacy, Complutense University of Madrid, 28040 Madrid (Spain)

2014-09-01

The present paper describes the synthesis and characterization of a new polymeric biomaterial mineralized with calcium phosphate using the reaction–diffusion method. The scaffold of this biomaterial was a hydrogel constituted by biocompatible polyethylene glycol methyl ether methacrylate (PEGMEM) and 2-(dimethylamino)ethyl methacrylate (DMAEM), which were cross-linked with N-N’-methylenebisacrylamide (BIS). The cross-linking content of the hydrogels was varied from 0.25% to 15% (w/w). The gels were used as matrix where two reactants (Na{sub 2}HPO{sub 4} and CaCl{sub 2}) diffused from both ends of the gel and upon encountering produced calcium phosphate crystals that precipitated within the polymer matrix forming bands. The shape of the crystals was tuned by modifying the matrix porosity in such a way that when the polymer matrix was slightly reticulated the diffusion reaction produced round calcium phosphate microcrystals, whilst when the polymer matrix was highly reticulated the reaction yielded flat calcium phosphate crystals. Selected area electron diffraction performed on the nanocrystals that constitute the microcrystals showed that they were formed by Brushite (CaHPO{sub 4}.2H{sub 2}O). This new composite material could be useful in medical and dentistry applications such as bone regeneration, bone repair or tissue engineering. - Highlights: • New polymeric biomaterial mineralized with calcium phosphate using the reaction-diffusion method.-Growing of brushite nanocrystals within a polymeric matrix. • Mineralization by reaction diffusion method controls the crystal growth within gels.

Obtaining new composite biomaterials by means of mineralization of methacrylate hydrogels using the reaction–diffusion method

International Nuclear Information System (INIS)

Ramadan, Yousof; González-Sánchez, M. Isabel; Hawkins, Karl; Rubio-Retama, Jorge; Valero, Edelmira; Perni, Stefano; Prokopovich, Polina; López-Cabarcos, Enrique

2014-01-01

The present paper describes the synthesis and characterization of a new polymeric biomaterial mineralized with calcium phosphate using the reaction–diffusion method. The scaffold of this biomaterial was a hydrogel constituted by biocompatible polyethylene glycol methyl ether methacrylate (PEGMEM) and 2-(dimethylamino)ethyl methacrylate (DMAEM), which were cross-linked with N-N’-methylenebisacrylamide (BIS). The cross-linking content of the hydrogels was varied from 0.25% to 15% (w/w). The gels were used as matrix where two reactants (Na 2 HPO 4 and CaCl 2 ) diffused from both ends of the gel and upon encountering produced calcium phosphate crystals that precipitated within the polymer matrix forming bands. The shape of the crystals was tuned by modifying the matrix porosity in such a way that when the polymer matrix was slightly reticulated the diffusion reaction produced round calcium phosphate microcrystals, whilst when the polymer matrix was highly reticulated the reaction yielded flat calcium phosphate crystals. Selected area electron diffraction performed on the nanocrystals that constitute the microcrystals showed that they were formed by Brushite (CaHPO 4 .2H 2 O). This new composite material could be useful in medical and dentistry applications such as bone regeneration, bone repair or tissue engineering. - Highlights: • New polymeric biomaterial mineralized with calcium phosphate using the reaction-diffusion method.-Growing of brushite nanocrystals within a polymeric matrix. • Mineralization by reaction diffusion method controls the crystal growth within gels

Sulfide Precipitation in Wastewater at Short Timescales

DEFF Research Database (Denmark)

Kiilerich, Bruno; van de Ven, Wilbert; Nielsen, Asbjørn Haaning

2017-01-01

Abatement of sulfides in sewer systems using iron salts is a widely used strategy. When dosing at the end of a pumping main, the reaction kinetics of sulfide precipitation becomes important. Traditionally the reaction has been assumed to be rapid or even instantaneous. This work shows that this i......Abatement of sulfides in sewer systems using iron salts is a widely used strategy. When dosing at the end of a pumping main, the reaction kinetics of sulfide precipitation becomes important. Traditionally the reaction has been assumed to be rapid or even instantaneous. This work shows...... that this is not the case for sulfide precipitation by ferric iron. Instead, the reaction time was found to be on a timescale where it must be considered when performing end-of-pipe treatment. For real wastewaters at pH 7, a stoichiometric ratio around 14 mol Fe(II) (mol S(−II))−1 was obtained after 1.5 s, while the ratio...

Mineral Carbonation Employing Ultramafic Mine Waste

Science.gov (United States)

Southam, G.; McCutcheon, J.; Power, I. M.; Harrison, A. L.; Wilson, S. A.; Dipple, G. M.

2014-12-01

Carbonate minerals are an important, stable carbon sink being investigated as a strategy to sequester CO2 produced by human activity. A natural playa (Atlin, BC, CAN) that has demonstrated the ability to microbially-accelerate hydromagnesite formation was used as an experimental model. Growth of microbial mats from Atlin, in a 10 m long flow-through bioreactor catalysed hydromagnesite precipitation under 'natural' conditions. To enhance mineral carbonation, chrysotile from the Clinton Creek Asbestos Mine (YT, CAN) was used as a target substrate for sulphuric acid leaching, releasing as much as 94% of the magnesium into solution via chemical weathering. This magnesium-rich 'feedstock' was used to examine the ability of the microbialites to enhance carbonate mineral precipitation using only atmospheric CO2 as the carbon source. The phototrophic consortium catalysed the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] accompanied by magnesite [MgCO3], aragonite [CaCO3], and minor dypingite [Mg5(CO3)4(OH)2·5H2O]. Scanning Electron Microscopy-Energy Dispersive Spectroscopy indicated that cell exteriors and extracellular polymeric substances (EPS) served as nucleation sites for carbonate precipitation. In many cases, entire cyanobacteria filaments were entombed in magnesium carbonate coatings, which appeared to contain a framework of EPS. Cell coatings were composed of small crystals, which intuitively resulted from rapid crystal nucleation. Excess nutrient addition generated eutrophic conditions in the bioreactor, resulting in the growth of a pellicle that sealed the bioreactor contents from the atmosphere. The resulting anaerobic conditions induced fermentation and subsequent acid generation, which in turn caused a drop in pH to circumneutral values and a reduction in carbonate precipitation. Monitoring of the water chemistry conditions indicated that a high pH (> 9.4), and relatively high concentrations of magnesium (> 3000 ppm), compared with the natural

Modification the Oxalic Co-precipitation Method on a Novel Catalyst Cu/Zn/Al2O3/Cr2O3 for Autothermal Reforming Reaction of Methanol

Directory of Open Access Journals (Sweden)

Cheng- Hsin Kuo

2013-12-01

Full Text Available This study addresses the catalytic performance of Cu/ZnO/Al2O3/Cr2O3 in low-temperature of autothermal reforming (ATR reaction. Various operating conditions were used to decide the optimum reaction conditions: type of promoter (ZrO2, CeO2, and Cr2O3, precipitation temperature, precipitation pH, operation temperature, molar ratio of O2/CH3OH (O/C, and weight hourly space velocity (WHSV. The catalysts were prepared using the oxalic coprecipitation method. Characterization of the catalyst was conducted using a porosity analyzer, XRD, and SEM. The methanol conversion and volumetric percentage of hydrogen using the best catalyst (Cu/ZnO/Al2O3/Cr2O3 exceeded 93% and 43%, respectively. A catalyst prepared by precipitation at -5 oC and at pH of 1 converted methanol to 40% H2 and less than 3000 ppm CO at reaction temperature of 200 oC. The size and dispersion of copper and the degradation rate and turnover frequency of the catalyst was also calculated. Deactivation of the Cu catalyst at a reaction temperature of 200 oC occurred after 30 h. © 2013 BCREC UNDIP. All rights reservedReceived: 8th May 2013; Revised: 10th August 2013; Accepted: 18th August 2013[How to Cite: Cheng, H.K., Lesmana, D., Wu, H.S. (2013. Modification the Oxalic Co-precipitation Method on a Novel Catalyst Cu/Zn/Al2O3/Cr2O3 for Autothermal Reforming Reaction of Methanol. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 110-124. (doi:10.9767/bcrec.8.2.4844.110-124][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4844.110-124

Mineral paragenesis on Mars: The roles of reactive surface area and diffusion.

Science.gov (United States)

Fairén, Alberto G; Gil-Lozano, Carolina; Uceda, Esther R; Losa-Adams, Elisabeth; Davila, Alfonso F; Gago-Duport, Luis

2017-09-01

Geochemical models of secondary mineral precipitation on Mars generally assume semiopen systems (open to the atmosphere but closed at the water-sediment interface) and equilibrium conditions. However, in natural multicomponent systems, the reactive surface area of primary minerals controls the dissolution rate and affects the precipitation sequences of secondary phases, and simultaneously, the transport of dissolved species may occur through the atmosphere-water and water-sediment interfaces. Here we present a suite of geochemical models designed to analyze the formation of secondary minerals in basaltic sediments on Mars, evaluating the role of (i) reactive surface areas and (ii) the transport of ions through a basalt sediment column. We consider fully open conditions, both to the atmosphere and to the sediment, and a kinetic approach for mineral dissolution and precipitation. Our models consider a geochemical scenario constituted by a basin (i.e., a shallow lake) where supersaturation is generated by evaporation/cooling and the starting point is a solution in equilibrium with basaltic sediments. Our results show that cation removal by diffusion, along with the input of atmospheric volatiles and the influence of the reactive surface area of primary minerals, plays a central role in the evolution of the secondary mineral sequences formed. We conclude that precipitation of evaporites finds more restrictions in basaltic sediments of small grain size than in basaltic sediments of greater grain size.

Origin and nature of the aluminium phosphate-sulfate minerals (APS) associated with uranium mineralization in triassic red-beds (Iberian Range, Spain)

Energy Technology Data Exchange (ETDEWEB)

Marfil, R.; Iglesia, A. la; Estupinan, J.

2013-10-01

This study focuses on the mineralogical and chemical study of an Aluminium-phosphate-sulphate (APS) mineralization that occurs in a classic sequence from the Triassic (Buntsandstein) of the Iberian Range. The deposit is constituted by sandstones, mud stones, and conglomerates with arenaceous matrix, which were deposited in fluvial to shallow-marine environments. In addition to APS minerals, the following diagenetic minerals are present in the classic sequence: quartz, K-feldspar, kaolinite group minerals, illite, Fe-oxides-hydroxides, carbonate-sulphate cement-replacements and secondary uraniferous minerals. APS minerals were identified and characterized by optical microscopy, X-ray diffraction, scanning electron microscopy, and electron microprobe. Microcrystalline APS crystals occur replacing uraniferous minerals, associated with kaolinite, mica and filling pores, in distal fluvial-to-tidal arkoses-subarkoses. Given their Ca, Sr, and Ba contents, the APS minerals can be defined as a solid solution of crandallite- goyacite-gorceixite (0.53 Ca, 0.46 Sr and 0.01 Ba). The chemical composition, low LREE concentration and Sr > S suggest that the APS mineral were originated during the supergene alteration of the Buntsandstein sandstones due to the presence of the mineralizing fluids which causes the development of Ubearing sandstones in a distal alteration area precipitating from partially dissolved and altered detrital minerals. Besides, the occurrence of dickite associated with APS minerals indicates they were precipitated at diagenetic temperatures (higher than 80 degree centigrade), related to the uplifting occurred during the late Cretaceous post-rift thermal stage.(Author)

Origin and nature of the aluminium phosphate-sulfate minerals (APS) associated with uranium mineralization in triassic red-beds (Iberian Range, Spain)

International Nuclear Information System (INIS)

Marfil, R.; Iglesia, A. la; Estupinan, J.

2013-01-01

This study focuses on the mineralogical and chemical study of an Aluminium-phosphate-sulphate (APS) mineralization that occurs in a classic sequence from the Triassic (Buntsandstein) of the Iberian Range. The deposit is constituted by sandstones, mud stones, and conglomerates with arenaceous matrix, which were deposited in fluvial to shallow-marine environments. In addition to APS minerals, the following diagenetic minerals are present in the classic sequence: quartz, K-feldspar, kaolinite group minerals, illite, Fe-oxides-hydroxides, carbonate-sulphate cement-replacements and secondary uraniferous minerals. APS minerals were identified and characterized by optical microscopy, X-ray diffraction, scanning electron microscopy, and electron microprobe. Microcrystalline APS crystals occur replacing uraniferous minerals, associated with kaolinite, mica and filling pores, in distal fluvial-to-tidal arkoses-subarkoses. Given their Ca, Sr, and Ba contents, the APS minerals can be defined as a solid solution of crandallite- goyacite-gorceixite (0.53 Ca, 0.46 Sr and 0.01 Ba). The chemical composition, low LREE concentration and Sr > S suggest that the APS mineral were originated during the supergene alteration of the Buntsandstein sandstones due to the presence of the mineralizing fluids which causes the development of Ubearing sandstones in a distal alteration area precipitating from partially dissolved and altered detrital minerals. Besides, the occurrence of dickite associated with APS minerals indicates they were precipitated at diagenetic temperatures (higher than 80 degree centigrade), related to the uplifting occurred during the late Cretaceous post-rift thermal stage.(Author)

Integrated Experimental and Modeling Studies of Mineral Carbonation as a Mechanism for Permanent Carbon Sequestration in Mafic/Ultramafic Rocks

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhengrong [Yale Univ., New Haven, CT (United States); Qiu, Lin [Yale Univ., New Haven, CT (United States); Zhang, Shuang [Yale Univ., New Haven, CT (United States); Bolton, Edward [Yale Univ., New Haven, CT (United States); Bercovici, David [Yale Univ., New Haven, CT (United States); Ague, Jay [Yale Univ., New Haven, CT (United States); Karato, Shun-Ichiro [Yale Univ., New Haven, CT (United States); Oristaglio, Michael [Yale Univ., New Haven, CT (United States); Zhu, Wen-Iu [Univ. of Maryland, College Park, MD (United States); Lisabeth, Harry [Univ. of Maryland, College Park, MD (United States); Johnson, Kevin [Univ. of Hawaii, Honolulu, HI (United States)

2014-09-30

that could have been removed if the olivine initially present had fully dissolved and the cations released had subsequently precipitated in carbonate minerals. The carbonation fractions observed in batch experiments with olivine grains and powders varied significantly, from less than 0.01 (1%) to more than 0.5 (50%). Over time, the carbonation fractions reached an upper limit after about 24 to 72 hours of reaction, then stayed constant or decreased. The peak Final Scientific/Technical Report DE-FE0004275 | Mineral Carbonation | 4 coincided with the appearance of secondary magnesium-bearing silicate minerals, whose formation competes for magnesium ions in solution and can even promote conditions that dissolve magnesite. The highest carbonation fractions resulted from experiments with low ratios of concentrated solution to olivine, during which amorphous silica spheres or meshes formed, instead of secondary silicate minerals. The highest carbonation fractions appear to result from competing effects. Precipitation of silica layers on olivine reduces the reactive surface area and, thus, the rate of olivine dissolution (which ultimately limits the carbonation rate), but these same silica layers can also inhibit the formation of secondary silicate minerals that consume magnesite formed in earlier stages of carbonation. Simulation of these experiments with simple geochemical models using the software program EQ3/6 reproduces the general trends observed—especially the results for the carbonation fraction in short-run experiments. Although further experimentation and better models are needed, this study nevertheless provides a framework for understanding the optimal conditions for sequestering carbon dioxide by reacting CO₂-bearing fluids with rocks containing olivine minerals. A series of experiments at the Rock Physics Laboratory at the University of Maryland studied the carbonation process during deformation of thermally cracked olivine-rich rock samples (dunite

[Histochemical stains for minerals by hematoxylin-lake method].

Science.gov (United States)

Miyagawa, Makoto

2013-04-01

The present study was undertaken to establish the experimental animal model by histological staining methods for minerals. After intraperitoneal injections of minerals, precipitates deposited on the surface of the liver. Liver tissues were fixed in paraformaldehyde, embedded in paraffin and cut into thin sections which were used as minerals containing standard section. Several reagents for histological stains and spectrophotometry for minerals were applied in both test-tube experiments and stainings of tissue sections to test for minerals. Hematoxylin-lake was found of capable of staining minerals in tissue. A simple technique used was described for light microscopic detection of minerals.

Morphological control of strontium oxalate particles by PSMA-mediated precipitation reaction

Energy Technology Data Exchange (ETDEWEB)

Yu Jiaguo [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)]. E-mail: jiaguoyu@yahoo.com; Tang Hua [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Cheng Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

2005-05-15

In this paper, strontium oxalate particles with different morphologies could be easily obtained by a precipitation reaction of sodium oxalate with strontium chloride in the absence and presence of poly-(styrene-alt-maleic acid) (PSMA). The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The effects of pH, aging time and concentration of PSMA on the phase structures and morphologies of the as-prepared strontium oxalate particles were investigated and discussed. The results showed that strontium oxalate particles with various morphologies, such as, bi-pyramids, rods, peanuts, and spherical particles, etc., could be obtained by varying the experimental conditions. PSMA promoted the formation of strontium oxalate dihydrate (SOD) phase. Suitable pH values (pH 7 and 8) favor the formation of the peanut-shaped SrC{sub 2}O{sub 4} particles. This research may provide new insight into the control of morphologies and phase structures of strontium oxalate particles and the biomimetic synthesis of novel inorganic materials.

Experimental and numerical simulation of dissolution and precipitation: implications for fracture sealing at Yucca Mountain, Nevada

Science.gov (United States)

Dobson, Patrick F.; Kneafsey, Timothy J.; Sonnenthal, Eric L.; Spycher, Nicolas; Apps, John A.

2003-05-01

Plugging of flow paths caused by mineral precipitation in fractures above the potential repository at Yucca Mountain, Nevada could reduce the probability of water seeping into the repository. As part of an ongoing effort to evaluate thermal-hydrological-chemical (THC) effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation under anticipated temperature and pressure conditions in the repository. To replicate mineral dissolution by vapor condensate in fractured tuff, water was flowed through crushed Yucca Mountain tuff at 94 °C. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/l; silica was the dominant dissolved constituent. A portion of the steady-state mineralized water was flowed into a vertically oriented planar fracture in a block of welded Topopah Spring Tuff that was maintained at 80 °C at the top and 130 °C at the bottom. The fracture began to seal with amorphous silica within 5 days. A 1-D plug-flow numerical model was used to simulate mineral dissolution, and a similar model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The mineral precipitation simulations predicted the precipitation of amorphous silica at the base of the boiling front, leading to a greater than 50-fold decrease in fracture permeability in 5 days, consistent with the laboratory experiment. These results help validate the use of a numerical model to simulate THC processes at Yucca Mountain. The experiment and simulations indicated that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. However

Significance, mechanisms and environmental implications of microbial bio-mineralization

International Nuclear Information System (INIS)

Benzerara, K.; Miot, J.; Morin, G.; Ona-Nguema, G.; Skouri-Panet, F.; Ferard, C.

2011-01-01

Microorganisms can mediate the formation of minerals by a process called bio-mineralization. This process offers an efficient way to sequester inorganic pollutants within relatively stable solid phases. Here we review some of the main mechanisms involved in the mediation of mineral precipitation by microorganisms. This includes supersaturation caused by metabolic activity, the triggering of nucleation by production of more or less specific organic molecules, and the impact of mineral growth. While these processes have been widely studied in the laboratory, assessment of their importance in the environment is more difficult. We illustrate this difficulty using a case study on an As-contaminated acid mine drainage located in the South of France (Carnoules, Gard). In particular, we explore the potential relationships that might exist between microbial diversity and mineral precipitation. The present review, far from being exhaustive, highlights some recent advances in the field of bio-mineralogy and provides non-specialists an introduction to some of the main approaches and some questions that remain unanswered. (authors)

Evolution of models for conversion of smectite to non-expandable minerals

International Nuclear Information System (INIS)

Pusch, R.

1993-12-01

Hydrothermal alteration of smectite has long been regarded as conversion to illite and chlorite as concluded from investigations of Gulf sediments. As manifested by statements given earlier at various international scientific meetings and in the literature, smectite-to-illite conversion (S→I) has been assumed to be a solid-state reaction with layer-by-layer alteration via mixed layer I/S to illite. In the last 10 years this opinion has successively changed and in recent years the concept of dissolution of smectite and accessory minerals and precipitation of illite and possibly I/S has been favored by many investigators. The present report reports laboratory and field investigations on bentonite and also calculations based on geochemical codes, which all support the dissolution/precipitation process. Applying Pytte's model for calculating the rate of conversion to illite, one finds good agreement with a number of experiments and field data, and this model is therefore recommended for practical use

Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface.

Energy Technology Data Exchange (ETDEWEB)

Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.; Wang, Yifeng; Matteo, Edward N.; Meserole, Stephen P.; Tallant, David Robert

2013-09-01

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopy methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for

Laboratory batch experiments and geochemical modelling of water-rock-supercritical CO2 reactions in Southern San Joaquin Valley, California oil field sediments: Implications for future carbon capture and sequestration projects.

Science.gov (United States)

Mickler, P. J.; Rivas, C.; Freeman, S.; Tan, T. W.; Baron, D.; Horton, R. A.

2015-12-01

Storage of CO2 as supercritical liquid in oil reservoirs has been proposed for enhanced oil recovery and a way to lower atmospheric CO2 levels. The fate of CO2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this study, core samples from three potential storage formations, the Vedder Fm. (Rio Bravo oil field), Stevens Fm. (Elk Hills oil field) and Temblor Fm. (McKittrick oil field) were reacted with a synthetic brine and CO2(sc) at reservoir temperature (110°C) and pressure (245-250 bar). A combination of petrographic, SEM-EDS and XRD analyses, brine chemistry, and PHREEQ-C modelling were used to identify geochemical reactions altering aquifer mineralogy. XRD and petrographic analyses identified potentially reactive minerals including calcite and dolomite (~2%), pyrite (~1%), and feldspars (~25-60%). Despite the low abundance, calcite dissolution and pyrite oxidation were dominant geochemical reactions. Feldspar weathering produced release rates ~1-2 orders of magnitude slower than calcite dissolution. Calcite dissolution increased the aqueous concentrations of Ca, HCO3, Mg, Mn and Sr. Silicate weathering increased the aqueous concentrations of Si and K. Plagioclase weathering likely increased aqueous Ca concentrations. Pyrite oxidation, despite attempts to remove O2 from the experiment, increased the aqueous concentration of Fe and SO4. SEM-EDS analysis of post-reaction samples identified mixed-layered illite-smectites associated with feldspar grains suggesting clay mineral precipitation in addition to calcite, pyrite and feldspar dissolution. The Vedder Fm. sample underwent complete disaggregation during the reaction due to cement dissolution. This may adversely affect Vedder Formation CCS projects by impacting injection well integrity.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

Science.gov (United States)

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Ceria powders by homogeneous precipitation technique

International Nuclear Information System (INIS)

Ramanathan, S.; Roy, S.K.

2003-01-01

Formation of precursors for ceria by two homogeneous precipitation reactions - (cerium chloride + urea at 95 degC - called reaction A and cerium chloride + hexamethylenetetramine at 85 degC - called reaction B) - has been studied. The variation of size of the colloidal particles formed and the zeta potential of the suspensions with progress of reactions exhibited similar trends for both the precipitation processes. Particle size increased from 100 to 300 nm with increasing temperature and extent of reaction. The zeta potential was found to decrease with increasing extent of precipitation in the pH range of 5 to 7. Filtration and drying led to agglomeration of the fine particles in case of the precursor from reaction B. The as-formed precursors were crystalline - a basic carbonate in case of reaction A and hydrous oxide in case of reaction B. It was found that nano-crystalline ceria powders (average crystallite size -10 nm) formed above 400 degC from both these precursors. The agglomerate size (D50) of the precursors and ceria powders formed after calcination at 600 degC varied from 0.7 to 3 μm. Increasing calcination temperature up to 800 degC, increased the crystallite size (50 nm). The zeta potential variation with pH and concentration of an anionic dispersant (Calgon) for the ceria powders formed was studied to determine the ideal conditions for suspension stability. It was found to be maximum (i.e., the suspensions stable) in the pH range of 3 to 4 or Calgon concentration of 0.01 to 0.1 weight percent. (author)

Predicting when precipitation-driven synthesis is feasible : application to biocatalysis

NARCIS (Netherlands)

Ulijn, R.V.; Janssen, A.E.M.; Moore, B.D.; Halling, P.J.

2001-01-01

Precipitation-driven synthesis offers the possibility of obtaining high reaction yields using very low volume reactors and is finding increasing applications in biocatalysis. Here, a model that allows straightforward prediction of when such a precipitation-driven reaction will be thermodynamically

Characterization of iron and manganese minerals and their associated microbiota in different mine sites to reveal the potential interactions of microbiota with mineral formation.

Science.gov (United States)

Park, Jin Hee; Kim, Bong-Soo; Chon, Chul-Min

2018-01-01

Different environmental conditions such as pH and dissolved elements of mine stream induce precipitation of different minerals and their associated microbial community may vary. Therefore, mine precipitates from various environmental conditions were collected and their associated microbiota were analyzed through metagenomic DNA sequencing. Various Fe and Mn minerals including ferrihydrite, schwertmannite, goethite, birnessite, and Mn-substituted δ-FeOOH (δ-(Fe 1-x , Mn x )OOH) were found in the different environmental conditions. The Fe and Mn minerals were enriched with toxic metal(loid)s including As, Cd, Ni and Zn, indicating they can act as scavengers of toxic metal(loid)s in mine streams. Under acidic conditions, Acidobacteria was dominant phylum and Gallionella (Fe oxidizing bacteria) was the predominant genus in these Fe rich environments. Manganese oxidizing bacteria, Hyphomicrobium, was found in birnessite forming environments. Leptolyngbya within Cyanobacteria was found in Fe and Mn oxidizing environments, and might contribute to Fe and Mn oxidation through the production of molecular oxygen. The potential interaction of microbial community with minerals in mine sites can be traced by analysis of microbial community in different Fe and Mn mineral forming environments. Iron and Mn minerals contribute to the removal of toxic metal(loid)s from mine water. Therefore, the understanding characteristics of mine precipitates and their associated microbes helps to develop strategies for the management of contaminated mine water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

Science.gov (United States)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

Science.gov (United States)

Freund, F.; Batllo, F.; Leroy, R. C.; Lersky, S.; Masuda, M. M.; Chang, S.

1991-01-01

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Jae-Hyung Yoo; Eung-Ho Kim

1999-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, some experimental work of photochemical decomposition of oxalate was carried out to prove its feasibility as a step of partitioning process. The decomposition of oxalic acid in the presence of nitric acid was performed in advance in order to understand the mechanistic behaviour of oxalate destruction, and then the decomposition of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was examined. The decomposition rate of neodymium oxalate was found as 0.003 mole/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Simulation of the long term alteration of clay minerals in engineered bentonite barriers: nucleation and growth of secondary clay particles

International Nuclear Information System (INIS)

Fritz, B.; Clement, A.; Zwingmann, H.; Noguera, C.

2010-01-01

with elevated temperature. Thermodynamic effects are then combined with solubility products and kinetic effects on nucleation and growth of precipitated particles. It is a real challenge for geo-chemists to be able to account for precipitation kinetics in water-rock interaction models, particularly considering systems on short to mid terms (x 1000 y) compared to geological timescales. The recently developed code NANOKIN models dissolution processes of primary minerals as well as the kinetics of precipitation of secondary minerals taking into account the first steps of nucleation and growth and the subsequent evolution of the classes of particles precipitated. With these modellings the predicted evolution of the clay phase gives information on the crystal size distribution of secondary particles precipitated as a function of time. The model also examines the state of the aqueous solution with various mineral phases and combines the classical theory of crystal nucleation with size and morphology dependent kinetic rate laws for growth and/or dissolution of particles i.e. Oswald ripening processes. Ion exchange in mineral phases, and particularly in clay minerals has to be considered as a possible geochemical process taking place in clay barriers under storage conditions. This process might control first the transfer or the fixation of the major cations present in aqueous solutions (Ca 2+ , Mg 2+ , K + , Na + mainly but also H + , Fe 2+ , Al 3+ ) but also radionuclide cations if they might diffuse in the barriers after corrosion of the canisters on long term. When one considers this process from the simulation point of view, the challenge is not so easy. The same simulation has to combine kinetic processes with largely different time scales: near equilibrium cationic exchange reactions, which can be considered as quasi-instantaneous, and clay mineral precipitation which occurs on longer term in over-saturation state with respect to the solution. We have extended the code

An investigation of reaction parameters on geochemical storage of non-pure CO2 streams in iron oxides-bearing formations

Energy Technology Data Exchange (ETDEWEB)

Garcia, Susana; Liu, Q.; Bacon, Diana H.; Maroto-Valer, M. M.

2014-08-26

Hematite deposit that is the main FeIII-bearing mineral in sedimentary red beds was proposed as a potential host repository for converting CO2 into carbonate minerals such as siderite (FeCO3), when CO2–SO2 gas mixtures are co-injected. This work investigated CO2 mineral trapping using hematite and sensitivity of the reactive systems to different parameters, including particle size, gas composition, temperature, pressure, and solid-to-liquid ratio. Experimental and modelling studies of hydrothermal experiments were conducted, which emulated a CO2 sequestration scenario by injecting CO2-SO2 gas streams into a NaCl-NaOH brine hosted in iron oxide-containing aquifer. This study provides novel information on the mineralogical changes and fluid chemistry derived from the co-injection of CO2-SO2 gas mixtures in hematite deposit. It can be concluded that the amount of siderite precipitate depends primarily on the SO2 content of the gas stream. Increasing SO2 content in the system could promote the reduction of Fe3+ from the hematite sample to Fe2+, which will be further available for its precipitation as siderite. Moreover, siderite precipitation is enhanced at low temperatures and high pressures. The influence of the solid to liquid ratio on the overall carbonation reaction suggests that the conversion increases if the system becomes more diluted.

Precipitation of the rare earth double sodium and rare earths from the sulfuric liquor and the conversion into rare earth hydroxides through meta ethic reaction

International Nuclear Information System (INIS)

Abreu, Renata D.; Oliveira, Ester F.; Brito, Walter de; Morais, Carlos A.

2007-01-01

This work presents the purification study of the rare earths through precipitation of rare earth and sodium (Na TR (SO 4 ) 2 . x H 2 O)) double sulfate and his conversion to rare earths hydroxide TR(OH) 3 by meta ethic reaction through the addition of sodium hydroxide solution to the solid double sulfate. The study used the sulfuric liquor as rare earth sample, generated in the chemical processing of the monazite with sulfuric acid by the Industrias Nucleares do Brasil - INB, Brazil, after the thorium and uranium extraction. The work investigated the influence of the main variables involved in the precipitation of Na TR(SO 4 ) 2 .xH 2 O and in the conversion for the TR(OH) 3 , as follows: type and excess of the precipitation agent, temperature and time reaction. The obtained solid composites were characterized by X-ray diffraction, infrared and chemical analysis. The double sulfate diffractogram indicated the Na TR(SO 4 ) 2 mono-hydrated. The characterization of the metatese products has shown that, for obtaining the complete conversion of NaTR(SO 4 ) 2 .H 2 O into TR(OH) 3 , the reaction must be hot processed (∼70 deg C) and with small excess of Na OH (≤ 5 percent). (author)

Water-Soluble Cellulose Derivatives Are Sustainable Additives for Biomimetic Calcium Phosphate Mineralization

Directory of Open Access Journals (Sweden)

Andreas Taubert

2016-10-01

Full Text Available The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.

Effect of Aqueous Media on the Recovery of Scandium by Selective Precipitation

Directory of Open Access Journals (Sweden)

Bengi Yagmurlu

2018-05-01

Full Text Available This research presents a novel precipitation method for scandium (Sc concentrate refining from bauxite residue leachates and the effect of aqueous media on this triple-stage successive precipitation process. The precipitation pattern and the precipitation behavior of the constituent elements was investigated using different precipitation agents in three major mineral acid media, namely, H2SO4, HNO3, and HCl in a comparative manner. Experimental investigations showed behavioral similarities between HNO3 and HCl media, while H2SO4 media was different from them because of the nature of the formed complexes. NH4OH was found to be the best precipitation agent in every leaching media to remove Fe(III with low Sc co-precipitation. To limit Sc loss from the system, Fe(III removal was divided into two steps, leading to more than 90% of Fe(III removal at the end of the process. Phosphate concentrates were produced in the final step of the precipitation process with dibasic phosphates which have a strong affinity towards Sc. Concentrates containing more than 50% of ScPO4 were produced in each case from the solutions after Fe(III removal, as described. A flow diagram of the selective precipitation process is proposed for these three mineral acid media with their characteristic parameters.

The precipitation of double fluoride salts of uranium

Energy Technology Data Exchange (ETDEWEB)

Muir, C. W.A.

1963-02-15

Bench-scale kinetic tests were conducted to study the reduction and precipitation reactions involved in the preparation of ammonium uranous fluoride from high-purity uranyl nitrate solutions. Sulphur dioxide and formic acid were used to form the active reducing agent, nascent hyposulphite ion. The reduction was affected in the presence of ammonium fluoride, resulting in the precipitation of the highly insoluble double salt. It was found that uranium was precipituted at a constant rate throughout the progress of the reaction. It is postulated that the reducing agent was continuously regenerated, and that this reaction was rate controlling. As a result of this study, a reaction mechanism is proposed. (auth)

Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

Energy Technology Data Exchange (ETDEWEB)

Peters, Catherine A

2013-02-28

Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevant in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of

[Organic carbon and carbon mineralization characteristics in nature forestry soil].

Science.gov (United States)

Yang, Tian; Dai, Wei; An, Xiao-Juan; Pang, Huan; Zou, Jian-Mei; Zhang, Rui

2014-03-01

Through field investigation and indoor analysis, the organic carbon content and organic carbon mineralization characteristics of six kinds of natural forest soil were studied, including the pine forests, evergreen broad-leaved forest, deciduous broad-leaved forest, mixed needle leaf and Korean pine and Chinese pine forest. The results showed that the organic carbon content in the forest soil showed trends of gradual decrease with the increase of soil depth; Double exponential equation fitted well with the organic carbon mineralization process in natural forest soil, accurately reflecting the mineralization reaction characteristics of the natural forest soil. Natural forest soil in each layer had the same mineralization reaction trend, but different intensity. Among them, the reaction intensity in the 0-10 cm soil of the Korean pine forest was the highest, and the intensities of mineralization reaction in its lower layers were also significantly higher than those in the same layers of other natural forest soil; comparison of soil mineralization characteristics of the deciduous broad-leaved forest and coniferous and broad-leaved mixed forest found that the differences of litter species had a relatively strong impact on the active organic carbon content in soil, leading to different characteristics of mineralization reaction.

Precipitates/Salts Model Sensitivity Calculation

International Nuclear Information System (INIS)

Mariner, P.

2001-01-01

The objective and scope of this calculation is to assist Performance Assessment Operations and the Engineered Barrier System (EBS) Department in modeling the geochemical effects of evaporation on potential seepage waters within a potential repository drift. This work is developed and documented using procedure AP-3.12Q, ''Calculations'', in support of ''Technical Work Plan For Engineered Barrier System Department Modeling and Testing FY 02 Work Activities'' (BSC 2001a). The specific objective of this calculation is to examine the sensitivity and uncertainties of the Precipitates/Salts model. The Precipitates/Salts model is documented in an Analysis/Model Report (AMR), ''In-Drift Precipitates/Salts Analysis'' (BSC 2001b). The calculation in the current document examines the effects of starting water composition, mineral suppressions, and the fugacity of carbon dioxide (CO 2 ) on the chemical evolution of water in the drift

Experimental deformation of a mafic rock - interplay between fracturing, reaction and viscous deformation

Science.gov (United States)

Marti, Sina; Stünitz, Holger; Heilbronner, Renée; Plümper, Oliver; Drury, Martyn

2016-04-01

Deformation experiments were performed on natural Maryland Diabase (˜ 55% Plg, 42% Px, 3% accessories, 0.18 wt.-% H2O added) in a Griggs-type deformation apparatus in order to explore the brittle-viscous transition and the interplay between deformation and mineral reactions. Shear experiments at strain rates of ˜ 2e-5 /s are performed, at T=600, 700 and 800°C and confining pressures Pc=1.0 and 1.5 GPa. Deformation localizes in all experiments. Below 700°C, the microstructure is dominated by brittle deformation with a foliation formed by cataclastic flow and high strain accommodated along 3-5 major ultracataclasite shear bands. At 700°C, the bulk of the material still exhibits abundant microfractures, however, deformation localizes into an anastomosing network of shear bands (SB) formed from a fine-grained (<< 1 μm) mixture of newly formed Plg and Amph. These reaction products occur almost exclusively along syn-kinematic structures such as fractures and SB. Experiments at 800°C show extensive mineral reactions, with the main reaction products Amph+Plg (+Zo). Deformation is localized in broad C' and C SB formed by a fine-grained (0.1 - 0.8 μm) mixture of Plg+Amph (+Zo). The onset of mineral reactions in the 700°C experiments shows that reaction kinetics and diffusional mass transport are fast enough to keep up with the short experimental timescales. While in the 700°C experiments brittle processes kinematically contribute to deformation, fracturing is largely absent at 800°C. Diffusive mass transfer dominates. The very small grain size within SB favours a grain size sensitive deformation mechanism. Due to the presence of water (and relatively high supported stresses), dissolution-precipitation creep is interpreted to be the dominant strain accommodating mechanism. From the change of Amph coronas around Px clasts with strain, we can determine that Amph is re-dissolved at high stress sites while growing in low stress sites, showing the ability of Amph to

Ammonia gas transport and reactions in unsaturated sediments: Implications for use as an amendment to immobilize inorganic contaminants

International Nuclear Information System (INIS)

Zhong, L.; Szecsody, J.E.; Truex, M.J.; Williams, M.D.; Liu, Y.

2015-01-01

Highlights: • Ammonia transport can be predicted from gas movement and equilibrium partitioning. • Ammonia diffusion rate in unsaturated sediment is a function of water contents. • High pH induced by ammonia causes mineral dissolution and sequential precipitation. • Ammonia treatment effectively immobilized uranium from contaminated sediments. - Abstract: Use of gas-phase amendments for in situ remediation of inorganic contaminants in unsaturated sediments of the vadose zone may be advantageous, but there has been limited development and testing of gas remediation technologies. Treatment with ammonia gas has a potential for use in treating inorganic contaminants (such as uranium) because it induces a high pore-water pH, causing mineral dissolution and subsequent formation of stable precipitates that decrease the mobility of some contaminants. For field application of this treatment, further knowledge of ammonia transport in porous media and the geochemical reactions induced by ammonia treatment is needed. Laboratory studies were conducted to support calculations needed for field treatment design, to quantify advective and diffusive ammonia transport in unsaturated sediments, to evaluate inter-phase (gas/sediment/pore water) reactions, and to study reaction-induced pore-water chemistry changes as a function of ammonia delivery conditions, such as flow rate, gas concentration, and water content. Uranium-contaminated sediment was treated with ammonia gas to demonstrate U immobilization. Ammonia gas quickly partitions into sediment pore water and increases the pH up to 13.2. Injected ammonia gas advection front movement can be reasonably predicted by gas flow rate and equilibrium partitioning. The ammonia gas diffusion rate is a function of the water content in the sediment. Sodium, aluminum, and silica pore-water concentrations increase upon exposure to ammonia and then decline as aluminosilicates precipitate when the pH declines due to buffering. Up to 85% of

Properties of precipitates formed during ammonization of extractional phosphoric acid

International Nuclear Information System (INIS)

Zakharova, B.S.; Komissarova, L.N.; Naumov, S.V.; Traskin, V.Yu.

1992-01-01

Dimensions of precipitated rare-earth phosphate particles -(0.1 μm)- are near the boundary of colloidal system sedimentation stability range at neutralization of extraction phosphoric acid. Thus, formation of multiple aggregates of colloidal particles results in immediate sedimentation of the precipitate. Processes occurring within the system may be described using second order reaction equation. Average efficient size of precipitates grows at reduction of reaction mixture pH. About 30% of rare-earth elements and yttrium in the extraction phosphoric acid is extracted from it; concentration of rare-earth elements, yttrium and scandium in precipitate is maximum 2 mass. %

Fumed and Precipitated Hydrophilic Silica Suspension Gels in Mineral Oil: Stability and Rheological Properties

Directory of Open Access Journals (Sweden)

Yoshiki Sugino

2017-08-01

Full Text Available Hydrophilic fumed silica (FS and precipitated silica (PS powders were suspended in mineral oil; increasing the silica volume fraction (φ in the suspension led to the formation of sol, pre-gel, and gel states. Gelation took place at lower φ values in the FS than the PS suspension because of the lower silanol density on the FS surface. The shear stresses and dynamic moduli of the FS and PS suspensions were measured as a function of φ. Plots of the apparent shear viscosity against shear rate depended on φ and the silica powder. The FS suspensions in the gel state exhibited shear thinning, followed by a weak shear thickening or by constant viscosity with an increasing shear rate. In contrast, the PS suspensions in the gel state showed shear thinning, irrespective of φ. The dynamic moduli of the pre-gel and gel states were dependent on the surface silanol density: at a fixed φ, the storage modulus G′ in the linear viscoelasticity region was larger for the FS than for the PS suspension. Beyond the linear region, the G′ of the PS suspensions showed strain hardening and the loss modulus G″ of the FS and PS suspensions exhibited weak strain overshoot.

Using MicroFTIR to Map Mineral Distributions in Serpentinizing Systems

Science.gov (United States)

Johnson, A.; Kubo, M. D.; Cardace, D.

2016-12-01

Serpentinization, the water-rock reaction forming serpentine mineral assemblages from ultramafic precursors, can co-occur with the production of hydrogen, methane, and diverse organic compounds (McCollom and Seewald, 2013), evolving water appropriate for carbonate precipitation, including in ophiolite groundwater flow systems and travertine-producing seeps/springs. Serpentinization is regarded as a geologic process important to the sustainability of the deep biosphere (Schrenk et al., 2013) and the origin of life (Schulte et al., 2006). In this study, we manually polished wafers of ultramafic rocks/associated minerals (serpentinite, peridotite, pyroxenite, dunite; olivine, diopside, serpentine, magnetite), and travertine/constituent minerals (carbonate crusts; calcite, dolomite), and observed mineral boundaries and interfaces using µFTIR analysis in reflection mode. We used a Thermo Nicolet iS50 FTIR spectrometer coupled with a Continuum IR microscope to map minerals/boundaries. We identify, confirm, and document FTIR wavenumber regions linked to serpentinite- and travertine-associated minerals by referencing IR spectra (RRUFF) and aligning with x-ray diffraction. The ultramafic and carbonate samples are from the following field localities: McLaughlin Natural Reserve - a UC research reserve, Lower Lake, CA; Zambales, PH; Ontario, CA; Yellow Dog, MI; Taskesti, TK; Twin Sisters Range, WA; Sharon, MA; Klamath Mountains, CA; Dun Mountain, NZ; and Sussex County, NJ. Our goals are to provide comprehensive µFTIR characterization of mineral profiles important in serpentinites and related rocks, and evaluate the resolving power of µFTIR for the detection of mineral-encapsulated, residual organic compounds from biological activity. We report on µFTIR data for naturally occurring ultramafics and travertines and also estimate the limit of detection for cell membrane components in mineral matrices, impregnating increasing mass proportions of xanthan gum in a peridotite sand

Effects of iron type in Fenton reaction on mineralization and biodegradability enhancement of hazardous organic compounds.

Science.gov (United States)

Khan, Eakalak; Wirojanagud, Wanpen; Sermsai, Nawarat

2009-01-30

The mineralization and biodegradability increase and their combination of two traditional and two relatively new organic contaminants by Fenton reagents with three different types of iron, Fe(2+), Fe(3+), and Fe(0) were investigated. The traditional contaminants examined were trichloroethene (TCE) and 2,4-dichlorophenol (2,4-DCP) while 1,4-dioxane (1,4-D) and 1,2,3-trichloropropane (TCP) were studied for the relatively new contaminants. The mineralization and biodegradability were represented by dissolved organic carbon (DOC) reduction and the ratio of biodegradable dissolved organic carbon and DOC, respectively. For all four contaminants, Fenton reagent using Fe(2+) was more effective in the DOC reduction than Fenton reagents using Fe(3+) and Fe(0) in most cases. The types of Fe that provided maximum biodegradability increase were not the same for all four compounds, Fe(3+) for TCE, Fe(0) for 2,4-DCP, Fe(2+) for 1,4-D, and Fe(3+) for TCP. When the combination of DOC elimination and biodegradability increase (least refractory fraction) was considered, Fe(2+) was the best choice except for 2,4-DCP which was susceptible to Fe(0) catalyzed Fenton reagent the most. The least refractory fractions remaining after 120 min of reaction were 20-25% for TCE, 2,4-DCP, and TCP and 30-40% for 1,4-D. The iron type in Fenton reaction also affected the type of mineralization kinetics of TCE, 2,4-DCP, and TCP as well as the types of degradation by-products of these contaminants. Some of the by-products found, such as isopropanol and propionic aldehyde, which were produced from Fe(0) catalyzed Fenton degradation of TCP, have not been previously reported.

Effect of indifferent anions on reactions of cadmium ferrocyanide precipitation

Energy Technology Data Exchange (ETDEWEB)

Gyunner, Eh A; Mel' nichenko, L M; Vel' mozhnyj, I S [Simferopol' skij Gosudarstvennyj Univ. (Ukrainian SSR)

1982-08-01

To clarify the effect of indifferent anions on the processes of cadmium ferrocyanide precipitation the interaction in six systems of the type CdXsub(m)-Msub(4)R-Hsub(2)O (X-Cl/sup -/, CH/sub 3/COO/sup -/, SO/sub 4//sup 2 -/; M-K/sup +/, NH/sub 4//sup +/; R-(Fe(CN)/sub 6/)/sup 4 -/) is studied using the methods of physicochemical analysis (the method of residual concentrations, refractometry). Composition and formation regions of low-soluble interaction products are determined. Effect of anion X nature on interaction character is stated in the series Cl/sup -/, CH/sub 3/COO/sup -/, SO/sub 4//sup 2 -/ in mixtures with incomplete Cd/sup 2 +/ precipitation a tendency for the increase of Cd/sup 2 +/:R/sup 4 -/ ratios in precipitates formed is observed.

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation

Science.gov (United States)

Zeng, Zhirui; Tice, Michael M.

2018-01-01

Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms.

Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

Science.gov (United States)

Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

2017-03-01

Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

Kinetics of Z-Phase Precipitation in 9 to 12 pct Cr Steels

DEFF Research Database (Denmark)

Danielsen, Hilmar Kjartansson; Nunzio, Paolo Emilio di; Hald, John

2013-01-01

precipitated Z-phase 20 to 50 times faster than the 9 pct Cr steel. Transmission electron microscopy (TEM) was applied to follow the Z-phase precipitation, using energy-dispersive X-ray spectroscopy (EDS) line scans and atomic resolution imaging. © The Minerals, Metals & Materials Society and ASM International...

Reactor design considerations in mineral sequestration of carbon dioxide

International Nuclear Information System (INIS)

Ityokumbul, M.T.; Chander, S.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.

2001-01-01

One of the promising approaches to lowering the anthropogenic carbon dioxide levels in the atmosphere is mineral sequestration. In this approach, the carbon dioxide reacts with alkaline earth containing silicate minerals forming magnesium and/or calcium carbonates. Mineral carbonation is a multiphase reaction process involving gas, liquid and solid phases. The effective design and scale-up of the slurry reactor for mineral carbonation will require careful delineation of the rate determining step and how it changes with the scale of the reactor. The shrinking core model was used to describe the mineral carbonation reaction. Analysis of laboratory data indicates that the transformations of olivine and serpentine are controlled by chemical reaction and diffusion through an ash layer respectively. Rate parameters for olivine and serpentine carbonation are estimated from the laboratory data

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

Science.gov (United States)

Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi

2015-04-28

The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

Iron Isotope Fractionation in Microbial and Non-Biological Precipitates, and the Human Body

Science.gov (United States)

von Blanckenburg, F.; Boettcher, M. E.; Hofmann, B.; Walczyk, T.

2001-12-01

We have investigated biotic and abiotic stable iron isotope fractionation pathways in experiments, the low-T natural environment, and the human body. Fe samples were analysed using a Nu Plasma Multicollector ICP-MS. All measured samples plot on the theoretically predicted exponential fractionation line in the Delta57Fe versus Delta56Fe space, demonstrating absence of ArN or ArO interferences. An experimental calibration of Fe isotope fractionation during abiotic formation of iron (III) oxyhydroxide and iron(II) minerals from aqueous solution resulted in significant differences: (a) During fast precipitation of FeOOH during alkalization of a Fe(III)Cl3 solution at room temperature the solid is only slightly enriched by about 0.1permil in 57Fe compared to the solution. (b) Slow precipitation of akaganeite (beta-FeOOH) from aqueous Fe(III)Cl3 solution leads to a depletion of 57Fe by about -2.2permil in the solid phase without a significant influence of temperature. (c) Precipitation of FeOOH during oxidation of aqueous Fe(II) solutions by oxygen yields an enrichment of up to 4.8permil in 57Fe in the solid phase. (d) Iron(II) carbonate precipitation between 20 and 60C leads to an almost negligible depletion in 57Fe compared to aqueous ferrous ions. Interpretation: Large enrichment of the heavy isotope is observed where Fe is oxidised, whereas small to interme-diate depletions of heavy Fe isotopes occur upon forma-tion of Fe-minerals without change in redox state. Addi-tionally, kinetic effects, the speciation of the aqueous solution, or the effect of crystal structures may have to be considered. Biotic isotope fractionation by microorganisms was investigated at two field sites. In a Fe mine (Gonzen, Switzerland), Fe-precipitating microbes (Gallionella ferrugina and Leptohrix ochtraceae) have formed Fe(III)-oxyhydroxides that are ca. 0.6permil heavier in Delta57Fe than the Fe-rich parent solutions. At Cady Mts, California, filamentous fabrics of goethite, thought to

Effects of freshwater Synechococcus sp. cyanobacteria pH buffering on CaCO3 precipitation: Implications for CO2 sequestration

International Nuclear Information System (INIS)

Martinez, Raul E.; Weber, Sebastian; Grimm, Christian

2016-01-01

In the present study, a mixed-flow steady-state bio-reactor was designed to biomineralize CO 2 as a consequence of photosynthesis from active Synechococcus sp. Dissolved CO 2 , generated by constant air bubbling of inorganic and cyanobacteria stock solutions, was the only source of inorganic carbon. The release of hydroxide ion by cyanobacteria from photosynthesis maintained highly alkaline pH conditions. In the presence of Ca 2+ and carbonate species, this led to calcite supersaturation under steady state conditions. Ca 2+ remained constant throughout the experiments showing the presence of steady state conditions. Similarly, the Synechococcus sp. biomass concentration remained stable within uncertainty. A gradual pH decrease was observed for the highest Ca 2+ condition coinciding with the formation of CaCO 3 . The high degree of supersaturation, under steady-state conditions, contributed to the stabilization of calcite and maintained a constant driving force for the mineral nucleation and growth. For the highest Ca 2+ condition a fast crystal growth rate was consistent with rapid calcite precipitation as suggested further by affinity calculations. Although saturation state based kinetic precipitation models cannot accurately reflect the controls on crystal growth kinetics or reliably predict growth mechanisms, the relatively reaction orders obtained from modeling of calcite precipitation rates as function of decreasing carbonate concentration suggest that the precipitation occurred via surface-controlled rate determining reactions. These high reaction orders support in addition the hypothesis that crystal growth proceeded through complex surface controlled mechanisms. In conclusion, the steady state supersaturated conditions generated by a constant cyanobacteria biomass and metabolic activity strongly suggest that these microorganisms could be used for the development of efficient CO 2 sequestration methods in a controlled large-scale environment. - Highlights: �

Physiology, Fe(II oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

Directory of Open Access Journals (Sweden)

Elizabeth D. Swanner

2015-10-01

Full Text Available Evidence for Fe(II oxidation and deposition of Fe(III-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF. While the exact mechanisms of Fe(II oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II-rich waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM are consistent with extracellular precipitation of Fe(III (oxyhydroxide minerals, but that >10% of Fe(III sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS in Fe(II toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II. These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways.

Science.gov (United States)

Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

2009-12-15

Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann's approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin's law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst's law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.

Reaction-sintered porous mineral-based mullite ceramic membrane supports made from recycled materials.

Science.gov (United States)

Dong, Yingchao; Zhou, Jian-Er; Lin, Bin; Wang, Yongqing; Wang, Songlin; Miao, Lifeng; Lang, Ying; Liu, Xingqin; Meng, Guangyao

2009-12-15

Bulk porous mullite supports for ceramic membranes were prepared directly using a mixture of industrial waste fly ash and bauxite by dry-pressing, followed by sintering between 1200 and 1550 degrees C. The effects of sintering temperature on the phase composition and shrinkage percent of porous mullite were studied. The XRD results indicate that secondary mullitization reaction took place above 1200 degrees C, and completed at 1450 degrees C. During sintering, the mixture samples first shrunk, then expanded abnormally between 1326 and 1477 degrees C, and finally shrunk again above 1477 degrees C. This unique volume self-expansion is ascribed to the secondary mullitization reaction between bauxite and fly ash. More especially, the micro-structural variations induced by this self-expansion sintering were verified by SEM, porosity, pore size distribution and nitrogen gas permeation flux. During self-expansion sintering, with increasing temperature, an abnormal increase in both open porosity and pore size is observed, which also results in the increase of nitrogen gas flux. The mineral-based mullite supports with increased open porosity were obtained. Furthermore, the sintered porous mullite membrane supports were characterized in terms of thermal expansion co-efficient and mechanical strength.

Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. BoFeN1.

Science.gov (United States)

Dippon, Urs; Pantke, Claudia; Porsch, Katharina; Larese-Casanova, Phil; Kappler, Andreas

2012-06-19

The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.

Competing retention pathways of uranium upon reaction with Fe(II)

Science.gov (United States)

Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

2014-10-01

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

Science.gov (United States)

Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

2017-04-01

Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

Science.gov (United States)

Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

2017-12-01

Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

Modification of asphaltic concrete with a mineral polymeric additive based on butadiene-styrene rubber and chemically precipitated calcium carbonate

Directory of Open Access Journals (Sweden)

S. I. Niftaliev

2016-01-01

Full Text Available Modification of asphaltic concrete with a mineral polymeric additive based on butadiene – styrene rubber and chemically precipitated calcium carbonate. This paper presents the results of the study of physical – mechanical and service properties of the asphaltic concrete modified with the mineral polymeric composition. Calcium carbonate is used both as a filler and a coagulant. The chalk was preliminarily ground and hydrophobizated by stearic acid. These operations contribute to even distribution of the filler and interfere with lump coagulation. As a result of the experiments, it was found that the best results were obtained by combining the operations of dispersion and hydrophobization. The optimal amount of stearic acid providing the finest grinding in a ball mill is a content from 3 to 5% by weight. The optimal grinding time of the filler was found (4–6 hours. With increasing dispersion time the particles form agglomerates. Filling the butadiene styrene latex with the hydrophobic fine-grained calcium carbonate was carried out in the laboratory mixer. As a result of the experimental works, it was found that the best distribution of the filler takes place with ratio of rubber: chalk – 100:400. The resulting modifier was subjected to the thermal analysis on the derivatograph to determine its application temperature interval. A marked reduction in weight of the mineral polymeric modifier begins at 350 °C. Thus, high temperature of the modifier destruction allows to use it at the temperature of the technological process of asphaltic concrete preparation (up to 170 °C. It was found that an increase in the amount of the carbonate filler in the rubber SKS 30АRК significantly increases its thermal resistance and connection of the polymer with the chalk in the composition.

Precipitates/Salts Model Sensitivity Calculation

Energy Technology Data Exchange (ETDEWEB)

P. Mariner

2001-12-20

The objective and scope of this calculation is to assist Performance Assessment Operations and the Engineered Barrier System (EBS) Department in modeling the geochemical effects of evaporation on potential seepage waters within a potential repository drift. This work is developed and documented using procedure AP-3.12Q, ''Calculations'', in support of ''Technical Work Plan For Engineered Barrier System Department Modeling and Testing FY 02 Work Activities'' (BSC 2001a). The specific objective of this calculation is to examine the sensitivity and uncertainties of the Precipitates/Salts model. The Precipitates/Salts model is documented in an Analysis/Model Report (AMR), ''In-Drift Precipitates/Salts Analysis'' (BSC 2001b). The calculation in the current document examines the effects of starting water composition, mineral suppressions, and the fugacity of carbon dioxide (CO{sub 2}) on the chemical evolution of water in the drift.

Hydrothermal minerals

Digital Repository Service at National Institute of Oceanography (India)

Nath, B.N.

flux. Circulation of seawater through the oceanic crust and upper mantle gives rise to a complex series of physical and chemical reactions that lead to the 1) formation of seafloor mineral deposits; 2) alteration of oceanic crust; 3) control... temperature in the high-temperature reaction zone near the heat source. Important parameters in determining the high- temperature fluid composition are • pressure, • temperature, • water/rock ratio, • rock composition, • recharge fluid...

comparison of authigenic minerals in sandstones and interbedded

African Journals Online (AJOL)

a

Mechanically compacted mudstones, siltstones and shales expelled large ... quartz, and (16) hydrocarbon migration; pyrite and apatite precipitation [1, 7, 12]. ... relationship of the authigenic minerals, burial history and fluid inclusions studies.

Electron Transfer Strategies Regulate Carbonate Mineral and Micropore Formation.

Science.gov (United States)

Zeng, Zhirui; Tice, Michael M

2018-01-01

Some microbial carbonates are robust biosignatures due to their distinct morphologies and compositions. However, whether carbonates induced by microbial iron reduction have such features is unknown. Iron-reducing bacteria use various strategies to transfer electrons to iron oxide minerals (e.g., membrane-bound enzymes, soluble electron shuttles, nanowires, as well as different mechanisms for moving over or attaching to mineral surfaces). This diversity has the potential to create mineral biosignatures through manipulating the microenvironments in which carbonate precipitation occurs. We used Shewanella oneidensis MR-1, Geothrix fermentans, and Geobacter metallireducens GS-15, representing three different strategies, to reduce solid ferric hydroxide in order to evaluate their influence on carbonate and micropore formation (micro-size porosity in mineral rocks). Our results indicate that electron transfer strategies determined the morphology (rhombohedral, spherical, or long-chained) of precipitated calcium-rich siderite by controlling the level of carbonate saturation and the location of carbonate formation. Remarkably, electron transfer strategies also produced distinctive cell-shaped micropores in both carbonate and hydroxide minerals, thus producing suites of features that could potentially serve as biosignatures recording information about the sizes, shapes, and physiologies of iron-reducing organisms. Key Words: Microbial iron reduction-Micropore-Electron transfer strategies-Microbial carbonate. Astrobiology 18, 28-36.

Biogenic iron mineralization at Iron Mountain, CA with implications for detection with the Mars Curiosity rover

Science.gov (United States)

Williams, Amy J.; Sumner, Dawn Y.; Alpers, Charles N.; Campbell, Kate M.; Nordstrom, D. Kirk

2014-01-01

(Introduction) Microbe-mineral interactions and biosignature preservation in oxidized sulfidic ore bodies (gossans) are prime candidates for astrobiological study. Such oxidized iron systems have been proposed as analogs for some Martian environments. Recent studies identified microbial fossils preserved as mineral-coated filaments. This study documents microbially-mediated mineral biosignatures in hydrous ferric oxide (HFO) and ferric oxyhydroxysulfates (FOHS) in three environments at Iron Mountain, CA. We investigated microbial community preservation via HFO and FOHS precipitation and the formation of filamentous mineral biosignatures. These environments included 1) actively precipitating (1000's yrs), naturally weathered HFO from in situ gossan, and 3) remobilized iron deposits, which contained lithified clastics and zones of HFO precipitate. We used published biogenicity criteria as guidelines to characterize the biogenicity of mineral filaments. These criteria included A) an actively precipitating environment where microbes are known to be coated in minerals, B) presence of extant microbial communities with carbon signatures, C) structures observable as a part of the host rock, and D) biological morphology, including cellular lumina, multiple member population, numerous taxa, variable and 3-D preservation, biological size ranges, uniform diameter, and evidence of flexibility. This study explores the relevance and detection of these biosignatures to possible Martian biosignatures. Similar filamentous biosignatures are resolvable by the Mars Hand Lens Imager (MAHLI) onboard the Mars Science Laboratory (MSL) rover, Curiosity, and may be identifiable as biogenic if present on Mars.

Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

Science.gov (United States)

Morrison, Stan J.; Metzler, Donald R.; Dwyer, Brian P.

2002-05-01

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe 3O 4), calcite (CaCO 3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH) 2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO 2, V 2O 3), sulfides (As 2S 3, ZnS), iron minerals (FeSe 2, FeMoO 4) and carbonate (MnCO 3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

Engineering analysis of the two-stage trifluoride precipitation process

International Nuclear Information System (INIS)

Luerkens, D.w.W.

1984-06-01

An engineering analysis of two-stage trifluoride precipitation processes is developed. Precipitation kinetics are modeled using consecutive reactions to represent fluoride complexation. Material balances across the precipitators are used to model the time dependent concentration profiles of the main chemical species. The results of the engineering analysis are correlated with previous experimental work on plutonium trifluoride and cerium trifluoride

Carbon dioxide sequestration by direct mineral carbonation with carbonic acid

Energy Technology Data Exchange (ETDEWEB)

O' Connor, William K.; Dahlin, David C.; Nilsen, David N.; Walters, Richard P.; Turner, Paul C.

2000-01-01

The Albany Research Center (ARC) of the U.S. Dept. of Energy (DOE) has been conducting a series of mineral carbonation tests at its Albany, Oregon, facility over the past 2 years as part of a Mineral Carbonation Study Program within the DOE. Other participants in this Program include the Los Alamos National Laboratory, Arizona State University, Science Applications International Corporation, and the DOE National Energy Technology Laboratory. The ARC tests have focused on ex-situ mineral carbonation in an aqueous system. The process developed at ARC utilizes a slurry of water mixed with a magnesium silicate mineral, olivine [forsterite end member (Mg2SiO4)], or serpentine [Mg3Si2O5(OH)4]. This slurry is reacted with supercritical carbon dioxide (CO2) to produce magnesite (MgCO3). The CO2 is dissolved in water to form carbonic acid (H2CO3), which dissociates to H+ and HCO3 -. The H+ reacts with the mineral, liberating Mg2+ cations which react with the bicarbonate to form the solid carbonate. The process is designed to simulate the natural serpentinization reaction of ultramafic minerals, and for this reason, these results may also be applicable to in-situ geological sequestration regimes. Results of the baseline tests, conducted on ground products of the natural minerals, have been encouraging. Tests conducted at ambient temperature (22 C) and subcritical CO2 pressures (below 73 atm) resulted in very slow conversion to the carbonate. However, when elevated temperatures and pressures are utilized, coupled with continuous stirring of the slurry and gas dispersion within the water column, significant reaction occurs within much shorter reaction times. Extent of reaction, as measured by the stoichiometric conversion of the silicate mineral (olivine) to the carbonate, is roughly 90% within 24 hours, using distilled water, and a reaction temperature of 185?C and a partial pressure of CO2 (PCO2) of 115 atm. Recent tests using a bicarbonate solution, under identical reaction

Carbon dioxide sequestration by direct mineral carbonation with carbonic acid

Energy Technology Data Exchange (ETDEWEB)

O' Connor, W.K.; Dahlin, D.C.; Nilsen, D.N.; Walters, R.P.; Turner, P.C.

2000-07-01

The Albany Research Center (ARC) of the US Department of Energy (DOE) has been conducting a series of mineral carbonation tests at its Albany, Oregon, facility over the past 2 years as part of a Mineral Carbonation Study Program within the DOE. The ARC tests have focused on ex-situ mineral carbonation in an aqueous system. The process developed at ARC utilizes a slurry of water mixed with a magnesium silicate mineral, olivine [forsterite and member (mg{sub 2}SiO{sub 4})], or serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}]. This slurry is reacted with supercritical carbon dioxide (CO{sub 2}) to produce magnesite (MgCO{sub 3}). The CO{sub 2} is dissolved in water to form carbonic acid (H{sub 2}CO{sub 3}), which dissociates to H{sup +} and HCO{sub 3}{sup {minus}}. The H{sup +} reacts with the mineral, liberating Mg{sup 2+} cations which react with the bicarbonate to form the solid carbonate. The process is designed to simulate the natural serpentinization reaction of ultramafic minerals, and for this reason, these results may also be applicable to in-situ geological sequestration regimes. Results of the baseline tests, conducted on ground products of the natural minerals, have been encouraging. Tests conducted at ambient temperature (22 C) and subcritical CO{sub 2} pressures (below 73 atm) resulted in very slow conversion to the carbonate. However, when elevated temperatures and pressures are utilized, coupled with continuous stirring of the slurry and gas dispersion within the water column, significant reaction occurs within much shorter reaction times. Extent of reaction, as measured by the stoichiometric conversion of the silicate mineral (olivine) to the carbonate, is roughly 90% within 24 hours, using distilled water, and a reaction temperature of 185 C and a partial pressure of CO{sub 2} (P{sub CO{sub 2}}) of 115 atm. Recent tests using a bicarbonate solution, under identical reaction conditions, have achieved roughly 83% conversion of heat treated serpentine

Fe-Ca-phosphate, Fe-silicate, and Mn-oxide minerals in concretions from the Monterey Formation

Science.gov (United States)

Medrano, M.D.; Piper, D.Z.

1997-01-01

Concentrically zoned phosphatic-enriched concretions were collected at three sites from the Monterey Formation. The following minerals were identified: vivianite, lipscombite, rockbridgeite, leucophosphite, mitridatite, carbonate fluorapatite, nontronite, todorokite, and barite. The mineralogy of the concretions was slightly different at each of the three collection sites. None of the concretions contains all of the minerals, but the spatial distribution of minerals in individual concretions, overlapping mineralogies between different concretions, and the geochemical properties of the separate minerals suggest a paragenesis represented by the above order. Eh increased from the precipitation of vivianite to that of rockbridgeite/lipscombite. The precipitation of leucophosphite, then mitridatite, carbonate fluorapatite and todorokite/Fe-oxide indicates increasing pH. Concretion growth culminated with the precipitation of todorokite, a Mn oxide, and minor amounts of barite along microfractures. Conspicuously absent are Fe-sulfide and Mn-phosphate minerals. The concretions are hosted by finely laminated diatomite. The laminations exhibit little to no deformation around the concretions, requiring that the concretions formed after compaction. We interpret this sediment feature and the paragenesis as recording the evolving pore-water chemistry as the formation was uplifted into the fresh-ground-water zone.

A method for permanent CO2 mineral carbonation

Energy Technology Data Exchange (ETDEWEB)

Dahlin, David C.; O' Connor, William K.; Nilsen, David N.; Rush, G.E.; Walters, Richard P.; Turner, Paul C.

2000-01-01

The Albany Research Center (ARC) of the U.S. Department of Energy (DOE) has been conducting research to investigate the feasibility of mineral carbonation as a method for carbon dioxide (CO2) sequestration. The research is part of a Mineral Carbonation Study Program within the Office of Fossil Energy in DOE. Other participants in this Program include DOE?s Los Alamos National Laboratory and National Energy Technology Laboratory, Arizona State University, and Science Applications International Corporation. The research has focused on ex-situ mineral carbonation in an aqueous system. The process developed at ARC reacts a slurry of magnesium silicate mineral with supercritical CO2 to produce a solid magnesium carbonate product. To date, olivine and serpentine have been used as the mineral reactant, but other magnesium silicates could be used as well. The process is designed to simulate the natural serpentinization reaction of ultramafic minerals, and consequently, these results may also be applicable to strategies for in-situ geological sequestration. Baseline tests were begun in distilled water on ground products of foundry-grade olivine. Tests conducted at 150 C and subcritical CO2 pressures (50 atm) resulted in very slow conversion to carbonate. Increasing the partial pressure of CO2 to supercritical (>73 atm) conditions, coupled with agitation of the slurry and gas dispersion within the water column, resulted in significant improvement in the extent of reaction in much shorter reaction times. A change from distilled water to a bicarbonate/salt solution further improved the rate and extent of reaction. When serpentine, a hydrated mineral, was used instead of olivine, extent of reaction was poor until heat treatment was included prior to the carbonation reaction. Removal of the chemically bound water resulted in conversion to carbonate similar to those obtained with olivine. Recent results have shown that conversions of nearly 80 pct are achievable after 30 minutes

Selective precipitation reaction: a novel diagnostic test for tissue pathology in Atlantic salmon, Salmo salar, infected with salmonid alphavirus (SAV3).

Science.gov (United States)

Braceland, M; Tinsley, J; Cockerill, D; Bickerdike, R; McLoughlin, M F; Eckersall, P D

2017-08-01

While investigating biomarkers for infection with salmonid alphavirus (SAV), the cause of pancreas disease (PD), a selective precipitation reaction (SPR) has been discovered in serum which could be an on-farm qualitative test and an in-laboratory quantitative assay for health assessments in aquaculture. Mixing serum from Atlantic salmon, Salmo salar, with SAV infection with a sodium acetate buffer caused a visible precipitation which does not occur with serum from healthy salmon. Proteomic examination of the precipitate has revealed that the components are a mix of muscle proteins, for example enolase and aldolase, along with serum protein such as serotransferrin and complement C9. The assay has been optimized for molarity, pH, temperature and wavelength so that the precipitation can be measured as the change in optical density at 340 nm (Δ 340 ). Application of the SPR assay to serum samples from a cohabitation trial of SAV infection in salmon showed that the Δ 340 in infected fish rose from undetectable to a maximum at 6 weeks post-infection correlating with histopathological score of pancreas, heart and muscle damage. This test may have a valuable role to play in the diagnostic evaluation of stock health in salmon. © 2016 The Authors. Journal of Fish Diseases Published by John Wiley & Sons Ltd.

Encoding information into precipitation structures

International Nuclear Information System (INIS)

Martens, Kirsten; Bena, Ioana; Droz, Michel; Rácz, Zoltan

2008-01-01

Material design at submicron scales would be profoundly affected if the formation of precipitation patterns could be easily controlled. It would allow the direct building of bulk structures, in contrast to traditional techniques which consist of removing material in order to create patterns. Here, we discuss an extension of our recent proposal of using electrical currents to control precipitation bands which emerge in the wake of reaction fronts in A + + B – → C reaction–diffusion processes. Our main result, based on simulating the reaction–diffusion–precipitation equations, is that the dynamics of the charged agents can be guided by an appropriately designed time-dependent electric current so that, in addition to the control of the band spacing, the width of the precipitation bands can also be tuned. This makes straightforward the encoding of information into precipitation patterns and, as an amusing example, we demonstrate the feasibility by showing how to encode a musical rhythm

Precipitation of hydrated Mg carbonate with the aid of carbonic anhydrase for CO2 sequestration

Science.gov (United States)

Power, I. M.; Harrison, A. L.; Dipple, G. M.

2011-12-01

Strategies for sequestering CO2 directly from the atmosphere are likely required to achieve the desired reduction in CO2 concentration and avoid the most damaging effects of climate change [1]. Numerous studies have demonstrated the accelerated precipitation of calcium carbonate minerals with the aid of carbonic anhydrase (CA) as a means of sequestering CO2 in solid carbonate form; however, no study has examined precipitation of magnesium carbonate minerals using CA. Precipitation of magnesite (MgCO3) is kinetically inhibited [2]; therefore, Mg2+ must be precipitated as hydrated carbonate minerals. In laboratory experiments, the uptake of atmospheric CO2 into brine solutions (0.1 M Mg) was rate-limiting for the precipitation of dypingite [Mg5(CO3)4(OH)2-5H2O] with initial precipitation requiring 15 days [3]. It was also found that dypingite precipitation outpaced the uptake of CO2 gas into solution. CO2 uptake is limited by the hydration of CO2 to form carbonate ions [4]. Carbonic anhydrase (CA) enzymes are among the fastest known in nature and are able to catalyze the hydration of CO2, i.e., converting CO2(aq) to CO32- and HCO3- [5]. CA plays an important role in the carbon concentrating mechanism of photoautotrophic, chemoautotrophic, and heterotrophic prokaryotes and is involved in pH homeostasis, facilitated diffusion of CO2, ion transport, and the interconversion of CO2 and HCO3- [6]. Introducing CA into buffered Mg-rich solutions should allow for more rapid precipitation of hydrated magnesium carbonate minerals. Batch experiments were conducted using 125 mL flasks containing 100 mL of Millipore deionized water with 0.2 M of MgCl2-6H2O. To buffer pH, 1.0 g of pulverized brucite [Mg(OH)2] or 1.0 g of NaOH was added to the systems, which were amended with Bovine carbonic anhydrase (BCA) (Sigma-Aldrich). Solutions were stirred continuously and kept at room temperature (~22°C) with laboratory air introduced by bubbling. Temperature and pH were measured routinely

Method for strontium isolation from high-mineralized water

International Nuclear Information System (INIS)

Evzhanov, Kh.; Andriyasova, G.M.

1983-01-01

A method to isolate strontium from high-mineralized waters containing sodium, magnesium, calcium and strontium chlorides, which differ from the prototype method in a considerable decrease in energy consumption with the preservation of a high degree of Sr, Mg and Ca isolation selectivity, has been suggested. According to the method suggested mineralized waters are treated with alkali (NaOH) in the amount of 95-97% of stoichiometry by magnesium, then after separation of magnesium hydroxide precipitate mother liquor is treated with sodium carbonate in the amount of 50-60% of stoichiometry by calcium. After separation of calcium carbonate precipitate mother liquor is treated with NaOH in the amount of 130-135% of stoichiometry by calcium. After separation of calcium hydroxide precipitate from mother liquor by means of sodium carbonate introduction strontium carbonate is isolated. The degree of strontium extraction in the form of SrCO 3 constitutes 90.5% of its content in the initial solution. The method presented can be used for strontium separation from natural and waste waters

Technetium behavior in sulfide and ferrous iron solutions

International Nuclear Information System (INIS)

Lee, S.Y.; Bondietti, E.A.

1982-01-01

Pertechnetate oxyanion ( 99 TcO 4- ), a potentially mobile species in leachate from a breached radioactive waste repository, was removed from a brine solution by precipitation with sulfide, iron, and ferrous sulfide at environmental pH's. Maghemite (ν-Fe 2 O 3 ) and geothite (α-FeOOH) were the dominant minerals in the precipitate obtained from the TcO 4- -ferrous iron reaction. The observation of small particle size and poor crystallinity of the minerals formed in the presence of Tc suggested that the Tc was incorporated into the mineral structure after reduction to a lower valence state. Amorphous ferrous sulfide, an initial phase precipitating in the TcO 4- -ferrous iron-sulfide reaction, was transformed to goethite and hematite (α-Fe 2 O 3 ) on aging. The black precipitate obtained from the TcO 4- -sulfide reaction was poorly crystallized technetium sulfide (Tc 2 S 7 ) which was insoluble in both acid and alkaline solution in the absence of strong oxidents. The results suggested that ferrous- and/or sulfide-bearing groundwaters and minerals in host rocks or backfill barriers could reduce the mobility of Tc through the formation of less-soluble Tc-bearing iron and/or sulfide minerals

Precipitation of iron in windopane oyster shells by marine shell-boring cyanobacteria

Digital Repository Service at National Institute of Oceanography (India)

Raghukumar, C.; Rao, V.P.; Iyer, S.D.

filaments encrusted with black precipitate. Microchemical test (Prussian blue reaction) and wavelength dispersive x-ray analysis confirmed this precipitate to be of iron. Mineralogical studies of this black precipitate, using x-ray diffraction and scanning...

Experimental Precipitation of Carbonate Minerals: Effect of pH, Supersaturation and Substrate

OpenAIRE

Tetteh, Abednego

2012-01-01

Understanding the controlling factors and elucidating the requirements and conditions necessary for carbon dioxide (CO2) storage by mineral trapping (or carbonation) is of paramount interest for any technical application as a means for carbon dioxide capture and storage (CCS). The effect of pH, supersaturation and substrate has been studied using non-stirred batch reactors at initial constant temperature of 150 oC. These conditions are relevant for mineral trapping. A set of experiments was c...

Combining water-rock interaction experiments with reaction path and reactive transport modelling to predict reservoir rock evolution in an enhanced geothermal system

Science.gov (United States)

Kuesters, Tim; Mueller, Thomas; Renner, Joerg

2016-04-01

Reliably predicting the evolution of mechanical and chemical properties of reservoir rocks is crucial for efficient exploitation of enhanced geothermal systems (EGS). For example, dissolution and precipitation of individual rock forming minerals often result in significant volume changes, affecting the hydraulic rock properties and chemical composition of fluid and solid phases. Reactive transport models are typically used to evaluate and predict the effect of the internal feedback of these processes. However, a quantitative evaluation of chemo-mechanical interaction in polycrystalline environments is elusive due to poorly constrained kinetic data of complex mineral reactions. In addition, experimentally derived reaction rates are generally faster than reaction rates determined from natural systems, likely a consequence of the experimental design: a) determining the rate of a single process only, e.g. the dissolution of a mineral, and b) using powdered sample materials and thus providing an unrealistically high reaction surface and at the same time eliminating the restrictions on element transport faced in-situ for fairly dense rocks. In reality, multiple reactions are coupled during the alteration of a polymineralic rocks in the presence of a fluid and the rate determining process of the overall reactions is often difficult to identify. We present results of bulk rock-water interaction experiments quantifying alteration reactions between pure water and a granodiorite sample. The rock sample was chosen for its homogenous texture, small and uniform grain size (˜0.5 mm in diameter), and absence of pre-existing alteration features. The primary minerals are plagioclase (plg - 58 vol.%), quartz (qtz - 21 vol.%), K-feldspar (Kfs - 17 vol.%), biotite (bio - 3 vol.%) and white mica (wm - 1 vol.%). Three sets of batch experiments were conducted at 200 ° C to evaluate the effect of reactive surface area and different fluid path ways using (I) powders of the bulk rock with

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

The effect of precipitation on contaminant dissolution and transport: Analytic solutions

International Nuclear Information System (INIS)

Light, W.B.; Chambre, P.L.; Pigford, T.H.; Lee, W.W.L.

1988-09-01

We analysed the effect of precipitation on the dissolution and transport rates of a nondecaying contaminant. Precipitation near the waste surface can have a profound effect on dissolution and transport rates. The mass-transfer rate at the waste surface is controlled by the solid-liquid reaction rate to an extent determined by the modified reaction-rate modulus, α. At later times extending to steady state, the mass-transfer rate depends on the location of the precipitation front r/sub p/ and on the solubility ratio C/sub o//C/sub p/. A precipitation front very near the waste surface can change the dissolution mechanism from solubility-diffusion-controlled to chemical-reaction-rate controlled. Precipitation limits the concentration of the contaminant at r > r/sub p/ to C/sub p/, steepening the concentration gradient for dissolution on the waste package side of the front and flattening the gradient for transport in the region outside the front. This increases the rate of contaminant transport from the waste to the front while decreasing the rate of transport away from the front, when compared to the situation without precipitation. The difference in the transport rates at the front is the rate of precipitation. For large changes in solubility, most of the contaminant is immobilized by precipitation, as was observed in a parallel study. The effect of a precipitation front located nearby in surrounding rock is to increase the release rate at the waste surface/rock interface. The increase in release rate at the waste surface is greater the closer the precipitation and the larger the ratio C/sub o//C/sub p/, also observed by others. The release rates of other waste constituents that dissolve congruently with the solubility-controlling matrix can be increased by a local high-solubility region between the waste surface and the precipitation front. 10 refs., 5 figs

Effect of pH change on the primary uran-mica mineralization

Energy Technology Data Exchange (ETDEWEB)

Shmariovich, E M; Zhil' tsova, I G; Pakul' nis, G V; Shugina, G A [Ministerstvo Geologii SSR, Moscow

1982-01-01

Conditions of the formation of ore bodies of hexavalent uranium minerals represented by uranyl vanadates and phosphates which are primary and sedimented from low temperature solutions (carnotite deposits in calcretes and carnotite - autunite deposits in black shale formations) are considered. Thermodynamic curves of the solubility dependence of various uranyl minerals on pH medium in the absence of SO/sub 4//sup 2 -/ and CO/sub 3//sup 2 -/ ions and for sulphate-carbonate solutions have been calculated using dissociation constants of corresponding acids and ..delta..G/sup 0/f(298.15) values. It has been ascertained that uranyl mineral compounds according to the dependence of their solubility on ph medium form a distinct series from molybdates through arsenates, phosphates, vanadates and silicates to minerals of uranophane and kasolite group. It is shown that during the formation of infiltration deposits with uranyl mineralization a decisive role is played by the contrast change of pH value of medium caused by the presence of acid geochemical barrier (uranyl molybdates, arsenates, phosphates and vanadates are precipitating) or neutralizing alkaline barriers (uran-mica and uranyl silicates are precipitating) on the path of movement of oxygen metal-bearing solutions.

Mathematical modeling and simulation of nanopore blocking by precipitation

KAUST Repository

Wolfram, M-T

2010-10-29

High surface charges of polymer pore walls and applied electric fields can lead to the formation and subsequent dissolution of precipitates in nanopores. These precipitates block the pore, leading to current fluctuations. We present an extended Poisson-Nernst-Planck system which includes chemical reactions of precipitation and dissolution. We discuss the mathematical modeling and present 2D numerical simulations. © 2010 IOP Publishing Ltd.

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle, USA

Science.gov (United States)

Ranalli, Anthony J.; Yager, Douglas B.

2016-01-01

This study investigated the potential for the uranium mineral carnotite (K2(UO2)2(VO4)2·3H2O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO2. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO4 + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and  mHCO3− + 2mCO3−2) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO3 + CO3) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa+2 < mHCO3- + 2mCO3−2) carnotite saturation was not achieved. In systems open to CO2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO2 ranging from 10−3.5 to 10−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO2 equal to 10−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed

Carbonate Precipitates During Heat Evolution in FP-Type Cells

International Nuclear Information System (INIS)

Bruce L. Cain

2000-01-01

In previous work, we reported measurement of large amounts of heat generated during experiments using an FP-type open cell with concentrated LiOH/D 2 O electrolytes and thin-film Pd cathodes. During the heat evolution in several runs, which produced >100 W for more than 20 h, we consistently observed the concomitant evolution of gases from the electrolyte and the precipitation of large amounts of lithium carbonate. The carbonate production was clearly visible during production of heat, creating an opaque electrolyte even during long periods with no electrolysis current. These results indicated an unusual chemical reaction, either catalyzed by the heating process or possibly creating the heat itself. The total energy released during the earlier experiments was ∼7 MJ, while the heat of formation for the lithium carbonate in the cell was only 0.8 MJ. Hence, only ∼10% of the heat signatures from these experiments can be attributed to the precipitate formation, the balance of the heat presumably arising from nonchemical sources in the cells. The earlier experiments that produced heat also suffered from problems of reproducibility, with only 5 of 38 runs producing any heat at all. The unsuccessful runs also did not produce precipitates, and the only gas produced in these cells was due to the normal electrolysis of D 2 O to produce oxygen and deuterium in the electrodes. Recent work has focused on recreating the chemical precipitation reaction, in efforts to understand and/or trigger the heat production process. With findings from these experiments, new experiments were conducted using larger (1 L LiOH/D 2 O) cells with Pt anodes and Pd film cathodes immersed but left open-circuited. After the addition of H 2 O 2 , and subsequent heating and cooling, these cells visually reproduced the precipitation and gas evolution of the earlier heat-producing runs. However, these new runs only produced a few watts of power for several minutes, consistent with the normal exothermal

Variations in soil carbon sequestration and their determinants along a precipitation gradient in seasonally dry tropical forest ecosystems.

Science.gov (United States)

Campo, Julio; Merino, Agustín

2016-05-01

The effect of precipitation regime on the C cycle of tropical forests is poorly understood, despite the existence of models that suggest a drier climate may substantially alter the source-sink function of these ecosystems. Along a precipitation regime gradient containing 12 mature seasonally dry tropical forests growing under otherwise similar conditions (similar annual temperature, rainfall seasonality, and geological substrate), we analyzed the influence of variation in annual precipitation (1240 to 642 mm) and duration of seasonal drought on soil C. We investigated litterfall, decomposition in the forest floor, and C storage in the mineral soil, and analyzed the dependence of these processes and pools on precipitation. Litterfall decreased slightly - about 10% - from stands with 1240 mm yr(-1) to those with 642 mm yr(-1), while the decomposition decreased by 56%. Reduced precipitation strongly affected C storage and basal respiration in the mineral soil. Higher soil C storage at the drier sites was also related to the higher chemical recalcitrance of litter (fine roots and forest floor) and the presence of charcoal across sites, suggesting an important indirect influence of climate on C sequestration. Basal respiration was controlled by the amount of recalcitrant organic matter in the mineral soil. We conclude that in these forest ecosystems, the long-term consequences of decreased precipitation would be an increase in organic layer and mineral soil C storage, mainly due to lower decomposition and higher chemical recalcitrance of organic matter, resulting from changes in litter composition and, likely also, wildfire patterns. This could turn these seasonally dry tropical forests into significant soil C sinks under the predicted longer drought periods if primary productivity is maintained. © 2016 John Wiley & Sons Ltd.

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Energy Technology Data Exchange (ETDEWEB)

Wu, Y.; Ajo-Franklin, J.B.; Spycher, N.; Hubbard, S.S.; Zhang, G.; Williams, K.H.; Taylor, J.; Fujita, Y.; Smith, R.

2011-07-15

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH{sub 4}{sup

Study of calcium carbonate and sulfate co-precipitation

KAUST Repository

Zarga, Y.

2013-06-01

Co-precipitation of mineral based salts in scaling is still not well understood and/or thermodynamically well defined in the water industry. This study focuses on investigating calcium carbonate (CaCO3) and sulfate mixed precipitation in scaling which is commonly observed in industrial water treatment processes including seawater desalination either by thermal-based or membrane-based processes. Co-precipitation kinetics were studied carefully by monitoring several parameters simultaneously measured, including: pH, calcium and alkalinity concentrations as well as quartz microbalance responses. The CaCO3 germination in mixed precipitation was found to be different than that of simple precipitation. Indeed, the co-precipitation of CaCO3 germination time was not anymore related to supersaturation as in a simple homogenous precipitation, but was significantly reduced when the gypsum crystals appeared first. On the other hand, the calcium sulfate crystals appear to reduce the energetic barrier of CaCO3 nucleation and lead to its precipitation by activating heterogeneous germination. However, the presence of CaCO3 crystals does not seem to have any significant effect on gypsum precipitation. IR spectroscopy and the Scanning Electronic Microscopy (SEM) were used to identify the nature of scales structures. Gypsum was found to be the dominant precipitate while calcite and especially vaterite were found at lower proportions. These analyses showed also that gypsum crystals promote calcite crystallization to the detriment of other forms. © 2013 Elsevier Ltd.

Use of linear regression for the processing of curves of differential potentiometric titration of a binary mixture of heterovalent ions using precipitation reactions

International Nuclear Information System (INIS)

Mar'yanov, B.M.; Zarubin, A.G.; Shumar, S.V.

2003-01-01

A method is proposed for the computer processing of curve of differential potentiometric titration of a binary mixture of heterovalent ions using precipitation reactions. The method is based on the transformation of the titration curve to segment-line characteristics, whose parameters (within the accuracy of the least-squares method) determine the sequence of the equivalence points and solubility products of the resulting precipitation. The method is applied to the titration of Ag(I)-Cd)II), Hg(II)-Te(IV), and Cd(II)-Te(IV) mixtures by a sodium diethyldithiocarbamate solution with membrane sulfide and glassy carbon indicator electrodes. For 4 to 11 mg of the analyte in 50 ml of the solution, RSD varies from 1 to 9% [ru

Pyrophosphate synthesis in iron mineral films and membranes simulating prebiotic submarine hydrothermal precipitates

Science.gov (United States)

Barge, Laura M.; Doloboff, Ivria J.; Russell, Michael J.; VanderVelde, David; White, Lauren M.; Stucky, Galen D.; Baum, Marc M.; Zeytounian, John; Kidd, Richard; Kanik, Isik

2014-03-01

Cells use three main ways of generating energy currency to drive metabolism: (i) conversion of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) by the proton motive force through the rotor-stator ATP synthase; (ii) the synthesis of inorganic phosphate˜phosphate bonds via proton (or sodium) pyrophosphate synthase; or (iii) substrate-level phosphorylation through the direct donation from an active phosphoryl donor. A mechanism to produce a pyrophosphate bond as “energy currency” in prebiotic systems is one of the most important considerations for origin of life research. Baltscheffsky (1996) suggests that inorganic pyrophosphate (PO74-; PPi) may have preceded ATP/ADP as an energy storage molecule in earliest life, produced by an H+ pyrophosphatase. Here we test the hypothesis that PPi could be synthesized in inorganic precipitates simulating hydrothermal chimney structures transected by thermal and/or ionic gradients. Appreciable yields of PPi were obtained via substrate phosphorylation by acetyl phosphate within the iron sulfide/silicate precipitates at temperatures expected for an alkaline hydrothermal system. The formation of PPi only occurred in the solid phase, i.e. when both Pi and the phosphoryl donor were precipitated with Fe-sulfides or Fe-silicates. The amount of Ac-Pi incorporated into the precipitate was a significant factor in the amount of PPi that could form, and phosphate species were more effectively incorporated into the precipitate at higher temperatures (⩾50 to >85 °C). Thus, we expect that the hydrothermal precipitate would be more enriched in phosphate (and especially, Ac-Pi) near the inner margins of a hydrothermal mound where PPi formation would be at a maximum. Iron sulfide and iron silicate precipitates effectively stabilized Ac-Pi and PPi against hydrolysis (relative to hydrolysis in aqueous solution). Thus it is plausible that PPi could accumulate as an energy currency up to useful concentrations for early life in a

Precipitation process for supernate decontamination

International Nuclear Information System (INIS)

Lee, L.M.; Kilpatrick, L.L.

1982-11-01

A precipitation and adsorption process has been developed to remove cesium, strontium, and plutonium from water-soluble, high-level radioactive waste. An existing waste tank serves as the reaction vessel and the process begins with the addition of a solution of sodium tetraphenylborate and a slurry of sodium titanate to the contained waste salt solution. Sodium tetraphenylborate precipitates the cesium and sodium titanate adsorbs the strontium and plutonium. The precipitate/adsorbate is then separated from the decontaminated salt solution by crossflow filtration. This new process offers significant capital savings over an earlier ion exchange process for salt decontamination. Chemical and small-scale engineering studies with actual waste are reported. The effect of many variables on the decontamination factors and filter performance are defined

Mineralization of Carbon Dioxide: Literature Review

Energy Technology Data Exchange (ETDEWEB)

Romanov, V; Soong, Y; Carney, C; Rush, G; Nielsen, B; O' Connor, W

2015-01-01

CCS research has been focused on CO2 storage in geologic formations, with many potential risks. An alternative to conventional geologic storage is carbon mineralization, where CO2 is reacted with metal cations to form carbonate minerals. Mineralization methods can be broadly divided into two categories: in situ and ex situ. In situ mineralization, or mineral trapping, is a component of underground geologic sequestration, in which a portion of the injected CO2 reacts with alkaline rock present in the target formation to form solid carbonate species. In ex situ mineralization, the carbonation reaction occurs above ground, within a separate reactor or industrial process. This literature review is meant to provide an update on the current status of research on CO2 mineralization. 2

The utilization of waste by-products for removing silicate from mineral processing wastewater via chemical precipitation.

Science.gov (United States)

Kang, Jianhua; Sun, Wei; Hu, Yuehua; Gao, Zhiyong; Liu, Runqing; Zhang, Qingpeng; Liu, Hang; Meng, Xiangsong

2017-11-15

This study investigates an environmentally friendly technology that utilizes waste by-products (waste acid and waste alkali liquids) to treat mineral processing wastewater. Chemical precipitation is used to remove silicate from scheelite (CaWO 4 ) cleaning flotation wastewater and the waste by-products are used as a substitute for calcium chloride (CaCl 2 ). A series of laboratory experiments is conducted to explain the removal of silicate and the characterization and formation mechanism of calcium silicate. The results show that silicate removal reaches 90% when the Ca:Si molar ratio exceeds 1.0. The X-ray diffraction (XRD) results confirm the characterization and formation of calcium silicate. The pH is the key factor for silicate removal, and the formation of polysilicic acid with a reduction of pH can effectively improve the silicate removal and reduce the usage of calcium. The economic analysis shows that the treatment costs with waste acid (0.63 $/m 3 ) and waste alkali (1.54 $/m 3 ) are lower than that of calcium chloride (2.38 $/m 3 ). The efficient removal of silicate is confirmed by industrial testing at a plant. The results show that silicate removal reaches 85% in the recycled water from tailings dam. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effects of secondary mineral precipitates on {sup 90}Sr mobility at the Hanford Site, USA

Energy Technology Data Exchange (ETDEWEB)

Um, Wooyong [Pacific Northwest National Laboratory, 902 Battelle Blvd., MSIN P7-54, Richland, WA 99354 (United States); Division of Advanced Nuclear Engineering, Pohang University of Science and Technology - POSTECH (Korea, Republic of); Wang, Guohui; Serne, R. Jeffrey [Pacific Northwest National Laboratory, 902 Battelle Blvd., MSIN P7-54, Richland, WA 99354 (United States)

2013-07-01

The effects of secondary precipitates on {sup 90}Sr transport at the Hanford Site were investigated using quartz column experiments with simulated caustic tank waste leachates (STWL). Significantly enhanced retardation of Sr transport was observed in the column contacted with STWL due to Sr sorption and co-precipitation with neo-formed nitrate cancrinite. However, the column results also suggest that neo-formed secondary precipitates could behave like native mobile colloids that can enhance Sr transport. Initially immobilized Sr within secondary precipitates could re-mobilize given a change in the pore water background conditions. The mobility of the neo-formed Sr-bearing precipitates increased with increased solution flow rate. In the field, pore water contents and flow rates can be changed by snow-melt (or storm water) events or artificial infiltration. The increased pore water flow rate caused by these events could affect the mobility of {sup 90}Sr-containing secondary precipitates, which can be a potential source for facilitated Sr transport in Hanford Site subsurface environments. (authors)

From bulk soil to intracrystalline investigation of plant-mineral interaction

Science.gov (United States)

Lemarchand, D.; Voinot, A.; Chabaux, F.; Turpault, M.

2011-12-01

Understanding the controls and feedbacks regulating the flux of matter between bio-geochemical reservoirs in forest ecosystems receives a fast growing interest for the last decades. A complex question is to understand how minerals and vegetation interact in soils to sustain life and, to a broader scope, how forest ecosystems may respond to human activity (acid rain, harvesting,...) and climate perturbations (temperature, precipitation,...). Many mineralogical and biogeochemical approaches have longtime been developed, and occasionally coupled, in order to investigate the mechanisms by which chemical elements either are exchanged between soil particles and solutions, or are transferred to plants or to deeper soil layers and finally leave the system. But the characterization of particular processes like the contribution of minor reactive minerals to plant nutrition and global fluxes or the mechanisms by which biology can modify reaction rates and balance the bioavailability of nutrients in response to environmental perturbation sometimes fails because of the lack of suitable tracers. Recent analytical and conceptual advances have opened new perspectives for the use of light "non traditional" stable isotopes. Showing a wild range of concentrations and isotopic compositions between biogeochemical reservoirs in forest ecosystem, boron has physico-chemical properties particularly relevant to the investigation of water/rock interactions even when evolving biologically-mediated reactions. In this study, we focused on the distribution of boron isotopes from intracrystalline to bulk soil scales. An overview of the boron distribution and annual fluxes in the soil-plant system clearly indicates that the vegetation cycling largely controls the mobility of boron. We also observe that the mineral and biological B pools have drastically different isotopic signature that makes the transfer of B between them very easy to follow. In particular, the podzol soil we analyzed shows a

The Relationships Between Insoluble Precipitation Residues, Clouds, and Precipitation Over California's Southern Sierra Nevada During Winter Storms

Science.gov (United States)

Creamean, Jessie M.; White, Allen B.; Minnis, Patrick; Palikonda, Rabindra; Spangenberg, Douglas A.; Prather, Kimberly A.

2016-01-01

Ice formation in orographic mixed-phase clouds can enhance precipitation and depends on the type of aerosols that serve as ice nucleating particles (INP). The resulting precipitation from these clouds is a viable source of water, especially for regions such as the California Sierra Nevada. Thus, a better understanding of the sources of INP that impact orographic clouds is important for assessing water availability in California. This study presents a multi-site, multi-year analysis of single particle insoluble residues in precipitation samples that likely influenced cloud ice and precipitation formation above Yosemite National Park. Dust and biological particles represented the dominant fraction of the residues (64% on average). Cloud glaciation, determined using GOES satellite observations, not only depended on high cloud tops (greater than 6.2 km) and low temperatures (less than -26 C), but also on the composition of the dust and biological residues. The greatest prevalence of ice-phase clouds occurred in conjunction with biologically-rich residues and mineral dust rich in calcium, followed by iron and aluminosilicates. Dust and biological particles are known to be efficient INP, thus these residues are what likely influenced ice formation in clouds above the sites and subsequent precipitation quantities reaching the surface during events with similar meteorology. The goal of this study is to use precipitation chemistry information to gain a better understanding of the potential sources of INP in the south-central Sierra Nevada, where cloud-aerosol-precipitation interactions are under-studied and where mixed-phase orographic clouds represent a key element in the generation of precipitation and thus the water supply in California.

Comparison of three mineral candidates in middle and low-pressure condition. Experimental study

Energy Technology Data Exchange (ETDEWEB)

Yan, Heng; Zhang, Jun-ying; Zhao, Yong-chun; Wang, Zhi-lang; Pan, Xia; Xu, Jun; Zheng, Chu-guang [Huazhong Univ. of Science and Technology, Wuhan (China). State Key Lab. of Coal Combustion

2013-07-01

''Greenhouse Effect'', which is scientifically proven to be main caused by the increasing concentration of CO{sub 2}, has become a topic of national and international concern. Mineral carbonation, such as carbonation of alkaline silicate Ca/Mg minerals, analogous to natural weathering processes, is a potentially attractive route to mitigate possible global warming on the basis of industrial imitation of natural weathering processes. In this paper, three typical natural mineral candidates in China, serpentine, olivine and wollastonite, were selected as carbonation raw materials for direct mineral carbonation experiments under middle and low-pressure. A series number of experiments were carried out to investigate the factors that influence the conversion of carbonation reaction, such as reaction temperature, reaction pressure, particle size, solution composition and pretreatment. The solid products from carbonation experiments were filtered, collected, dried and analyzed by X-ray diffraction (XRD) and field scanning electron microscopy equipped with energy dispersive X-ray analysis (FSEM-EDX) to identify the reaction of mineral carbonation. And the method of mass equilibrium after heat decomposition was used to calculate the mineral carbonation conversion. All the XRD and FSEM analysis validate that carbonation reaction was occurred during the experiments and mineral carbonation is one of the potential techniques for carbon dioxide sequestration. The data of mass equilibrium after heat decomposition was collected and then the conversion formula was used to calculate the carbonation conversion of all the three mineral candidates. The mass equilibrium results show that, for all of the three mineral materials, the carbonation conversion increases with the increasing of reaction temperature. But once the temperature increases above 150 C, the conversion of serpentine decreases a little. Reaction pressure is also an important factor to mineral

Phosphate adsorption and precipitation on calcite under calco-carbonic equilibrium condition.

Science.gov (United States)

Li, Zhenxuan; Sun, Xiaowen; Huang, Lidong; Liu, Dagang; Yu, Luji; Wu, Hongsheng; Wei, Dongyang

2017-09-01

Phosphate (PO 4 3- ) removal on calcite often entails two processes: adsorption and precipitation. Separating these two processes is of great importance for assessment of PO 4 3- stability after removal. Thus, this study was aimed at finding a critical range of conditions for separating these two processes in calco-carbonic equilibrium, by adjusting PO 4 3- concentration, reaction time and pH. PO 4 3- removal kinetic results showed that: (I) At pH7.7, PO 4 3- removal was mainly by adsorption at initial PO 4 3- concentration ≤2.2 mg L -1 and reaction time ≤24 h, with dominant precipitation occurring at initial PO 4 3- concentration ≥3 mg L -1 after 24 h reaction; (II) At pH8.3, adsorption was the key removal process at initial PO 4 3- concentration ≤7.5 mg L -1 and reaction time ≤24 h, whereas precipitation was observed at initial PO 4 3- concentration of 10 mg L -1 after 24 h reaction, (III) At pH 9.1 and 10.1, PO 4 3- removal mechanism was mainly by adsorption at initial PO 4 3- concentration ≤10 mg L -1 within 24 h reaction. Based on the kinetic results, it is suggested that PO 4 3- precipitation will occur after 24 h reaction when saturation index of amorphous calcium phosphate is between 1.97 and 2.19. Besides, increasing PO 4 3- concentration does not cause a continuous decline of PO 4 3- removal percentage. Moreover, experimental removal data deviated largely from the theoretical adsorption value by CD-MUSIC model. These indicate occurrence of precipitation which is in agreement with the kinetic result. Therefore our study will provide fundamental reference information for better understanding of phosphorous stabilization after removal by calcite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Precipitation hardening in a 12%Cr-9%Ni-4%Mo-2%Cu stainless steel

International Nuclear Information System (INIS)

Haettestrand, Mats; Nilsson, Jan-Olof; Stiller, Krystyna; Liu Ping; Andersson, Marcus

2004-01-01

A combination of complementary techniques including one-dimensional and three-dimensional atom probe, energy-filtered transmission electron microscopy and conventional transmission electron microscopy has been used to assess the precipitation reactions at 475 deg. C in a 12%Cr-9%Ni-4%Mo-2%Cu precipitation hardening stainless steel. The continuous hardening up to at least 1000 h of ageing was attributed to a sequence of precipitation reactions involving nickel-rich precipitates nucleating at copper clusters followed by molybdenum-rich quasicrystalline precipitates and nickel-rich precipitates of type L1 0 . An estimate of the relative contributions to the strength increment during tempering based on measurements of particle densities was performed. Nickel-rich precipitates were found to play the most important role up to about 40 h of ageing after which the effect of quasicrystalline particles became increasingly important

Magnesium hydroxide extracted from a magnesium-rich mineral for CO2 sequestration in a gas-solid system.

Science.gov (United States)

Lin, Pao-Chung; Huang, Cheng-Wei; Hsiao, Ching-Ta; Teng, Hsisheng

2008-04-15

Magnesium hydroxide extracted from magnesium-bearing minerals is considered a promising agent for binding CO2 as a carbonate mineral in a gas-solid reaction. An efficient extraction route consisting of hydrothermal treatment on serpentine in HCl followed by NaOH titration for Mg(OH)2 precipitation was demonstrated. The extracted Mg(OH)2 powder had a mean crystal domain size as small as 12 nm and an apparent surface area of 54 m2/g. Under one atmosphere of 10 vol% CO2/N2, carbonation of the serpentine-derived Mg(OH)2 to 26% of the stoichiometric limit was achieved at 325 degrees C in 2 h; while carbonation of a commercially available Mg(OH)2, with a mean crystal domain size of 33 nm and an apparent surface area of 3.5 m2/g, reached only 9% of the stoichiometric limit. The amount of CO2 fixation was found to be inversely proportional to the crystal domain size of the Mg(OH)2 specimens. The experimental data strongly suggested that only a monolayer of carbonates was formed on the crystal domain boundary in the gas-solid reaction, with little penetration of the carbonates into the crystal domain.

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump

Energy Technology Data Exchange (ETDEWEB)

Dong, Liang; Xie, Yun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Du, Liang [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); School of Radiation Medicine and Protection (SRMP), School for Radiological and Interdisciplinary Sciences (RAD-X), Suzhou 215000 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Tan, Zhaoyi, E-mail: zhyitan@126.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

2015-04-28

Highlights: • This is the first theoretical investigation about T–H exchange in vacuum oil. • T–H isotope exchange is accomplished through two different change mechanisms. • Isotope exchange is selective, molecules with −OH and −COOH exchange more easily. • The methyl and methylene radicals in waste oil were observed by {sup 1}HNMR. - Abstract: The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium–hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T–H exchange mechanism and the hyrogenation–dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation–dehydrogenation exchange mechanism, the T–H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with −OH and −COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T–H isotope exchange can be determined by the hydrogenation of T{sub 2} or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

Reduction of iron-bearing lunar minerals for the production of oxygen

Science.gov (United States)

Massieon, Charles; Cutler, Andrew; Shadman, Farhang

1992-01-01

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user's guide, and related documentation (Version 7.0)

International Nuclear Information System (INIS)

Wolery, T.J.; Daveler, S.A.

1992-01-01

EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ''single-point'' thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics

Biologically enhanced mineral weathering: what does it look like, can we model it?

Science.gov (United States)

Schulz, M. S.; Lawrence, C. R.; Harden, J. W.; White, A. F.

2011-12-01

The interaction between plants and minerals in soils is hugely important and poorly understood as it relates to the fate of soil carbon. Plant roots, fungi and bacteria inhabit the mineral soil and work symbiotically to extract nutrients, generally through low molecular weight exudates (organic acids, extracelluar polysachrides (EPS), siderophores, etc.). Up to 60% of photosynthetic carbon is allocated below ground as roots and exudates, both being important carbon sources in soils. Some exudates accelerate mineral weathering. To test whether plant exudates are incorporated into poorly crystalline secondary mineral phases during precipitation, we are investigating the biologic-mineral interface. We sampled 5 marine terraces along a soil chronosequence (60 to 225 ka), near Santa Cruz, CA. The effects of the biologic interactions with mineral surfaces were characterized through the use of Scanning Electron Microscopy (SEM). Morphologically, mycorrhizal fungi were observed fully surrounding minerals, fungal hyphae were shown to tunnel into primary silicate minerals and we have observed direct hyphal attachment to mineral surfaces. Fungal tunneling was seen in all 5 soils by SEM. Additionally, specific surface area (using a nitrogen BET method) of primary minerals was measured to determine if the effects of mineral tunneling are quantifiable in older soils. Results suggest that fungal tunneling is more extensive in the primary minerals of older soils. We have also examined the influence of organic acids on primary mineral weathering during soil development using a geochemical reactive transport model (CrunchFlow). Addition of organic acids in our models of soil development at Santa Cruz result in decreased activity of Fe and Al in soil pore water, which subsequently alters the spatial extent of primary mineral weathering and kaolinite precipitation. Overall, our preliminary modeling results suggest biological processes may be an important but underrepresented aspect of

Pore to core scale simulation of the mass transfer with mineral reaction in porous media

International Nuclear Information System (INIS)

Bekri, S.; Renard, S.; Delprat-Jannaud, F.

2015-01-01

Pore Network Model (PNM) is used to simulate mass transfer with mineral reaction in a single phase flow through porous medium which is here a sandstone sample from the reservoir formation of the Pakoslaw gas field. The void space of the porous medium is represented by an idealized geometry of pore-bodies joined by pore-throats. Parameters defining the pore-bodies and the pore-throats distribution are determined by an optimization process aiming to match the experimental Mercury Intrusion Capillary Pressure (MICP) curve and petrophysical properties of the rock such as intrinsic permeability and formation factor. The generated network is used first to simulate the multiphase flow by solving Kirchhoff's laws. The capillary pressure and relative permeability curves are derived. Then, reactive transport is addressed under asymptotic regime where the solute concentration undergoes an exponential evolution with time. The porosity/ permeability relationship and the three phenomenological coefficients of transport, namely the solute velocity, the dispersion and the mean reaction rate are determined as functions of Peclet and Peclet-Damkohler dimensionless numbers. Finally, the role of the dimensionless numbers on the reactive flow properties is highlighted. (authors)

Formation of secondary minerals in a lysimeter approach - A mineral-microbe interaction

Science.gov (United States)

Schäffner, F.; Merten, D.; De Giudici, G.; Beyer, A.; Akob, D. M.; Ricci, P. C.; Küsel, K.; Büchel, G.

2012-04-01

Heavy metal contamination of large areas due to uranium mining operations poses a serious long-term environmental problem. In the Ronneburg district (eastern Thuringia, Germany), leaching of low grade uranium bearing ores (uranium content metals, especially Cd, Ni, Co, Cu and Zn due to a residual contamination even after remediation efforts. To reveal the processes of secondary mineral precipitation in the field a laboratory lysimeter approach was set up under in situ-like conditions. Homogenized soil from the field site and pure quartz sand were used as substrates. In general, in situ measurements of redox potentials in the substrates showed highly oxidizing conditions (200-750 mV). Water was supplied to the lysimeter from below via a mariottés bottle containing contaminated groundwater from the field. Evaporation processes were allowed, providing a continuous flow of water. This led to precipitation of epsomite and probably aplowite on the top layer of substrate, similar to what is observed in field investigations. After 4 weeks, the first iron and manganese bearing secondary minerals became visible. Soil water samples were used to monitor the behaviour of metals within the lysimeter. Saturation indices (SI) for different secondary minerals were calculated with PHREEQC. The SI of goethite showed oversaturation with respect to the soil solution. SEM-EDX analyses and IR spectroscopy confirmed the formation of goethite. Geochemical data revealed that goethite formation was mainly dominated by Eh/pH processes and that heavy metals, e.g. Zn and U, could be enriched in this phase. Although Eh/pH data does not support formation of manganese minerals, Mn(II)-oxidizing bacteria (MOB) could be isolated from field soil samples, supporting the fact that microorganisms may influence this natural attenuation process. Laser ablation ICP-MS data reveal accumulation of manganese in MOB biomass on Mn(II)-containing agar plates. Furthermore, it was possible to show the importance

Oak Forest Responses to Episodic-Seasonal-Drought, Chronic Multi-year Precipitation Change and Acute Drought Manipulations in a Region With Deep Soils and High Precipitation

Science.gov (United States)

Hanson, Paul J.; Wullschleger, Stan D.; Todd, Donald E.; Auge, Robert M.; Froberg, Mats; Johnson, Dale W.

2010-05-01

drying, but no change in mineral soil carbon pools attributable to changing precipitation. Measured changes in nitrogen and other element pools suggested that long term immobilization of elements with chronic drying would lead to reduced growth, but that deep rooting access to the key base cations would moderate such effects by providing a source of minerals to be cycled in near surface soils. Cumulative changes in canopy foliar production were evident over time showing sustained or even increased production with chronic drying. This unexpected response is hypothesized to result from the retention of nutrients in highly-rooted surface horizons made available for plant uptake during spring mineralization.

Sorption mechanisms of selenium species (selenite and selenate) on copper-based minerals

International Nuclear Information System (INIS)

Devoy, J.

2001-09-01

The sorption of radionuclides on the surface of minerals represents a process capable to delay the migration of the elements from a spent fuel deep repository towards the biosphere. In the framework of a deep underground repository, an engineered clay barrier has a high trapping capacity for cationic radio-elements, in particular because of the negative charge of clay surfaces. However, anionic radioelements like selenium species, would be only weakly retained by chemical processes. In order to optimize the trapping capacity of a clay barrier with respect to anionic species, prospective studies are carried out in order to find and evaluate some minerals with specific chemical trapping functions. Among radionuclides, the case of selenium has to be considered because its isotope 79 Se is present in radioactive wastes and has a half life time of 6.5 10 4 years. It is also judicious to find a mineral capable of trapping simultaneously several anionic radio-elements. Copper oxides and sulfides (Cu 2 O, CuO, Cu 2 S, CuS, CuFeS 2 and Cu 5 FeS 4 ) are good adsorbents with respect to selenium species (selenite and selenate). These minerals, with their selenium retention properties, could be used also for the decontamination of soils and waters or to process industrial effluents. The sorption mechanisms have been studied in details for copper oxides (Cu 2 O and CuO) with respect to selenite and selenate. Chalcomenite precipitates in acid pH conditions when selenite is added to a Cu 2 O and CuO suspension. Selenate, in contact with cuprite (Cu 2 O) leads also to a selenium-based precipitate in acid pH environment. For higher pH values, selenite and selenate are adsorbed on copper oxides (Cu 2 O and CuO) and lead to internal and external sphere complexes, respectively. In the case of a selenite/cuprite mixture in basic pH environment and at the equilibrium, a chemical reaction occurs between the oxidation product of cuprite, Cu(OH) 2 and HSeO 3 . A preliminary study of

Spectroscopic studies on surface reactions between minerals and reagents in flotation systems

International Nuclear Information System (INIS)

Giesekke, E.W.

1981-01-01

A study of the adsorbed species at the interface between the minerals and the aqueous solution is reported in the hope that it will contribute to a better understanding of selective mineral flotation by various reagents. The results of infrared spectroscopic studies are cited from the author's investigation on the fluorite-sodium oleate and fluorite-linoleate systems. Electron-spectroscopic techniques, e.g., electron spectroscopy for chemical analysis (ESCA) have also been useful in the identification of adsorbed species on mineral surfaces. Some experimental data from the literature are discussed. These studies have the disadvantage that they are not in situ investigations of the interface between the mineral and the aqueous solution. The potential use of other spectroscopic techniques are discussed, photo-acoustic, Raman, and electron-spin-resonance spectroscopy being considered as possible alternatives. It is suggested that the relatively small surface areas of minerals used in flotation (i.e. smaller than 2m 2 .g- 1 ) impose severe restrictions on the use of such techniques

Iron and manganese oxide mineralization in the Pacific

Science.gov (United States)

Hein, J. R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Jung-Keuk, Kang; Lubick, N.

1997-01-01

Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. These processes are discussed.

Photocatalytic mineralization of commercial herbicides in a pilot-scale solar CPC reactor: photoreactor modeling and reaction kinetics constants independent of radiation field.

Science.gov (United States)

Colina-Márquez, Jose; Machuca-Martínez, Fiderman; Li Puma, Gianluca

2009-12-01

The six-flux absorption-scattering model (SFM) of the radiation field in the photoreactor, combined with reaction kinetics and fluid-dynamic models, has proved to be suitable to describe the degradation of water pollutants in heterogeneous photocatalytic reactors, combining simplicity and accuracy. In this study, the above approach was extended to model the photocatalytic mineralization of a commercial herbicides mixture (2,4-D, diuron, and ametryne used in Colombian sugar cane crops) in a solar, pilot-scale, compound parabolic collector (CPC) photoreactor using a slurry suspension of TiO(2). The ray-tracing technique was used jointly with the SFM to determine the direction of both the direct and diffuse solar photon fluxes and the spatial profile of the local volumetric rate of photon absorption (LVRPA) in the CPC reactor. Herbicides mineralization kinetics with explicit photon absorption effects were utilized to remove the dependence of the observed rate constants from the reactor geometry and radiation field in the photoreactor. The results showed that the overall model fitted the experimental data of herbicides mineralization in the solar CPC reactor satisfactorily for both cloudy and sunny days. Using the above approach kinetic parameters independent of the radiation field in the reactor can be estimated directly from the results of experiments carried out in a solar CPC reactor. The SFM combined with reaction kinetics and fluid-dynamic models proved to be a simple, but reliable model, for solar photocatalytic applications.

On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

Directory of Open Access Journals (Sweden)

Van Pham Thi

2012-06-01

Full Text Available Abstract Continental flood basalts (CFB are considered as potential CO2 storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO2 point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB we estimated the potential of CFB to store CO2 in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass and the local equilibrium assumption for secondary phases (weathering products. The simulations were divided into closed-system batch simulations at a constant CO2 pressure of 100 bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H2O in scCO2, and finally 1D reactive diffusion simulations giving reactivity at CO2 pressures varying from 0 to 100 bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO2 mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40 C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 – 100 C, magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO2 stored as solid carbonates, if CO2 is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO2 phase with limited amount of water, the total carbonation potential is limited by the amount of water present

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

Energy Technology Data Exchange (ETDEWEB)

Marques, Jose M. [Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001, Lisboa (Portugal)], E-mail: jose.marques@ist.ult.pt; Carreira, Paula M. [Instituto Tecnologico e Nuclear, Estrada Nacional No 10, 2686-953 Sacavem (Portugal); Carvalho, Maria Rosario [Departamento de Geologia, Faculdade de Ciencias, Universidade de Lisboa, Ed. C6, 3oP, Campo Grande, 1749-016 Lisboa (Portugal); Matias, Maria J. [Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001, Lisboa (Portugal); Goff, Fraser E. [Earth and Planetary Sciences Department MSCO3-2040, University of New Mexico, Albuquerque, New Mexico 87131-000 (United States); Basto, Maria J.; Graca, Rui C.; Aires-Barros, Luis [Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001, Lisboa (Portugal); Rocha, Luis [Junta de Freguesia, Av. da Libertacao, 45-D, 7460-002, Cabeco de Vide (Portugal)

2008-12-15

This paper reviews the geochemical, isotopic ({sup 2}H, {sup 18}O, {sup 13}C, {sup 3}H and {sup 14}C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na-Cl/Ca-OH mineral waters from the Cabeco de Vide region (Central-Portugal). Water-rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeco de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg-HCO{sub 3} type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na-Cl/Ca-OH mineral waters of Cabeco de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeco de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeco de Vide mineral waters. Similar {delta}{sup 2}H and {delta}{sup 18}O suggest a common meteoric origin and that the Mg-HCO{sub 3} type waters have evolved towards Cabeco de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca-HCO{sub 3} to Mg-HCO{sub 3} waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO{sub 2} (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeco de Vide mineral waters was determined as 2790 {+-} 40 a BP, on the basis of {sup 14}C and {sup 13}C values, which is in agreement with the {sup 3}H concentrations being below the detection limit.

Study on Thorium Hidroxide and Ammonium Diuranate precipitation

International Nuclear Information System (INIS)

Damunir; Sukarsono, R; Busron-Masduki; Indra-Suryawan

1996-01-01

Thorium hydroxide and ammonium diuranate precipitation studied by the reaction of mixed thorium nitrate and uranyl nitrate using ammonium hydroxide. The purposes of this research was study of pH condition. U/Th ratio and NH 4 OH concentration on the precipitation. Mixed of thorium nitrate and uranyl nitrate 50 ml was reacted by excess ammonium hydroxide 2 - 10 M, pH 4-8, 40-80 o C of temperature and 5 - 100 % ratio of U/Th. The best of precipitation depend on thorium and uranium content on the precipitation. The experiment result for the best condition of precipitation was 25 % of ratio U/Th, pH 6 - 8, 60-80 o C of temperature, and 6 - 10 M concentration of ammonium hydroxide, was produced precipitate by 3,938 - 5,455 weight percent of mean concentration of U and 22,365-31,873 weight percent of mean concentration of Th

Energy and economic considerations for ex-situ and aqueous mineral carbonation

Energy Technology Data Exchange (ETDEWEB)

O' Connor, William K.; Dahlin, David C.; Rush, G.E.; Gerdemann, Stephen J.; Penner, L.R.

2004-01-01

Due to the scale and breadth of carbon dioxide emissions, and speculation regarding their impact on global climate, sequestration of some portion of these emissions has been under increased study. A practical approach to carbon sequestration will likely include several options, which will be driven largely by the energy demand and economics of operation. Aqueous mineral carbonation of calcium and magnesium silicate minerals has been studied as one potential method to sequester carbon dioxide. Although these carbonation reactions are all thermodynamically favored, they occur at geologic rates of reaction. Laboratory studies have demonstrated that these rates of reaction are accelerated with increasing temperature, pressure, and particle surface area. Mineral-specific activation methods were identified, however, each of these techniques incurs energy as well as economic costs. An overview of the mineral availability, pretreatment options and energy demands, and process economics is provided.

A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways

OpenAIRE

Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

2009-01-01

Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann’s approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thu...

Pseudomonas, Pantoea and Cupriavidus isolates induce calcium carbonate precipitation for biorestoration of ornamental stone.

Science.gov (United States)

Daskalakis, M I; Magoulas, A; Kotoulas, G; Catsikis, I; Bakolas, A; Karageorgis, A P; Mavridou, A; Doulia, D; Rigas, F

2013-08-01

Bacterially induced calcium carbonate precipitation from various isolates was investigated aiming at developing an environmentally friendly technique for ornamental stone protection and restoration. Micro-organisms isolated from stone samples and identified using 16S rDNA and biochemical tests promoted calcium carbonate precipitation in solid and novel liquid growth media. Biomineral morphology was studied on marble samples with scanning electron microscopy. Most isolates demonstrated specimen weight increase, covering partially or even completely the marble surfaces mainly with vaterite. The conditions under which vaterite precipitated and its stability throughout the experimental runs are presented. A growth medium that facilitated bacterial growth of different species and promoted biomineralization was formulated. Most isolates induced biomineralization of CaCO3 . Micro-organisms may actually be a milestone in the investigation of vaterite formation facilitating our understanding of geomicrobiological interactions. Pseudomonas, Pantoea and Cupriavidus strains could be candidates for bioconsolidation of ornamental stone protection. Characterization of biomineralization capacity of different bacterial species improves understanding of the bacterially induced mineralization processes and enriches the list of candidates for biorestoration applications. Knowledge of biomineral morphology assists in differentiating mineral from biologically induced precipitates. © 2013 The Society for Applied Microbiology.

Preliminary conceptual model for mineral evolution in Yucca Mountain

International Nuclear Information System (INIS)

Duffy, C.J.

1993-12-01

A model is presented for mineral alteration in Yucca Mountain, Nevada, that suggests that the mineral transformations observed there are primarily controlled by the activity of aqueous silica. The rate of these reactions is related to the rate of evolution of the metastable silica polymorphs opal-CT and cristobalite assuming that a SiO 2(aq) is fixed at the equilibrium solubility of the most soluble silica polymorph present. The rate equations accurately predict the present depths of disappearance of opal-CT and cristobalite. The rate equations have also been used to predict the extent of future mineral alteration that may result from emplacement of a high-level nuclear waste repository in Yucca Mountain. Relatively small changes in mineralogy are predicted, but these predictions are based on the assumption that emplacement of a repository would not increase the pH of water in Yucca Mountain nor increase its carbonate content. Such changes may significantly increase mineral alteration. Some of the reactions currently occurring in Yucca Mountain consume H + and CO 3 2- . Combining reaction rate models for these reactions with water chemistry data may make it possible to estimate water flux through the basal vitrophyre of the Topopah Spring Member and to help confirm the direction and rate of flow of groundwater in Yucca Mountain

A study preliminary technician for the obtaining of concentrated de lanthanum and cerium to leave of national minerals

International Nuclear Information System (INIS)

Orrego A, P; Navarro D, Patricio; Mahu A, Susana; Vega V, Pilar

1999-01-01

A preliminary technical study was carried out to obtain concentrated oxides of Lanthanum (La) and Cerium (Ce), from a radioactively anomalous local mineral. This study is part of a joint project of the National Mining Company (ENAMI) and the Chilean Nuclear Energy Commission (CCHEN), G eological Investigation of Rare Earth in the Region III mountain range ; which aims to diversify the production of minerals that have potential economic interest in the short term. Three sections were defined over area of 100 km 2 , where the rare earth bearing metallic mineral is davidite ((AB-3(O, OH)-7), with A = Fe 2+ , RE, U, Ca, Na, Zr, Th; B = Ti 4+ , Fe 3+ U, V 3+ , Cr 3+ and varieties of anatase with Ti, RE, La, Ce and Nd. The metallurgical research includes the following stages: leaching with sulfuric acid, selective precipitation of purities and the rare earth, evaluating the reagents sodium hydroxide and ammonium hydroxide, dissolution of the precipitates containing rare earth with nitric acid and later precipitation with oxalic acid. According to the results obtained in the laboratory tests, the best operating conditions would be: (1) Leaching R(S/L) = 1, dosage 500 kg of acid /ton mineral; 90 , (2) Precipitation of impurities Ammonium Hydroxide, pH = 4.5 at 90 , (3) Precipitation elements of RE Ammonium Hydroxide, pH 7,5 at 90 , (4) Dissolution HNO-3, 70 , (5) Oxalic precipitation Oxalic acid, pH ∼ 1,0 at 70 . The results of each stage were evaluated with the following major points: Sulfuric acid is not a good leaching agent under normal conditions of temperature and pressure. For sulfuric solutions ammonium hydroxide provides the best precipitation efficiencies. Selective precipitation with oxalic acid produces bigger lanthanide recovery at a pH of less than 1.0. By means this design a concentrate of oxides of rare earth with an approximate of 43% may be obtained

Fluid inclusion and oxygen-isotope evidence for low-temperature Au-Pt-Pd (± U) mineralization at Corronation Hill, NT

International Nuclear Information System (INIS)

Mernagh, T.

1992-01-01

The fluid inclusion and isotope data have been used to constrain the ore genesis models for the Au-Pt-Pd-U mineralization at Coronation Hill. The fluid inclusions demonstrate that the ore fluid was strongly saline with an unusually high CaCl 2 content, and that the mineralisation was probably formed from a boiling fluid at around 140 deg C. Furthermore, the fluids were highly oxidised and the replacement of earlier chlorite by hematite is common throughout the deposit. It is concluded that both U-rich and U-poor Au-Pt-Pd mineralisation were formed by descending, low-temperature, highly oxidised, very saline, meteoric fluids. The segregation of U was controlled by fluid-rock interaction in the feldspathic or carbonate rocks. Interaction with carbonaceous or chloritic rocks resulted in a reduction in fO 2 , and consequent precipitation of U, Au, Pt and Pd. The other two types of metal associations can be explained by further reaction of the mineralizing fluids. 3 figs

Recent Developments on Discontinuous Precipitation

Directory of Open Access Journals (Sweden)

Zięba P.

2017-06-01

Full Text Available The discontinuous precipitation (DP belongs to a group of diffusive solid state phase transformations during which the formation of a new phase is heterogeneous and limited to a migrating reaction front (RF. The use of analytical electron microscopy provided reliable information that there is no differences in the diffusion rate at the stationary grain boundary and moving RF of DP reaction. On the other hand, the use of “in situ” transmission electron microscopy observations indicated the importance of stop-go motion or oscillatory movement of the RF.

Mineral scale management. Part II, Fundamental chemistry

Science.gov (United States)

Alan W. Rudie; Peter W. Hart

2006-01-01

The mineral scale that deposits in digesters and bleach plants is formed by a chemical precipitation process.As such, it is accurately modeled using the solubility product equilibrium constant. Although solubility product identifies the primary conditions that must be met for a scale problem to exist, the acid-base equilibria of the scaling anions often control where...

Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30, 1993

Energy Technology Data Exchange (ETDEWEB)

Somasundaran, P.

1994-07-01

The aim of this research project is to investigate mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy will be determined. A multi-pronged approach consisting of micro & nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability; is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the first year of this three year contract, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Surfactants studied include alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amount of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed.

Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

Science.gov (United States)

Jones, Brian; Peng, Xiaotong

2016-11-01

Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

Science.gov (United States)

Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

2016-04-01

Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

Experimental Study of Serpentinization Reactions

Science.gov (United States)

Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

2004-01-01

Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4

Energy Technology Data Exchange (ETDEWEB)

Wolery, T.J.; Daveler, S.A.

1992-10-09

EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.

The role of silicate surfaces on calcite precipitation kinetics

DEFF Research Database (Denmark)

Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas Emile

2014-01-01

The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite......, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a p...

γ' Precipitation Study of a Co-Ni-Based Alloy

Science.gov (United States)

Locq, D.; Martin, M.; Ramusat, C.; Fossard, F.; Perrut, M.

2018-05-01

A Co-Ni-based alloy strengthened by γ'-(L12) precipitates was utilized to investigate the precipitation evolution after various cooling rates and several aging conditions. In this study, the precipitate size and volume fraction have been studied via scanning electron microscopy and transmission electron microscopy. The influence of the precipitation evolution was measured via microhardness tests. The cooling rate study shows a more sluggish γ' precipitation reaction compared to that observed in a Ni-based superalloy. Following a rapid cooling rate, the application of appropriate double aging treatments allows for the increase of the γ' volume fraction as well as the control of the size and distribution of the precipitates. The highest hardness values reach those measured on supersolvus cast and wrought Ni-based superalloys. The observed γ' precipitation behavior should have implications for the production, the heat treatment, the welding, or the additive manufacturing of this new class of high-temperature materials.

Raoultella sp. SM1, a novel iron-reducing and uranium-precipitating strain.

Science.gov (United States)

Sklodowska, Aleksandra; Mielnicki, Sebastian; Drewniak, Lukasz

2018-03-01

The main aim of this study was the characterisation of novel Raoutella isolate, an iron-reducing and uranium-precipitating strain, originating from microbial mats occurring in the sediments of a closed down uranium mine in Kowary (SW Poland). Characterisation was done in the context of its potential role in the functioning of these mats and the possibility to use them in uranium removal/recovery processes. In our experiment, we observed the biological precipitation of iron and uranium's secondary minerals containing oxygen, potassium, sodium and phosphor, which were identified as ningyoite-like minerals. The isolated strain, Raoultella sp. SM1, was also able to dissimilatory reduce iron (III) and uranium (VI) in the presence of citrate as an electron donor. Our studies allowed us to characterise a new strain which may be used as a model microorganism in the study of Fe and U respiratory processes and which may be useful in the bioremediation of uranium-contaminated waters and sediments. During this process, uranium may be immobilised in ningyoite-like minerals and can then be recovered in nano/micro-particle form, which may be easily transformed to uraninite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Numerical Simulation of Tuff Dissolution and Precipitation Experiments: Validation of Thermal-Hydrologic-Chemical (THC) Coupled-Process Modeling

Science.gov (United States)

Dobson, P. F.; Kneafsey, T. J.

2001-12-01

As part of an ongoing effort to evaluate THC effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation. To replicate mineral dissolution by condensate in fractured tuff, deionized water equilibrated with carbon dioxide was flowed for 1,500 hours through crushed Yucca Mountain tuff at 94° C. The reacted water was collected and sampled for major dissolved species, total alkalinity, electrical conductivity, and pH. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/L; silica was the dominant dissolved constituent. A portion of the steady-state reacted water was flowed at 10.8 mL/hr into a 31.7-cm tall, 16.2-cm wide vertically oriented planar fracture with a hydraulic aperture of 31 microns in a block of welded Topopah Spring tuff that was maintained at 80° C at the top and 130° C at the bottom. The fracture began to seal within five days. A 1-D plug-flow model using the TOUGHREACT code developed at Berkeley Lab was used to simulate mineral dissolution, and a 2-D model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The fracture-plugging simulations result in the precipitation of amorphous silica at the base of the boiling front, leading to a hundred-fold decrease in fracture permeability in less than 6 days, consistent with the laboratory experiment. These results help validate the use of the TOUGHREACT code for THC modeling of the Yucca Mountain system. The experiment and simulations indicate that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. The TOUGHREACT code will be used

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

Science.gov (United States)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

Comparison of rat connective tissue reaction to two types of foreign and Iranian white Mineral Trioxide Aggregate

Directory of Open Access Journals (Sweden)

Vosough Hosseini S.

2008-11-01

Full Text Available "nBackground and Aim: Three Dimensional obturation of root canal is one of the main goals of root canal therapy to preserve health or reach the regeneration or healing of periapical tissues. Root end filling materials are used in numerous situations to reach the mentioned goals. One of the common root end- filling materials is mineral trioxide aggregate (MTA which the foreign and Iranian ones are different in their prices. The aim of this study was to compare the rat connective tissue reaction to Iranian and foreign MTA. "nMaterials and Methods: This was an animal study in which 40 rats were divided into 5 groups of each 8. The polyethylene tubes filled with foreign (Pro Root MTA and Iranian (Root MTA white MTA and were implanted in subcutaneous connective tissue. Similarly, the empty tubes were inserted in subcutaneous connective tissue as control group. The samples were examined histologically after 7, 14, 30, 60 and 90 days and were scored as followings: 0, was characterized to samples without inflammatory cells; without inflammatory reaction 1, for samples with less than 25 inflammatory cells; mild inflammatory reaction. 2, for samples with 25 to 125 inflammatory cells; moderate inflammatory reaction and 3, for ones with more than 125 inflammatory cells; severe inflammatory reaction. The data were analyzed using Kruskal-Wallis test and p<0.05 was considered as the level of significance. "nResults: In general, inflammatory reactions were reduced in all groups. Experimental groups had moderate to severe inflammation in the 7th day which had significant difference with the control group having mild to moderate inflammation (p=0.04. There was not any significant differences between experimental and control group in 14th, 30th, 60th and 90th days (p>0.05. "nConclusion: Based on the findings of this investigation, inflammatory subcutaneous connective tissue reaction to Iranian (Root MTA and foreign (Pro Root MTA MTA was the same.

-Heterocyclic Carbene Complexes of Mineral Acids

KAUST Repository

Brill, Marcel; Nahra, Fady; Gó mez-Herrera, Alberto; Zinser, Caroline; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.

2016-01-01

We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

-Heterocyclic Carbene Complexes of Mineral Acids

KAUST Repository

Brill, Marcel

2016-11-08

We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

Systematic front distortion and presence of consecutive fronts in a precipitation system

NARCIS (Netherlands)

Volford, A.; Izsak, F.; Ripszam, M.; Lagzi, I.

2006-01-01

A new simple reaction-diffusion system is presented focusing on pattern formation phenomena as consecutive precipitation fronts and distortion of the precipitation front.The chemical system investigated here is based on the amphoteric property of aluminum hydroxide and exhibits two unique phenomena.

Experimental Studies on the Interaction of scCO2 and scCO2-SO2 With Rock Forming Minerals at Conditions of Geologic Carbon Storages - First Results

Science.gov (United States)

Erzinger, J.; Wilke, F.; Wiersberg, T.; Vasquez Parra, M.

2010-12-01

alone, at which those with silicate phases have a lower pH (between 2 and 3) than experiments with carbonates. Fluid-mineral-interactions using scCO2-SO2 are thus much stronger and the concentrations of SO4 and cations in the reacting fluids are generally much higher, especially for Fe, Si and Al of silicates. However, intensity and rate of reactions are controlled by the availability of SO2 and apparently buffered by dissolution and precipitation processes. EMPA and Raman spectroscopy analyses are in progress to identify possible precipitated secondary products on mineral surfaces.

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO2 from Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Brent Constantz; Randy Seeker; Martin Devenney

2010-06-30

Calera's innovative Mineralization via Aqueous Precipitation (MAP) technology for the capture and conversion of CO{sub 2} to useful materials for use in the built environment was further developed and proven in the Phase 1 Department of Energy Grant. The process was scaled to 300 gallon batch reactors and subsequently to Pilot Plant scale for the continuous production of product with the production of reactive calcium carbonate material that was evaluated as a supplementary cementitious material (SCM). The Calera SCM{trademark} was evaluated as a 20% replacement for ordinary portland cement and demonstrated to meet the industry specification ASTM 1157 which is a standard performance specification for hydraulic cement. The performance of the 20% replacement material was comparable to the 100% ordinary portland cement control in terms of compressive strength and workability as measured by a variety of ASTM standard tests. In addition to the performance metrics, detailed characterization of the Calera SCM was performed using advanced analytical techniques to better understand the material interaction with the phases of ordinary portland cement. X-ray synchrotron diffraction studies at the Advanced Photon Source in Argonne National Lab confirmed the presence of an amorphous phase(s) in addition to the crystalline calcium carbonate phases in the reactive carbonate material. The presence of carboaluminate phases as a result of the interaction of the reactive carbonate materials with ordinary portland cement was also confirmed. A Life Cycle Assessment was completed for several cases based on different Calera process configurations and compared against the life cycle of ordinary portland cement. In addition to the materials development efforts, the Calera technology for the production of product using an innovative building materials demonstration plant was developed beyond conceptual engineering to a detailed design with a construction schedule and cost estimate.

Microbially-Mediated Precipitation of Calcium Carbonate Nanoparticles.

Science.gov (United States)

Kang, Ser Ku; Roh, Yul

2016-02-01

The objective of this study was to investigate the biomineralization of carbonate minerals using microorganisms (Wu Do-1) enriched from rhodoliths. A 16S rRNA sequence analysis showed that Wu Do-1 mainly contained Proteus mirabilis. The pH decreased from 6.5 to 5.3 over the first 4 days of incubation due to microbial oxidation of organic acids, after which it increased to 7.8 over the remaining incubation period. XRD analysis showed that the precipitates were Mg-rich cal- cite (MgxCa(1-x)CO3), whereas no precipitates were formed without the addition of Wu Do-1 in D-1 medium. SEM-EDS analyses showed that the Mg-rich calcite had a rhombohedron shape and consisted of Ca, Si and Mg with an extracelluar polymeric substance (EPS). In addition, TEM-EDS analyses revealed they were hexagon in shape, 500-700 nm in size, and composed of Ca, Mg, C, and O. These results indicated that Wu Do-1 induced precipitation of Mg-rich calcite on the cell walls and EPS via the accumulation of Ca and/or Mg ions. Therefore, microbial precipitation of carbonate nanoparticles may play an important role in metal and carbon biogeochemistry, as well as in carbon sequestration in natural environments.

The adsorption of chelating reagents on oxide minerals

International Nuclear Information System (INIS)

Bryson, M.A.W.

1984-06-01

This work constitutes a fundamental study of the interaction between chelating reagents and oxide minerals. The adsorption mechanisms have been elucidated for most of the systems generated by the oxides of copper(II) or iron(III) and chelating reagents octyl hydroxamate, N-phenylbenzohydroxamate, salicylaldoxime, 5-nitro-salicylaldoxime or 8-hydroxyquinoline. In order to better understand the adsorption process associated with copper(II) oxide, the oxide was recrystallized to produce a coarser material with a more uniform surface. This allowed the oxide surface to be viewed under the scanning electron microscope. A detailed investigation of the effect of the system variables; pH, conditioning period, concentration, temperature, surface area and dispersing reagent on the rate of precipitation of the copper chelate species of general form, Cu(chel) 2 , was made. In addition the chemical nature of the adsorbed species and the structural form of the precipitates were determined with the aid of infra-red spectroscopy and the scanning electron microscope. On the basis of these results a model has been formulated for the adsorption processes. The precipitation process was examined in more detail by the study of the adsorption of chelate on copper metal. Contact angle measurements of air bubbles on copper metal conditioned with chelate were related to the adsorption results in an attempt to isolate the optimum conditions for flotation of oxide minerals

Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation.

Science.gov (United States)

Tang, Yuanzhi; Zeiner, Carolyn A; Santelli, Cara M; Hansel, Colleen M

2013-04-01

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by six Mn(II)-oxidizing Ascomycete fungi. All fungal species substantially enhanced rhodochrosite dissolution and surface modification. Mineral-hosted Mn(II) was oxidized resulting in formation of Mn(III/IV) oxides that were all similar to δ-MnO2 but varied in morphology and distribution in relation to cellular structures and the MnCO3 surface. For four fungi, Mn(II) oxidation occurred along hyphae, likely mediated by cell wall-associated proteins. For two species, Mn(II) oxidation occurred via reaction with fungal-derived superoxide produced at hyphal tips. This pathway ultimately resulted in structurally unique Mn oxide clusters formed at substantial distances from any cellular structure. Taken together, findings for these two fungi strongly point to a role for fungal-derived organic molecules in Mn(III) complexation and Mn oxide templation. Overall, this study illustrates the importance of fungi in rhodochrosite dissolution, extends the relevance of biogenic superoxide-based Mn(II) oxidation and highlights the potential role of mycogenic exudates in directing mineral precipitation. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Precipitation of uranium concentrates by hydrogen peroxide

International Nuclear Information System (INIS)

Barbosa Filho, O.

1986-12-01

An experimental study on the (UO 4 .xH 2 ) uranyl peroxide precipitation from a uranium process strip solution is presented. The runs were performed in a batch reactor, in laboratory scale. The main objective was to assess the possibility of the peroxide route as an alternative to a conventional ammonium diuranate process. The chemical composition of process solution was obtained. The experiments were conducted according to a factorial design, aiming to evaluate the effects of initial pH, precipitation pH and H 2 O 2 /UO 2 2+ ratio upon the process. The responses were measured in terms of the efficiency of U precipitation, the content of U in the precipitates and the distribution of impurities in the precipitates. The results indicated that the process works is satisfactory on the studied conditions and depending on conditions, it is possible to achieve levels of U precipitation efficiency greater than 99.9% in reaction times of 2 hours. The precipitates reach grades around 99% U 3 O 8 after calcination (900 0 C) and impurities fall below the limit for penalties established by the ASTM and the Allied Chemical Standards. The precipitates are composed of large aggregates of crystals of 1-4 μm, are fast settling and filtering, and are free-flowing when dry. (Author) [pt

Surfactant loss control in chemical flooding spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30 1995

Energy Technology Data Exchange (ETDEWEB)

Casteel, J. [Bartlesville Project Office, OK (United States)

1996-07-01

The aim of this research project was to investigate mechanisms governing adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy have been determined. A multi-pronged approach consisting of micro & nano spectroscopy, electrokinetics, surface tension and wettability is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the three years contract period, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride were the surfactants studied. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes in interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amounts of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed. Changes of microstructure upon dilution (desorption) were also studied. Presence of the nonionic surfactants in mixed aggregate leads to shielding of the charge of ionic surfactants which in turn promotes aggregation but reduced electrostatic attraction between the charged surfactant and the mineral surface. Strong consequences of surfactant interactions in solution on adsorption as well as correlations between monomer concentration in mixtures and adsorption were revealed.

The skeletal organic matrix from Mediterranean coral Balanophyllia europaea influences calcium carbonate precipitation.

Science.gov (United States)

Goffredo, Stefano; Vergni, Patrizia; Reggi, Michela; Caroselli, Erik; Sparla, Francesca; Levy, Oren; Dubinsky, Zvy; Falini, Giuseppe

2011-01-01

Scleractinian coral skeletons are made mainly of calcium carbonate in the form of aragonite. The mineral deposition occurs in a biological confined environment, but it is still a theme of discussion to what extent the calcification occurs under biological or environmental control. Hence, the shape, size and organization of skeletal crystals from the cellular level through the colony architecture, were attributed to factors as diverse as mineral supersaturation levels and organic mediation of crystal growth. The skeleton contains an intra-skeletal organic matrix (OM) of which only the water soluble component was chemically and physically characterized. In this work that OM from the skeleton of the Balanophyllia europaea, a solitary scleractinian coral endemic to the Mediterranean Sea, is studied in vitro with the aim of understanding its role in the mineralization of calcium carbonate. Mineralization of calcium carbonate was conducted by overgrowth experiments on coral skeleton and in calcium chloride solutions containing different ratios of water soluble and/or insoluble OM and of magnesium ions. The precipitates were characterized by diffractometric, spectroscopic and microscopic techniques. The results showed that both soluble and insoluble OM components influence calcium carbonate precipitation and that the effect is enhanced by their co-presence. The role of magnesium ions is also affected by the presence of the OM components. Thus, in vitro, OM influences calcium carbonate crystal morphology, aggregation and polymorphism as a function of its composition and of the content of magnesium ions in the precipitation media. This research, although does not resolve the controversy between environmental or biological control on the deposition of calcium carbonate in corals, sheds a light on the role of OM, which appears mediated by the presence of magnesium ions.

The Skeletal Organic Matrix from Mediterranean Coral Balanophyllia europaea Influences Calcium Carbonate Precipitation

Science.gov (United States)

Goffredo, Stefano; Vergni, Patrizia; Reggi, Michela; Caroselli, Erik; Sparla, Francesca; Levy, Oren; Dubinsky, Zvy; Falini, Giuseppe

2011-01-01

Scleractinian coral skeletons are made mainly of calcium carbonate in the form of aragonite. The mineral deposition occurs in a biological confined environment, but it is still a theme of discussion to what extent the calcification occurs under biological or environmental control. Hence, the shape, size and organization of skeletal crystals from the cellular level through the colony architecture, were attributed to factors as diverse as mineral supersaturation levels and organic mediation of crystal growth. The skeleton contains an intra-skeletal organic matrix (OM) of which only the water soluble component was chemically and physically characterized. In this work that OM from the skeleton of the Balanophyllia europaea, a solitary scleractinian coral endemic to the Mediterranean Sea, is studied in vitro with the aim of understanding its role in the mineralization of calcium carbonate. Mineralization of calcium carbonate was conducted by overgrowth experiments on coral skeleton and in calcium chloride solutions containing different ratios of water soluble and/or insoluble OM and of magnesium ions. The precipitates were characterized by diffractometric, spectroscopic and microscopic techniques. The results showed that both soluble and insoluble OM components influence calcium carbonate precipitation and that the effect is enhanced by their co-presence. The role of magnesium ions is also affected by the presence of the OM components. Thus, in vitro, OM influences calcium carbonate crystal morphology, aggregation and polymorphism as a function of its composition and of the content of magnesium ions in the precipitation media. This research, although does not resolve the controversy between environmental or biological control on the deposition of calcium carbonate in corals, sheds a light on the role of OM, which appears mediated by the presence of magnesium ions. PMID:21799830

About the role of physico-chemical properties and hydrodynamics on the progress of a precipitation reaction: the case of cerium oxalate particles produced during the coalescence of drops

International Nuclear Information System (INIS)

Jehannin, Marie

2015-01-01

The nucleation and growth of solid particles resulting from a precipitation process is an important topic both for fundamental science and industrial applications. In a precipitation process, different reactants, which are individually soluble in the same solvent, get in contact and react to form insoluble solid particles (the precipitate). The properties of the produced particles are the result of a strong coupling between the chemical reaction and the reactants feed and mixing rates. The latter are mainly provided by diffusive and convective transport through a reaction-diffusion-convection process. In the emulsion precipitation process considered here the reactants are enclosed into droplets. The local transport conditions can be modified in many ways by tuning the relevant parameters and thus be used to control the properties of the precipitated particles. The aim of this study is to investigate the impact of local flow and mixing conditions during the coalescence on the precipitates properties, mainly their size, morphology and distribution. The test system consists of two coalescing droplets: one drop contains oxalic acid dissolved in an aqueous solution, while the other one contains cerium nitrate. Upon contact of the two miscible solutions a precipitate of cerium oxalate is formed. Besides, by adding chosen amounts of diols into the droplets, their surface tensions can be adjusted. Differences in surface tension cause a surface tension gradient in the section where both drops get in contact. This can lead to a Marangoni flow directed from the low surface tension interface to the high surface tension interface. This local convective flow will modify the local mixing conditions of the two solutions. This study focuses on how, where, when, which precipitate forms as function of the initial stoichiometry of the reactants and of the process conditions (e.g. the mixing conditions affected by the Marangoni flow). For this purpose, two configurations of coalescing

Mineral textures in Serpentine-hosted Alkaline Springs from the Oman ophiolite

Science.gov (United States)

Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Bach, Wolfgang; Garrido, Carlos J.; Los, Karin; Fussmann, Dario; Monien, Monien

2017-04-01

Meteoric water infiltration in ultramafic rocks leads to serpentinization and the formation of subaerial, low temperature, hydrothermal alkaline springs. Here, we present a detailed investigation of the mineral precipitation mechanisms and textural features of mineral precipitates, along as the geochemical and hydrological characterization, of two alkaline spring systems in the Semail ophiolite (Nasif and Khafifah sites, Wadi Tayin massif). The main aim of the study is to provide new insights into mineral and textural variations in active, on-land, alkaline vents of the Oman ophiolite. Discharge of circulating fluids forms small-scale, localized hydrological catchments consisting in unevenly interconnected ponds. Three different types of waters can be distinguished within the pond systems: i) Mg-type; alkaline (7.9 11.6), Ca-OH-rich waters; and iii) Mix-type waters arising from the mixing of Mg-type and Ca-type waters (9.6 ponds were carried out by X-ray diffraction (XRD), Raman spectroscopy and field-emission scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Aragonite and calcite are the dominant minerals (95 vol.%) of the total mineralogical index in all sites. Mg-type waters host hydrated magnesium carbonates (nesquehonite) and magnesium hydroxycarbonate hydrates (artinite) due to evaporation. Brucite, hydromagnesite and dypingite presence in Mix-type waters is spatially controlled by the hydrology of the system and is localized around mixing zones between Ca-type with Mg-type waters. Residence time of discharging waters in the ponds before mixing has an impact on fluid chemistry as it influences the equilibration time with the atmosphere. Acicular aragonite is the main textural type in hyper-alkaline Ca-type waters, acting as a substratum for the growth of calcite and brucite crystals. Low crystallinity, dumbbell shaped and double pyramid aragonite dominates in Mix-type water precipitates. Rate of supersaturation is essential

Precipitation patterns during channel flow

Science.gov (United States)

Jamtveit, B.; Hawkins, C.; Benning, L. G.; Meier, D.; Hammer, O.; Angheluta, L.

2013-12-01

Mineral precipitation during channelized fluid flow is widespread in a wide variety of geological systems. It is also a common and costly phenomenon in many industrial processes that involve fluid flow in pipelines. It is often referred to as scale formation and encountered in a large number of industries, including paper production, chemical manufacturing, cement operations, food processing, as well as non-renewable (i.e. oil and gas) and renewable (i.e. geothermal) energy production. We have studied the incipient stages of growth of amorphous silica on steel plates emplaced into the central areas of the ca. 1 meter in diameter sized pipelines used at the hydrothermal power plant at Hellisheidi, Iceland (with a capacity of ca 300 MW electricity and 100 MW hot water). Silica precipitation takes place over a period of ca. 2 months at approximately 120°C and a flow rate around 1 m/s. The growth produces asymmetric ca. 1mm high dendritic structures ';leaning' towards the incoming fluid flow. A novel phase-field model combined with the lattice Boltzmann method is introduced to study how the growth morphologies vary under different hydrodynamic conditions, including non-laminar systems with turbulent mixing. The model accurately predicts the observed morphologies and is directly relevant for understanding the more general problem of precipitation influenced by turbulent mixing during flow in channels with rough walls and even for porous flow. Reference: Hawkins, C., Angheluta, L., Hammer, Ø., and Jamtveit, B., Precipitation dendrites in channel flow. Europhysics Letters, 102, 54001

Scientific and Engineering Progress in CO2 Mineralization Using Industrial Waste and Natural Minerals

Directory of Open Access Journals (Sweden)

Heping Xie

2015-03-01

Full Text Available The issues of reducing CO2 levels in the atmosphere, sustainably utilizing natural mineral resources, and dealing with industrial waste offer challenging opportunities for sustainable development in energy and the environment. The latest advances in CO2 mineralization technology involving natural minerals and industrial waste are summarized in this paper, with great emphasis on the advancement of fundamental science, economic evaluation, and engineering applications. We discuss several leading large-scale CO2 mineralization methodologies from a technical and engineering-science perspective. For each technology option, we give an overview of the technical parameters, reaction pathway, reactivity, procedural scheme, and laboratorial and pilot devices. Furthermore, we present a discussion of each technology based on experimental results and the literature. Finally, current gaps in knowledge are identified in the conclusion, and an overview of the challenges and opportunities for future research in this field is provided.

A major change in precipitation gradient on the Chinese Loess Plateau at the Pliocene-Quaternary boundary

Science.gov (United States)

Peng, Wenbin; Nie, Junsheng; Wang, Zhao; Qiang, Xiaoke; Garzanti, Eduardo; Pfaff, Katharina; Song, Yougui; Stevens, Thomas

2018-04-01

Spatiotemporal variations in East Asian Monsoon (EAM) precipitation during the Quaternary have been intensively studied. However, spatial variations in pre-Quaternary EAM precipitation remain largely uninvestigated, preventing a clear understanding of monsoon dynamics during a warmer climatic period. Here we compare the spatial differences in heavy mineral assemblages between Quaternary loess and pre-Quaternary Red Clay on the Chinese Loess Plateau (CLP) to analyze spatial patterns in weathering. Prior studies have revealed that unstable hornblende is the dominant (∼50%) heavy mineral in Chinese loess deposited over the past 500 ka, whereas hornblende content decreases to climate at Jiaxian must have been initiated since ∼2.7 Ma, preventing hornblende dissolution to amounts change in climatic patterns at ∼2.7 Ma to decreased northward moisture transportation associated with Northern Hemisphere glaciation and cooling in the Quaternary. This study therefore demonstrates the potential usefulness of employing heavy mineral analysis in both paleoclimatic and paleooceanographic reconstructions.

Iron Hydroxide Minerals Drive Organic and Phosphorus Chemistry in Subsurface Redox / pH Gradients

Science.gov (United States)

Flores, E.; Barge, L. M.; VanderVelde, D.; Baum, M.

2017-12-01

Iron minerals, particularly iron oxides and oxyhydroxides, are prevalent on Mars and may exist in mixed valence or even reduced states beneath the oxidized surface. Iron (II,III) hydroxides, including green rust, are reactive and potentially catalytic minerals that can absorb and concentrate charged species, while also driving chemical reactions. These minerals are highly redox-sensitive and the presence of organics and/or phosphorus species could affect their mineralogy and/or stability. Conversely, the minerals might be able to drive chemical processes such as amino acid formation, phosphorus oxyanion reactions, or could simply selectively preserve organic species via surface adsorption. In an open aqueous sediment column, soluble products of mineral-driven reactions could also diffuse to sites of different chemical conditions to react even further. We synthesized Fe-hydroxide minerals under various conditions relevant to early Earth and ancient Mars (>3.0 Gyr), anoxically and in the presence of salts likely to have been present in surface or ground waters. Using these minerals we conducted experiments to test whether iron hydroxides could promote amino acid formation, and how the reaction is affected by subsurface gradients of redox, pH, and temperature. We also tested the adsorption of organic and phosphorus species onto Fe-hydroxide minerals at different conditions within the gradients. The suite of organic or phosphorus signatures that may be found in a particular mineral system is a combination of what is synthesized there, what is preferentially concentrated / retained there, and what is preserved against degradation. Further work is needed to determine how these processes could have proceeded on Mars and what mineral-organic signatures, abiotic or otherwise, would be produced from such processes.

Photocatalytic properties of BiVO4 prepared by the co-precipitation method: Degradation of rhodamine B and possible reaction mechanisms under visible irradiation

International Nuclear Information System (INIS)

Martinez-de la Cruz, A.; Perez, U.M. Garcia

2010-01-01

Bismuth vanadate (BiVO 4 ) was synthesized by the co-precipitation method at 200 o C. The photocatalytic activity of the oxide was tested for the photodegradation of rhodamine B under visible light irradiation. The analysis of the total organic carbon showed that the mineralization of rhodamine B over a BiVO 4 photocatalyst (∼40% after 100 h of irradiation) is feasible. In the same way, a gas chromatography analysis coupled with mass spectroscopy revealed the existence of organic intermediates during the photodegradation process such as ethylbenzene, o-xylene, m-xylene, and phthalic anhydride. The modification of variables such as dispersion pH, amount of dissolved O 2 , and irradiation source was studied in order to know the details about the photodegradation mechanism.

Methods of mineral potential assessment of uranium deposits: A mineral systems approach

International Nuclear Information System (INIS)

Jaireth, S.

2014-01-01

Mineral potential represents the likelihood (probability) that an economic mineral deposit could have formed in an area. Mineral potential assessment and prospectivity analysis use a probabilistic concepts to mineral deposits, where the probability of an event (formation of a mineral deposit) is conditional on two factors : i) geological processes occurring in the area, and ii) the presence of geological features indicative of those process. For instance, one of the geological processes critical for the formation of sandstone-hosted uranium deposits in an area is transport of uranium in groundwaters. Geological features indicative of this process in an area comprise, i) presence of leachable source rocks of uranium; ii) presence of highly permeable sandstone; and iii) suitable hydrogeological gradient driving flow groundwaters. Mineral deposits can also be conceptualised as mineral systems with more emphasis on mineralising processes. This concept has some clear parallels with the petroleum systems approach which has proven to be a useful in oil and gas exploration. Mineral systems are defined as ‘all geological factors that control the generation and preservation of mineral deposits’. Seven important geological factors are outlined to define the characteristics of a hydrothermal mineral system. These factors include: i) source of the mineralising fluids and transporting legends; ii) source of metals and other ore components; iii) migration pathways which may include inflow as well as outflow zones; iv) thermal gradients; v) source of energy to mobilised fluids; vi) mechanical and structural focusing mechanism at the trap site; and vii) chemical and/or physical cause for precipitation of ore minerals at the trap site. This approach, commonly known as the ‘source’, ‘transport’ and ‘trap’ paradigm has been redefined to introduce five questions as a basis to understand spatial and temporal evolution of a mineral system at all scales (regional to

Interactions of trace elements with fracture filling minerals from the Aespoe Hard Rock Laboratory

International Nuclear Information System (INIS)

Landstroem, O.; Tullborg, E.L.

1995-06-01

This report focuses on the distribution of stable elements and natural radionuclides (e.g. REEs, Th, Ra, Sr and Cs) in natural fracture systems. They have been redistributed by natural processes in the past; mobilization, transport and deposition of which the latter is manifested as 'enrichments' of the elements in fracture fillings. Fillings dominated by Fe-oxyhydroxide, calcite and clay minerals show the highest concentrations. Precipitates from different fractures show large variations in concentration levels of trace elements, REE patterns, and activity and activity ratios of natural radionuclides, reflecting variations in physical, chemical and hydrological properties of the fractures. The incorporation of REEs, Sr, Th and U in calcite is significant. The precipitation rate influences the amount of Sr incorporated and probably other elements as well. Clay minerals have high sorption capacity and are important in the retention of Cs and Sr as well as of REEs, Th, U and Ra. The importance of clay minerals in radionuclide retention is emphasized by the results from this study, even small amounts of clay minerals in fractures and fracture zones can significantly influence the radionuclide migration. Accurate determination of quantities and types of clay minerals is therefore very important for radionuclide migration modelling. 58 refs, 14 figs, 12 tabs

Interactions of trace elements with fracture filling minerals from the Aespoe Hard Rock Laboratory

Energy Technology Data Exchange (ETDEWEB)

Landstroem, O [Studsvik Eco and Safety AB, Nykoeping (Sweden); Tullborg, E L [Terralogica AB (Sweden)

1995-06-01

This report focuses on the distribution of stable elements and natural radionuclides (e.g. REEs, Th, Ra, Sr and Cs) in natural fracture systems. They have been redistributed by natural processes in the past; mobilization, transport and deposition of which the latter is manifested as `enrichments` of the elements in fracture fillings. Fillings dominated by Fe-oxyhydroxide, calcite and clay minerals show the highest concentrations. Precipitates from different fractures show large variations in concentration levels of trace elements, REE patterns, and activity and activity ratios of natural radionuclides, reflecting variations in physical, chemical and hydrological properties of the fractures. The incorporation of REEs, Sr, Th and U in calcite is significant. The precipitation rate influences the amount of Sr incorporated and probably other elements as well. Clay minerals have high sorption capacity and are important in the retention of Cs and Sr as well as of REEs, Th, U and Ra. The importance of clay minerals in radionuclide retention is emphasized by the results from this study, even small amounts of clay minerals in fractures and fracture zones can significantly influence the radionuclide migration. Accurate determination of quantities and types of clay minerals is therefore very important for radionuclide migration modelling. 58 refs, 14 figs, 12 tabs.

Use of a pulsed column contactor as a continuous oxalate precipitation reactor

International Nuclear Information System (INIS)

Borda, Gilles; Brackx, Emmanuelle; Boisset, Laurence; Duhamet, Jean; Ode, Denis

2011-01-01

Research highlights: → A new type of continuous precipitating device was patented by CEA and tested with reaction between a surrogate nitrate cerium(III) or neodymium(III) and oxalate complexing agent. → Precipitate is confined in aqueous phase emulsion in tetrapropylene hydrogen and does not form deposit on the vessel walls. → Measure size of the precipitate ranges from 20 to 40 μm, it meets the process requirements to filter, and the precipitation reaction is complete. → The laboratory design can be extrapolated to an industrial uranium(IV) and minor actinide(III) coprecipitating column. - Abstract: The current objective of coprecipitating uranium, and minor actinides in order to fabricate a new nuclear fuel by direct (co)precipitation for further transmutation, requires to develop specific technology in order to meet the following requirements: nuclear maintenance, criticity, and potentially high flowrates due to global coprecipitation. A new type of device designed and patented by the CEA was then tested in 2007 under inactive conditions and with uranium. The patent is for organic confinement in a pulsed column (PC). Actually, pulsed columns have been working for a long time in a nuclear environment, as they allow high capacity, sub-critical design (annular geometry) and easy high activity maintenance. The precipitation reaction between the oxalate complexing agent and a surrogate nitrate - cerium(III) or neodymium(III) alone, or coprecipitated uranium(IV) and cerium(III) - occurs within an emulsion created in the device by these two phases flowing with a counter-current chemically inert organic phase (for example tetrapropylene hydrogen-TPH) produced by the stirring action of the column pulsator. The precipitate is confined and thus does not form deposits on the vessel walls (which are also water-repellent); it flows downward by gravity and exits the column continuously into a settling tank. The results obtained for precipitation of cerium or

Some physicochemical aspects of water-soluble mineral flotation.

Science.gov (United States)

Wu, Zhijian; Wang, Xuming; Liu, Haining; Zhang, Huifang; Miller, Jan D

2016-09-01

Some physicochemical aspects of water-soluble mineral flotation including hydration phenomena, associations and interactions between collectors, air bubbles, and water-soluble mineral particles are presented. Flotation carried out in saturated salt solutions, and a wide range of collector concentrations for effective flotation of different salts are two basic aspects of water-soluble mineral flotation. Hydration of salt ions, mineral particle surfaces, collector molecules or ions, and collector aggregates play an important role in water-soluble mineral flotation. The adsorption of collectors onto bubble surfaces is suggested to be the precondition for the association of mineral particles with bubbles. The association of collectors with water-soluble minerals is a complicated process, which may include the adsorption of collector molecules or ions onto such surfaces, and/or the attachment of collector precipitates or crystals onto the mineral surfaces. The interactions between the collectors and the minerals include electrostatic and hydrophobic interactions, hydrogen bonding, and specific interactions, with electrostatic and hydrophobic interactions being the common mechanisms. For the association of ionic collectors with minerals with an opposite charge, electrostatic and hydrophobic interactions could have a synergistic effect, with the hydrophobic interactions between the hydrophobic groups of the previously associated collectors and the hydrophobic groups of oncoming collectors being an important attractive force. Association between solid particles and air bubbles is the key to froth flotation, which is affected by hydrophobicity of the mineral particle surfaces, surface charges of mineral particles and bubbles, mineral particle size and shape, temperature, bubble size, etc. The use of a collector together with a frother and the use of mixed surfactants as collectors are suggested to improve flotation. Copyright © 2016 Elsevier B.V. All rights reserved.

In-Drift Precipitates/Salts Model

International Nuclear Information System (INIS)

Mariner, P.

2003-01-01

As directed by ''Technical Work Plan For: Engineered Barrier System Department Modeling and Testing FY03 Work Activities'' (BSC 2003 [165601]), the In-Drift Precipitates/Salts (IDPS) model is developed and refined to predict the aqueous geochemical effects of evaporation in the proposed repository. The purpose of this work is to provide a model for describing and predicting the postclosure effects of evaporation and deliquescence on the chemical composition of water within the proposed Engineered Barrier System (EBS). Application of this model is to be documented elsewhere for the Total System Performance Assessment License Application (TSPA-LA). The principal application of this model is to be documented in REV 02 of ''Engineered Barrier System: Physical and Chemical Environment Model'' (BSC 2003 [165601]). The scope of this document is to develop, describe, and validate the IDPS model. This model is a quasi-equilibrium model. All reactions proceed to equilibrium except for several suppressed minerals in the thermodynamic database not expected to form under the proposed repository conditions within the modeling timeframe. In this revision, upgrades to the EQ3/6 code (Version 8.0) and Pitzer thermodynamic database improve the applicable range of the model. These new additions allow equilibrium and reaction-path modeling of evaporation to highly concentrated brines for potential water compositions of the system Na-K-H-Mg-Ca-Al-Cl-F-NO 3 -SO 4 -Br-CO 3 -SiO 2 -CO 2 -O 2 -H 2 O at temperatures in the range of 0 C to 125 C, pressures in the atmospheric range, and relative humidity in the range of 0 to 100 percent. This system applies to oxidizing conditions only, and therefore limits the model to applications involving oxidizing conditions. A number of thermodynamic parameters in the Pitzer database have values that have not been determined or verified for the entire temperature range. In these cases, the known values are used to approximate the values for the rest of

In-Drift Precipitates/Salts Model

Energy Technology Data Exchange (ETDEWEB)

P. Mariner

2003-10-21

As directed by ''Technical Work Plan For: Engineered Barrier System Department Modeling and Testing FY03 Work Activities'' (BSC 2003 [165601]), the In-Drift Precipitates/Salts (IDPS) model is developed and refined to predict the aqueous geochemical effects of evaporation in the proposed repository. The purpose of this work is to provide a model for describing and predicting the postclosure effects of evaporation and deliquescence on the chemical composition of water within the proposed Engineered Barrier System (EBS). Application of this model is to be documented elsewhere for the Total System Performance Assessment License Application (TSPA-LA). The principal application of this model is to be documented in REV 02 of ''Engineered Barrier System: Physical and Chemical Environment Model'' (BSC 2003 [165601]). The scope of this document is to develop, describe, and validate the IDPS model. This model is a quasi-equilibrium model. All reactions proceed to equilibrium except for several suppressed minerals in the thermodynamic database not expected to form under the proposed repository conditions within the modeling timeframe. In this revision, upgrades to the EQ3/6 code (Version 8.0) and Pitzer thermodynamic database improve the applicable range of the model. These new additions allow equilibrium and reaction-path modeling of evaporation to highly concentrated brines for potential water compositions of the system Na-K-H-Mg-Ca-Al-Cl-F-NO{sub 3}-SO{sub 4}-Br-CO{sub 3}-SiO{sub 2}-CO{sub 2}-O{sub 2}-H{sub 2}O at temperatures in the range of 0 C to 125 C, pressures in the atmospheric range, and relative humidity in the range of 0 to 100 percent. This system applies to oxidizing conditions only, and therefore limits the model to applications involving oxidizing conditions. A number of thermodynamic parameters in the Pitzer database have values that have not been determined or verified for the entire temperature range. In these cases

Impacts of Nickel Nanoparticles on Mineral Carbonation

Directory of Open Access Journals (Sweden)

Marius Bodor

2014-01-01

Full Text Available This work presents experimental results regarding the use of pure nickel nanoparticles (NiNP as a mineral carbonation additive. The aim was to confirm if the catalytic effect of NiNP, which has been reported to increase the dissolution of CO2 and the dissociation of carbonic acid in water, is capable of accelerating mineral carbonation processes. The impacts of NiNP on the CO2 mineralization by four alkaline materials (pure CaO and MgO, and AOD and CC steelmaking slags, on the product mineralogy, on the particle size distribution, and on the morphology of resulting materials were investigated. NiNP-containing solution was found to reach more acidic pH values upon CO2 bubbling, confirming a higher quantity of bicarbonate ions. This effect resulted in acceleration of mineral carbonation in the first fifteen minutes of reaction time when NiNP was present. After this initial stage, however, no benefit of NiNP addition was seen, resulting in very similar carbonation extents after one hour of reaction time. It was also found that increasing solids content decreased the benefit of NiNP, even in the early stages. These results suggest that NiNP has little contribution to mineral carbonation processes when the dissolution of alkaline earth metals is rate limiting.

Mechanism of calcium phosphates precipitation in liquid crystals; Mecanisme de precipitation de phosphates de calcium dans des cristaux liquides

Energy Technology Data Exchange (ETDEWEB)

Prelot, B.; Zemb, T

2004-04-01

The possibility of using as a precursor an easily wet meso-porous powder would be a breakthrough in the preparation of nuclear waste storage ceramics. A concentrated solution containing ions to be stored would wet a dry powder and then, subjected to mild compression, lead to a micro-crystalline matrix of calcium phosphate at acceptable temperatures. Since no porous calcium phosphate different from calcined bone (patented) is described as porous precursor, we have compared the different synthesis routes towards meso-porous ceramics. First, we considered homogeneous precipitation of slats in water: using initially off-stoichiometry in reaction, micron-sized hydroxyapatite particles are produced with a specific surface up to 100 m{sup 2}/g. Then, we consider the classical route of precipitation of an hybrid material in the miscibility gap of a phase diagram, when an hexagonal liquid crystal is used a matrix for precipitation. The surfactant family consists in single chain surfactants containing phosphates as head-group to poison the growing surface of calcium phosphate nano-domains. Since the reaction is still too brutal, we considered using a cat-anionic precursor material of controllable surface charge. For certain concentrations and molar ratios, a new structure not yet described in surfactant precipitation literature is observed: since the periodicity is lower than twice the chain length, a disordered constant curvature monolayer (instead of the classical cylinder of twice chain length diameter) of surfactant is implied. Finally, we have investigated synthesis routes implying slow dissolution of pre-formed calcium phosphate in an already existing hexagonal matrix. For all these routes of synthesis, micro-structural determinations using SAXS, WARS and BET are performed, with a special attention to comparison of the precipitation material, the matrix obtained with all elements present, and also the material obtained after calcinations. (authors)

SEASONALITY OF THE LEAF MINER, LEVEL OF PREDATION AND TEMPORAL OCCURRENCE OF RUST CORRELATED TO ABIOTIC FACTORS

Directory of Open Access Journals (Sweden)

B. M. R. Melo

2018-04-01

Full Text Available The coffee leaf miner and a rust are considered as major diseases that are able to reduce productivity in coffee plantations. These agents are influenced by abiotic factors, and their occurrence may suffer oscillation over the years. The objective of this study was to evaluate the seasonal fluctuation of the coffee leaf miner, incidence of coffee prediction and rust, correlated with abiotic factors. The study was performed IFSULDEMINAS-Campus Inconfidentes, in a coffee crop of the cultivar Rubi. A sample for a rust and a coffee leaf miner, in addition to the middle and upper third of the plants, totaling 42 plants in the study area. At the same sampling point, perform soil analysis to correlate nutrients as studied variables. The Pearson correlation of the biotic variables was performed with a precipitation and fertility, a rate of 1 and 5% probability. It was verified that the rust cycle alternated its incidence for the same period in different years and the miner showed behavior coincident to the driest periods of the year. Data not available on precipitation data and number of mines. These diseases had no significant correlation with the fertility parameter. The coffee leaf miner yielded higher rates of occurrence in June and December of 2014. It was concluded that the percentage of coffee leaf miner was higher in the months with lower rainfall indices or no longer summer period; What is it you want to know about the one-time development that may have been influenced by the nearby woods under study and the rust alternated the peaks of occurrence for the two autumners, correlating with a precipitation.

Granite-related hypothermal uranium mineralization in South China

International Nuclear Information System (INIS)

Liu, X.; Wu, J.; Pan, J.; Zhu, M.

2014-01-01

As one of the important geological types, granite-related uranium deposits account for about 29% of the total discovered natural uranium resources in China. Most of the granite-related uranium deposits located in Taoshan - Zhuguang uranium metallogenic belt, South China. In addition to the typical pitchblende vein-type uranium mineralization of epithermal metallogenic system, a new type of granite-related uranium mineralization with characteristics of hypothermal matallogenic system was discovered in South China by current studies. However, hypothermal is contact thermal to epithermal mineralization, and not the conventional intrusive high temperature mineralization. Hypothermal uranium mineralization is presented by disseminated uraninite or pitchblende stockwork in fissures in granites normally with extensive alkaline alteration. The high temperature mineral assemblage of uraninite associate with scheelite and tourmaline was identified in hypothermal uranium mineralization. Fluid inclusion studies on this type mineralization indicated the middle to high temperature (>250℃) mineralization with the mixing evidence of ore forming solution derived from deep level, and the boiling and mixing of ore forming solution are regarded as the dominant mineralization mechanism for the precipitating of uranium. In contrast to the mineralization ages of 67 Ma to 87 Ma for typical pitchblende vein mineralization of epithermal metallogenic system, the mineralization age is older than 100 Ma for hypothermal uranium mineralization in granite. In the Shituling deposit, Xiazhuang uranium ore field, uraninite and pitchblende micro veins with extensive potassic alteration, chloritization and sericitization are hosted in fissures of Indo-Chinese epoch granites with the uranium mineralization age of 130 Ma to 138 Ma with a mineralization temperature of 290℃ to 330℃ indicated. Other examples sharing the similar characters of hypothermal uranium mineralization have been recognized in

DSC and HRTEM investigation of the precipitates in Al-1.0%Mg{sub 2} Si-0.5%Ag alloy

Energy Technology Data Exchange (ETDEWEB)

Gaber, A.; Ali, A.M.; Zou, Y. [Toyama University (Japan). Venture Business Laboratory; Matsuda, K.; Ikeno, S. [Toyama University (Japan). Faculty of Engineering

2004-12-15

The understanding and control of nanoscale precipitation in an Al-1.0 wt-%Mg{sub 2} Si-0.5 wt-% Ag alloy during artificial aging is critical for achieving optimum mechanical properties. To achieve this objective, both differential scanning calorimetry (DSC) and high resolution transmission electron microscopy (HRTEM) have been utilised. The non-isothermal DSC thermograms exhibited eight reaction peaks; six are exothermic (precipitation) and two are endothermic (dissolution) reactions. The activation energies associated with the individual precipitates are determined. With the aid of HRTEM, the evolved precipitates have been characterised. (author)

Formation and Reactivity of Biogenic Iron Minerals

International Nuclear Information System (INIS)

Ferris, F. Grant

2002-01-01

Dissimilatory iron-reducing bacteria (DIRB) play an important role in regulating the aqueous geochemistry of iron and other metals in anaerobic, non-sulfidogenic groundwater environments; however, little work has directly assessed the cell surface electrochemistry of DIRB, or the nature of the interfacial environment around individual cells. The electrochemical properties of particulate solids are often inferred from titrations in which net surface charge is determined, assuming electroneutrality, as the difference between known added amounts of acid and base and measured proton concentration. The resultant titration curve can then be fit to a speciation model for the system to determine pKa values and site densities of reactive surface sites. Moreover, with the development of non-contact electrostatic force microscopy (EFM), it is now possible to directly inspect and quantify charge development on surfaces. A combination of acid-base titrations and EFM are being used to assess the electrochemical surface properties of the groundwater DIRB, Shewanella putrefaciens. The pKa spectra and EFM data show together that a high degree of electrochemical heterogeneity exists within the cell wall and at the cell surface of S. putrefaciens. Recognition of variations in the nature and spatial distribution of reactive sites that contribute to charge development on these bacteria implies further that the cell surface of these Fe(III)-reducing bacteria functions as a highly differentiated interfacial system capable of supporting multiple intermolecular interactions with both solutes and solids. These include surface complexation reactions involving dissolved metals, as well as adherence to mineral substrates such as hydrous ferric oxide through longer-range electrostatic interactions, and surface precipitation of secondary reduced-iron minerals

Influence of non-clay minerals on the interaction between metallic iron and Callovo-Oxfordian clay fraction

International Nuclear Information System (INIS)

Rivard, C.; Pelletier, M.; Villieras, F.; Michau, N.

2012-01-01

Document available in extended abstract form only. In the context of the geological disposal of high-level radioactive waste, it is of prime importance to understand the interaction mechanisms between the geological matrix, Callovo-Oxfordian clay rock (COx) and metallic iron, from the package overpack. In order to evidence the individual role of each clay component entering in the mineralogy of the COx, interactions between metallic iron and pure clays (smectites, illite and kaolinite) were first conducted. To investigate the role of the other minerals, the reactivity of COx, COx clay fraction (COxCF) and mixtures between COxCF and quartz, calcite or pyrite, was studied. Clays and additional minerals were put in contact with powder metallic iron with a weight ratio iron:clay fixed at 1:3 and a clay:solution ratio of 1:20. Proportions of non-clay minerals were deduced from the average COx composition: 50% clays, 24.5% quartz, 24.5% calcite and 1% pyrite. Batch experiments were carried out in anoxic conditions at 90 deg. C in the presence of background electrolyte (NaCl 0.02 M.L -1 , CaCl 2 0.04 M.L -1 ) in Parr reactors for durations of one, three or nine months. After reaction, solid and liquid phases were separated by centrifugation and characterized by classical techniques combining chemical analyses (liquid analyses, transmission electron microscopy combined with Energy Dispersive of X-rays spectroscopy TEM-EDS), mineralogical (X-ray diffraction), spectroscopic ( 57 Fe Moessbauer) and morphometric techniques (TEM, scanning electron microscopy and N 2 adsorption). For COx, COxCF and all the pure clay phases, major evolutions were observed during the first month, which shows that the oxidation of metallic iron is rapid in our experimental conditions. Release of iron cations in solution, pH increase (8-10) and Eh decrease (reductive conditions) are responsible for the partial dissolution of initial clay phases. Released iron is involved in the crystallization of Fe

Application of Monte Carlo Methods to Perform Uncertainty and Sensitivity Analysis on Inverse Water-Rock Reactions with NETPATH

Energy Technology Data Exchange (ETDEWEB)

McGraw, David [Desert Research Inst. (DRI), Reno, NV (United States); Hershey, Ronald L. [Desert Research Inst. (DRI), Reno, NV (United States)

2016-06-01

Methods were developed to quantify uncertainty and sensitivity for NETPATH inverse water-rock reaction models and to calculate dissolved inorganic carbon, carbon-14 groundwater travel times. The NETPATH models calculate upgradient groundwater mixing fractions that produce the downgradient target water chemistry along with amounts of mineral phases that are either precipitated or dissolved. Carbon-14 groundwater travel times are calculated based on the upgradient source-water fractions, carbonate mineral phase changes, and isotopic fractionation. Custom scripts and statistical code were developed for this study to facilitate modifying input parameters, running the NETPATH simulations, extracting relevant output, postprocessing the results, and producing graphs and summaries. The scripts read userspecified values for each constituent’s coefficient of variation, distribution, sensitivity parameter, maximum dissolution or precipitation amounts, and number of Monte Carlo simulations. Monte Carlo methods for analysis of parametric uncertainty assign a distribution to each uncertain variable, sample from those distributions, and evaluate the ensemble output. The uncertainty in input affected the variability of outputs, namely source-water mixing, phase dissolution and precipitation amounts, and carbon-14 travel time. Although NETPATH may provide models that satisfy the constraints, it is up to the geochemist to determine whether the results are geochemically reasonable. Two example water-rock reaction models from previous geochemical reports were considered in this study. Sensitivity analysis was also conducted to evaluate the change in output caused by a small change in input, one constituent at a time. Results were standardized to allow for sensitivity comparisons across all inputs, which results in a representative value for each scenario. The approach yielded insight into the uncertainty in water-rock reactions and travel times. For example, there was little

Characterization of Lignin Precipitated From The Soda Black Liquor of Oil Palm Empty Fruit Bunch Fibers by Various Mineral Acids

Directory of Open Access Journals (Sweden)

M.N Mohamad Ibrahim

2017-10-01

Full Text Available Soda lignin from oil palm empty fruit bunch was directly isolated by various mineral acids i.e. sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid at three levels of concentration (20% v/v, 60%v/v and concentrated. A comparison study was performed through physicochemical properties and structural features using FT-IR, UV, 13C-NMR and nitrobenzene oxidation. The FT-IR results showed that there is no significant difference between the main structures of the lignin isolated by various acids. However, low concentration of phosphoric acid is preferable because of its highest yield. The S: V: H ratio of 7-15:6-11:1 as evaluated by the nitrobenzene oxidation procedure suggests that soda lignin can be classified as belonging to either the cereal straw on grass type. The UV results indicate that phosphoric acid consistently gave the highest absorbance value among the four acids tested in this study regardless of its concentration level. The C13-FTNMR spectra, suggest that the lignin structure is independent of the type of acid used for precipitation.

An integrated modeling study on the effects of mineral dust and sea salt particles on clouds and precipitation

Directory of Open Access Journals (Sweden)

S. Solomos

2011-01-01

Full Text Available This report addresses the effects of pollution on the development of precipitation in clean ("pristine" and polluted ("hazy" environments in the Eastern Mediterranean by using the Integrated Community Limited Area Modeling System (ICLAMS (an extended version of the Regional Atmospheric Modeling System, RAMS. The use of this model allows one to investigate the interactions of the aerosols with cloud development. The simulations show that the onset of precipitation in hazy clouds is delayed compared to pristine conditions. Adding small concentrations of GCCN to polluted clouds promotes early-stage rain. The addition of GCCN to pristine clouds has no effect on precipitation amounts. Topography was found to be more important for the distribution of precipitation than aerosol properties. Increasing by 15% the concentration of hygroscopic dust particles for a case study over the Eastern Mediterranean resulted in more vigorous convection and more intense updrafts. The clouds that were formed extended about three kilometers higher, delaying the initiation of precipitation by one hour. Prognostic treatment of the aerosol concentrations in the explicit cloud droplet nucleation scheme of the model, improved the model performance for the twenty-four hour accumulated precipitation. The spatial distribution and the amounts of precipitation were found to vary greatly between the different aerosol scenarios. These results indicate the large uncertainty that remains and the need for more accurate description of aerosol feedbacks in atmospheric models and climate change predictions.

Separation of uranium and rare earth elements from Rirang ore leach solution by two-step precipitation

International Nuclear Information System (INIS)

Sradjono; Erni Rifandriyah, A.; Zahardi

1995-01-01

Separation of uranium and rare-earth elements from Rirang ore leach solution was carried out through a two-step precipitation. Several condition affecting the separation processes were examined including solution pH, reagent concentration, and reaction prepitation time. Optimum conditions for the first and second precipitation steps include adjustment of precipitation pH to 1.3 and 2.3, respectively by the addition of 7.3% of NH 4 OH solution and allowing 60 minutes precipitation/reaction time. Based on the conditions, about 6% of Th, 3% of U, 0.9% of PO 4 3- , and none of RE were recovered in the first precipitation step meanwhile, about 99% of RE, 55% of U, 76% of PO 4 3- , and of the Th were recovered in the second step. (author). 3 refs. 4 tabs. 4 figs

Commentary: Ex Situ Aqueous Mineral Carbonation

Energy Technology Data Exchange (ETDEWEB)

Gadikota, Greeshma, E-mail: gadikota@princeton.edu [Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ (United States)

2016-05-26

CO{sub 2} conversion to calcium and magnesium carbonates has garnered considerable attention since it is a thermodynamically downhill pathway to safely and permanently sequester large quantities of CO{sub 2}. This seminal work performed at The National Energy Technology Laboratory in Albany (NETL-Albany) reports the conversion of calcium- and magnesium-bearing silicate minerals, such as olivine [(Mg, Fe){sub 2}SiO{sub 4}], wollastonite (CaSiO{sub 3}), and serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}], as they are reacted with CO{sub 2} in an aqueous environment to form magnesium or calcium carbonates. This paper discusses various pretreatment methods of the starting materials, such as grinding or heat treatment of hydroxylated Mg silicates, to enhance the reaction kinetics. The effects of various chemical additives (e.g., NaCl and NaHCO{sub 3}), and reaction parameters, such as temperature, pressure, and reaction time, on the conversion are investigated. Feasibility assessments and energy and economic analyses of the direct carbonation of calcium- and magnesium-bearing minerals are presented.

Fluorometric determination of zirconium in minerals

Science.gov (United States)

Alford, W.C.; Shapiro, L.; White, C.E.

1951-01-01

The increasing use of zirconium in alloys and in the ceramics industry has created renewed interest in methods for its determination. It is a common constituent of many minerals, but is usually present in very small amounts. Published methods tend to be tedious, time-consuming, and uncertain as to accuracy. A new fluorometric procedure, which overcomes these objections to a large extent, is based on the blue fluorescence given by zirconium and flavonol in sulfuric acid solution. Hafnium is the only element that interferes. The sample is fused with borax glass and sodium carbonate and extracted with water. The residue is dissolved in sulfuric acid, made alkaline with sodium hydroxide to separate aluminum, and filtered. The precipitate is dissolved in sulfuric acid and electrolysed in a Melaven cell to remove iron. Flavonol is then added and the fluorescence intensity is measured with a photo-fluorometer. Analysis of seven standard mineral samples shows excellent results. The method is especially useful for minerals containing less than 0.25% zirconium oxide.

Changes of chemistry of precipitation on the area affected by imissions from hard coal power plant in the years 1977-1994

International Nuclear Information System (INIS)

Zablocki, Z.

1996-01-01

The changes of precipitation chemistry was studied on 9 sites in the distance 0.2-13.5 km from Dolna Odra power plant during the years 1977-1994. The results of long-term studies of changes of precipitation reaction and amounts of sulfur in precipitation on the area were shown as chronotoposequences. The results indicated on some positive changes in chemistry of precipitation in 1991-1994 years as compared to the period of 1986-1990 which manifested as decrease as yearly averages of amounts of sulfur and nitrate-nitrogen in precipitation and decrease of percentage of monthly measurements of precipitation with very acid reaction. (author). 11 refs, 2 figs, 1 tab

Cd Mobility in Anoxic Fe-Mineral-Rich Environments - Potential Use of Fe(III)-Reducing Bacteria in Soil Remediation

Science.gov (United States)

Muehe, E. M.; Adaktylou, I. J.; Obst, M.; Schröder, C.; Behrens, S.; Hitchcock, A. P.; Tylsizczak, T.; Michel, F. M.; Krämer, U.; Kappler, A.

2014-12-01

Agricultural soils are increasingly burdened with heavy metals such as Cd from industrial sources and impure fertilizers. Metal contaminants enter the food chain via plant uptake from soil and negatively affect human and environmental health. New remediation approaches are needed to lower soil metal contents. To apply these remediation techniques successfully, it is necessary to understand how soil microbes and minerals interact with toxic metals. Here we show that microbial Fe(III) reduction initially mobilizes Cd before its immobilization under anoxic conditions. To study how microbial Fe(III) reduction influences Cd mobility, we isolated a new Cd-tolerant, Fe(III)-reducing Geobacter sp. from a heavily Cd-contaminated soil. In lab experiments, this Geobacter strain first mobilized Cd from Cd-loaded Fe(III) hydroxides followed by precipitation of Cd-bearing mineral phases. Using Mössbauer spectroscopy and scanning electron microscopy, the original and newly formed Cd-containing Fe(II) and Fe(III) mineral phases, including Cd-Fe-carbonates, Fe-phosphates and Fe-(oxyhydr)oxides, were identified and characterized. Using energy-dispersive X-ray spectroscopy and synchrotron-based scanning transmission X-ray microscopy, Cd was mapped in the Fe(II) mineral aggregates formed during microbial Fe(III) reduction. Microbial Fe(III) reduction mobilizes Cd prior to its precipitation in Cd-bearing mineral phases. The mobilized Cd could be taken up by phytoremediating plants, resulting in a net removal of Cd from contaminated sites. Alternatively, Cd precipitation could reduce Cd bioavailability in the environment, causing less toxic effects to crops and soil microbiota. However, the stability and thus bioavailability of these newly formed Fe-Cd mineral phases needs to be assessed thoroughly. Whether phytoremediation or immobilization of Cd in a mineral with reduced Cd bioavailability are feasible mechanisms to reduce toxic effects of Cd in the environment remains to be

What do we really know about the role of microorganisms in iron sulfide mineral formation?

Science.gov (United States)

Picard, Aude A.; Gartman, Amy; Girguis, Peter R.

2016-01-01

Iron sulfide mineralization in low-temperature systems is a result of biotic and abiotic processes, though the delineation between these two modes of formation is not always straightforward. Here we review the role of microorganisms in the precipitation of extracellular iron sulfide minerals. We summarize the evidence that links sulfur-metabolizing microorganisms and sulfide minerals in nature and we present a critical overview of laboratory-based studies of the nucleation and growth of iron sulfide minerals in microbial cultures. We discuss whether biologically derived minerals are distinguishable from abiotic minerals, possessing attributes that are uniquely diagnostic of biomineralization. These inquiries have revealed the need for additional thorough, mechanistic and high-resolution studies to understand microbially mediated formation of a variety of sulfide minerals across a range of natural environments.

Storage of CO2 by mineral carbonation of olivine: Study of the global process for the recovery of the reaction products and the separation of chromite particles by flotation

International Nuclear Information System (INIS)

Turri, Laura

2017-01-01

This work deals with the study of direct carbonation of olivine in solution, for the chemical transformation of CO 2 emitted by the industries. The influence of operating conditions is evaluated in order to optimize the yield of the reaction. However, for environmental acceptability and economic viability of the project, the beneficiation of recoverable metals and products is considered. Chromite particles contained in olivine are unreactive during the carbonation reaction: the separation is developed by flotation upstream of the reaction. According to the results, the extraction of chromite by magnetic separation is also conceivable. Gravimetric separation by sedimentation is considered to recover residual olivine in the reaction products, in order to recycle them in the carbonation process. Products sieving allowed to concentrate carbonates (less than 40 μm) and silica (between 40 and 106 μm). However, the co-precipitation of mixed carbonates due to the presence of iron and nickel included in the magnesium matrix, compromises the purification and the optimal valorization of the solids. Moreover, the formation of a passivation layer on the particles surface limits the conversion of olivine. Pretreatment of olivine is envisaged for the leaching of nickel in ammoniac solution. Besides, preliminary dissolution of olivine and selective precipitation of species with pH control of the solution can be an interesting alternative for higher carbonation extent and more efficient purification of the products. (author)

Micro-scale experimental study of Microbial-Induced Carbonate Precipitation (MICP) by using microfluidic devices

Science.gov (United States)

Wang, Y.; Soga, K.; DeJong, J. T.; Kabla, A.

2017-12-01

Microbial-induced carbonate precipitation (MICP), one of the bio-mineralization processes, is an innovative subsurface improvement technique for enhancing the strength and stiffness of soils, and controlling their hydraulic conductivity. These macro-scale engineering properties of MICP treated soils controlled by micro-scale factors of the precipitated carbonate, such as its content, amount and distribution in the soil matrix. The precipitation process itself is affected by bacteria amount, reaction kinetics, porous medium geometry and flow distribution in the soils. Accordingly, to better understand the MICP process at the pore scale a new experimental technique that can observe the entire process of MICP at the pore-scale was developed. In this study, a 2-D transparent microfluidic chip made of Polydimethylsiloxane (PDMS) representing the soil matrix was designed and fabricated. A staged-injection MICP treatment procedure was simulated inside the microfluidic chip while continuously monitored using microscopic techniques. The staged-injection MICP treatment procedure started with the injection of bacteria suspension, followed with the bacteria setting for attachment, and then ended with the multiple injections of cementation liquid. The main MICP processes visualized during this procedure included the bacteria transport and attachment during the bacteria injection, the bacteria attachment and growth during the bacteria settling, the bacteria detachment during the cementation liquid injection, the cementation development during the cementation liquid injection, and the cementation development after the completion of cementation liquid injection. It is suggested that the visualization of the main MICP processes using the microfluidic technique can improve understating of the fundamental mechanisms of MICP and consequently help improve the treatment technique for in situ implementation of MICP.

Effect of precipitating agent on the catalytic behaviour of precipitated iron catalysts

International Nuclear Information System (INIS)

Motjope, T.R.; Dlamini, H.T.; Pollak, H.; Coville, N.J.

1999-01-01

Iron precipitated catalysts have been prepared using different precipitating agents (NH 4 OH, K 2 CO 3 ) at different pH values. In situ Moessbauer (MES) study of the reduced catalyst prepared using NH 4 OH revealed the presence of superparamagnetic Fe 2+ , Fe 3+ and magnetically split α-Fe only, whereas the catalyst prepared with K 2 CO 3 also showed an extra magnetic sextuplet of Fe 3 O 4 . For both catalyst systems, in situ MES revealed that during Fischer-Tropsch synthesis α-Fe was converted into ε'-Fe 2,2 C and finally into χ-Fe 2,5 C when the synthesis time was increased. The rate of formation of hydrocarbons was observed to increase with the increase in the degree of carburisation with the NH 4 OH catalyst showing a higher rate of reaction. The K 2 CO 3 catalyst exhibited higher olefin selectivity than the NH 4 OH catalyst under similar pH conditions

Effect of carbide precipitation on the corrosion behavior of Inconel alloy 690

International Nuclear Information System (INIS)

Sarver, J.M.; Crum, J.R.; Mankins, W.L.

1987-01-01

Intergranular carbide precipitation reactions have been shown to affect the stress corrosion cracking (SCC) resistance of nickel-chromium-iron alloys in environments relative to nuclear steam generators. Carbon solubility curves, time-temperature-sensitization plots and other carbide precipitation data are presented for alloy 690 as an aid in developing heat treatments for improved SCC resistance

Comparison of Four Strong Acids on the Precipitation Potential of Gypsum in Brines During Distillation of Pretreated, Augmented Urine

Science.gov (United States)

Muirhead, Dean; Carrier, Christopher

2012-01-01

In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines

Simplified models of transport and reactions in conditions of CO2 storage in saline aquifers

Science.gov (United States)

Suchodolska, Katarzyna; Labus, Krzysztof

2016-04-01

Simple hydrogeochemical models may serve as tools of preliminary assessment of CO2 injection and sequestraton impact on the aquifer and cap-rocks. In order to create models of reaction and transport in conditions of CO2 injection and storage, the TOUGHREACT simulator, and the Geochemist's Workbench software were applied. The chemical composition of waters for kinetic transport models based on the water - rock equilibrium calculations. Analyses of reaction and transport of substances during CO2 injection and storage period were carried out in three scenarios: one-dimensional radial model, and two-dimensional model of CO2 injection and sequestration, and one-dimensional model of aquifer - cap-rock interface. Modeling was performed in two stages. The first one simulated the immediate changes in the aquifer and insulating rocks impacted by CO2 injection (100 days in case of reaction model and 30 years in transport and reaction model), the second - enabled assessment of long-term effects of sequestration (20000 years). Reactions' quality and progress were monitored and their effects on formation porosity and sequestration capacity in form of mineral, residual and free phase of CO2 were calculated. Calibration of numerical models (including precipitation of secondary minerals, and correction of kinetics parameters) describing the initial stage of injection, was based on the experimental results. Modeling allowed to evaluate the pore space saturation with gas, changes in the composition and pH of pore waters, relationships between porosity and permeability changes and crystallization or dissolution minerals. We assessed the temporal and spatial extent of crystallization processes, and the amount of carbonates trapping. CO2 in mineral form. The calculated sequestration capacity of analyzed formations reached n·100 kg/m3 for the: dissolved phase - CO(aq), gas phase - CO2(g) and mineral phase, but as much as 101 kg/m3 for the supercritical phase - SCCO2. Processes of gas

[The role of the working conditions in shaping the specific and nonspecific body reactions of miners in vibration-hazardous jobs].

Science.gov (United States)

Lastkov, D O

1998-08-01

An analysis was carried out of bodily functional status in miners engaged in basic mining occupations with known vibration-related health hazards (coal hewers, drifters), presenting with different stages of vibration pathology. Patterns were ascertained of chief components of both specific and unspecific bodily systemic reactions to a combined action of physical industrial factors (vibration, noise, dust, heating, microclimate). Important for those subjects engaged in occupations with vibration-related health threats are parameters characterizing labour conditions, such as, in the first place, integral-and-service duration-related exposure doses of industrial factors which are believed to be probabilistic risk factors for vibration pathology.

Phosphates (V) recovery from phosphorus mineral fertilizers industry wastewater by continuous struvite reaction crystallization process.

Science.gov (United States)

Hutnik, Nina; Kozik, Anna; Mazienczuk, Agata; Piotrowski, Krzysztof; Wierzbowska, Boguslawa; Matynia, Andrzej

2013-07-01

Continuous DT MSMPR (Draft Tube Mixed Suspension Mixed Product Removal) crystallizer was provided with typical wastewater from phosphorus mineral fertilizers industry (pH < 4, 0.445 mass % of PO4(3-), inorganic impurities presence), dissolved substrates (magnesium and ammonium chlorides) and solution alkalising the environment of struvite MgNH4PO4·6H2O reaction crystallization process. Research ran in constant temperature 298 K assuming stoichiometric proportions of substrates or 20% excess of magnesium ions. Influence of pH (8.5-10) and mean residence time (900-3600 s) on product size distribution, its chemical composition, crystals shape, size-homogeneity and process kinetics was identified. Crystals of mean size ca. 25-37 μm and homogeneity CV 70-83% were produced. The largest crystals, of acceptable homogeneity, were produced using 20% excess of magnesium ions, pH 9 and mean residence time 3600 s. Under these conditions nucleation rate did not exceed 9 × 10(7) 1/(s m(3)) according to SIG (Size Independent Growth) MSMPR kinetic model. Linear crystal growth rate was 4.27 × 10(-9) m/s. Excess of magnesium ions influenced struvite reaction crystallization process yield advantageously. Concentration of phosphate(V) ions decreased from 0.445 to 9.2 × 10(-4) mass %. This can be regarded as a very good process result. In product crystals, besides main component - struvite, all impurities from wastewater were detected analytically. Copyright © 2013 Elsevier Ltd. All rights reserved.

Final Report - Montana State University - Microbial Activity and Precipitation at Solution-Solution Mixing Zones in Porous Media

Energy Technology Data Exchange (ETDEWEB)

Gerlach, Robin [Montana State University

2014-10-31

Background. The use of biological and chemical processes that degrade or immobilize contaminants in subsurface environments is a cornerstone of remediation technology. The enhancement of biological and chemical processes in situ, involves the transport, displacement, distribution and mixing of one or more reactive agents. Biological and chemical reactions all require diffusive transport of solutes to reaction sites at the molecular scale and accordingly, the success of processes at the meter-scale and larger is dictated by the success of phenomena that occur at the micron-scale. However, current understanding of scaling effects on the mixing and delivery of nutrients in biogeochemically dynamic porous media systems is limited, despite the limitations this imposes on the efficiency and effectiveness of the remediation challenges at hand. Objectives. We therefore proposed to experimentally characterize and computationally describe the growth, evolution, and distribution of microbial activity and mineral formation as well as changes in transport processes in porous media that receive two or more reactive amendments. The model system chosen for this project was based on a method for immobilizing 90Sr, which involves stimulating microbial urea hydrolysis with ensuing mineral precipitation (CaCO3), and co-precipitation of Sr. Studies at different laboratory scales were used to visualize and quantitatively describe the spatial relationships between amendment transport and consumption that stimulate the production of biomass and mineral phases that subsequently modify the permeability and heterogeneity of porous media. Biomass growth, activity, and mass deposition in mixing zones was investigated using two-dimensional micro-model flow cells as well as flow cells that could be analyzed using synchrotron-based x-ray tomography. Larger-scale flow-cell experiments were conducted where the spatial distribution of media properties, flow, segregation of biological activity and

A modular continuous flow reactor system for the selective bio-oxidation of iron and precipitation of schwertmannite from mine-impacted waters.

Science.gov (United States)

Hedrich, Sabrina; Johnson, D Barrie

2012-02-01

A novel modular bioremediation system which facilitates the selective removal of soluble iron from extremely acidic (pH ∼2) metal-rich wastewaters by ferrous iron oxidation and selective precipitation of the ferric iron produced is described. In the first of the three modules, rapid ferrous iron oxidation was mediated by the recently-characterized iron-oxidizing autotrophic acidophile, "Ferrovum myxofaciens", which grew as long "streamers" within the reactor. Over 90% of the iron present in influent test liquors containing 280mg/L iron was oxidized at a dilution rate of 0.41h(-1), in a proton-consuming reaction. The ferric iron-rich solutions produced were pumped into a second reactor where controlled addition of sodium hydroxide caused the water pH to increase to 3.5 and ferric iron to precipitate as the mineral schwertmannite. Addition of a flocculating agent promoted rapid aggregation and settling of the fine-grain schwertmannite particles. A third passive module (a packed-bed bioreactor, also inoculated with "Fv. myxofaciens") acted as a polishing reactor, lowering soluble iron concentrations in the processed water to iron from a synthetic acidic (pH 2.1) mine water that contained soluble aluminum, copper, manganese and zinc in addition to iron. Schwertmannite was again produced, with little or no co-precipitation of other metals. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enhanced⁹⁹Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

OpenAIRE

Um, W; Luksic, SA; Wang, G; Saslow, S; Kim, DS; Schweiger, MJ; Soderquist, CZ; Bowden, ME; Lukens, WW; Kruger, AA

2017-01-01

© 2017 Elsevier B.V. Technetium ( 99 Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt sample...

Mechanism of calcium phosphates precipitation in liquid crystals

International Nuclear Information System (INIS)

Prelot, B.; Zemb, T.

2004-04-01

The possibility of using as a precursor an easily wet meso-porous powder would be a breakthrough in the preparation of nuclear waste storage ceramics. A concentrated solution containing ions to be stored would wet a dry powder and then, subjected to mild compression, lead to a micro-crystalline matrix of calcium phosphate at acceptable temperatures. Since no porous calcium phosphate different from calcined bone (patented) is described as porous precursor, we have compared the different synthesis routes towards meso-porous ceramics. First, we considered homogeneous precipitation of slats in water: using initially off-stoichiometry in reaction, micron-sized hydroxyapatite particles are produced with a specific surface up to 100 m 2 /g. Then, we consider the classical route of precipitation of an hybrid material in the miscibility gap of a phase diagram, when an hexagonal liquid crystal is used a matrix for precipitation. The surfactant family consists in single chain surfactants containing phosphates as head-group to poison the growing surface of calcium phosphate nano-domains. Since the reaction is still too brutal, we considered using a cat-anionic precursor material of controllable surface charge. For certain concentrations and molar ratios, a new structure not yet described in surfactant precipitation literature is observed: since the periodicity is lower than twice the chain length, a disordered constant curvature monolayer (instead of the classical cylinder of twice chain length diameter) of surfactant is implied. Finally, we have investigated synthesis routes implying slow dissolution of pre-formed calcium phosphate in an already existing hexagonal matrix. For all these routes of synthesis, micro-structural determinations using SAXS, WARS and BET are performed, with a special attention to comparison of the precipitation material, the matrix obtained with all elements present, and also the material obtained after calcinations. (authors)

Mechanisms for chemostatic behavior in catchments: implications for CO2 consumption by mineral weathering

Science.gov (United States)

Clow, David W.; Mast, M. Alisa

2010-01-01

Concentrations of weathering products in streams often show relatively little variation compared to changes in discharge, both at event and annual scales. In this study, several hypothesized mechanisms for this “chemostatic behavior” were evaluated, and the potential for those mechanisms to influence relations between climate, weathering fluxes, and CO2 consumption via mineral weathering was assessed. Data from Loch Vale, an alpine catchment in the Colorado Rocky Mountains, indicates that cation exchange and seasonal precipitation and dissolution of amorphous or poorly crystalline aluminosilicates are important processes that help regulate solute concentrations in the stream; however, those processes have no direct effect on CO2 consumption in catchments. Hydrograph separation analyses indicate that old water stored in the subsurface over the winter accounts for about one-quarter of annual streamflow, and almost one-half of annual fluxes of Na and SiO2 in the stream; thus, flushing of old water by new water (snowmelt) is an important component of chemostatic behavior. Hydrologic flushing of subsurface materials further induces chemostatic behavior by reducing mineral saturation indices and increasing reactive mineral surface area, which stimulate mineral weathering rates. CO2 consumption by carbonic acid mediated mineral weathering was quantified using mass-balance calculations; results indicated that silicate mineral weathering was responsible for approximately two-thirds of annual CO2 consumption, and carbonate weathering was responsible for the remaining one-third. CO2 consumption was strongly dependent on annual precipitation and temperature; these relations were captured in a simple statistical model that accounted for 71% of the annual variation in CO2 consumption via mineral weathering in Loch Vale.

Birnessite catalysis of the Maillard Reaction: Its significance in natural humification

Science.gov (United States)

Jokic, A.; Frenkel, A. I.; Vairavamurthy, M. A.; Huang, P. M.

Although mineral colloids are known to play a significant role in transforming organic matter in soils and sediments, there still are many gaps in our understanding of the mechanisms of organic-mineral interactions. In this study, we investigated the role of a major oxide-mineral birnessite (a form of Mn(IV) oxide) in catalyzing the condensation reaction between sugars and amino acids, the Maillard reaction, for forming humic substances. The Maillard reaction is perceived to be a major pathway in natural humification. Using a suite of spectroscopic methods (including ESR, XANES, EXAFS and 13C NMR), our results show that Mn(IV) oxide markedly accelerates the Maillard reaction between glucose and glycine at ranges of temperatures and pH typical of natural environments. These results demonstrate the importance of manganese oxide catalysis in the Maillard reaction, and its significance in the natural abiotic formation of humic substances.

Mineral CO2 sequestration in alkaline solid residues

International Nuclear Information System (INIS)

Huijgen, W.J.J.; Comans, R.N.J.; Witkamp, G.J.

2004-12-01

Mineral carbonation is a promising sequestration route for the permanent and safe storage of carbon dioxide. In addition to calcium- or magnesium-containing primary minerals, suitable alkaline solid residues can be used as feedstock. The use of alkaline residues has several advantages, such as their availability close to CO2 sources and their higher reactivity for carbonation than primary minerals. In addition, the environmental quality of residues can potentially be improved by carbonation. In this study, key factors of the mineral CO2 sequestration process are identified, their influence on the carbonation process is examined, and environmental properties of the reaction products with regard to their possible beneficial utilization are investigated. The use of alkaline solid residues forms a potentially attractive alternative for the first mineral sequestration plants

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO2 from Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Devenney, Martin; Gilliam, Ryan; Seeker, Randy

2014-06-01

The objective of this project is to demonstrate an innovative process to mineralize CO2 from flue gas directly to reactive carbonates and maximize the value and versatility of its beneficial use products. The program scope includes the design, construction, and testing of a CO2 Conversion to Material Products (CCMP) Pilot Demonstration Plant utilizing CO2 from the flue gas of a power production facility in Moss Landing, CA as well as flue gas from coal combustion. This topical report covers Phase 2b, which is the construction phase of pilot demonstration subsystems that make up the integrated plant. The subsystems included are the mineralization subsystem, the Alkalinity Based on Low Energy (ABLE) subsystem, the waste calcium oxide processing subsystem, and the fiber cement board production subsystem. The fully integrated plant is now capable of capturing CO2 from various sources (gas and coal) and mineralizing into a reactive calcium carbonate binder and subsequently producing commercial size (4ftx8ft) fiber cement boards. The topical report provides a description of the “as built” design of these subsystems and the results of the commissioning activities that have taken place to confirm operability. At the end of Phase 2b, the CCMP pilot demonstration is fully ready for testing.

Assessment of CO2 Mineralization and Dynamic Rock Properties at the Kemper Pilot CO2 Injection Site

Science.gov (United States)

Qin, F.; Kirkland, B. L.; Beckingham, L. E.

2017-12-01

CO2-brine-mineral reactions following CO2 injection may impact rock properties including porosity, permeability, and pore connectivity. The rate and extent of alteration largely depends on the nature and evolution of reactive mineral interfaces. In this work, the potential for geochemical reactions and the nature of the reactive mineral interface and corresponding hydrologic properties are evaluated for samples from the Lower Tuscaloosa, Washita-Fredericksburg, and Paluxy formations. These formations have been identified as future regionally extensive and attractive CO2 storage reservoirs at the CO2 Storage Complex in Kemper County, Mississippi, USA (Project ECO2S). Samples from these formations were obtained from the Geological Survey of Alabama and evaluated using a suite of complementary analyses. The mineral composition of these samples will be determined using petrography and powder X-ray Diffraction (XRD). Using these compositions, continuum-scale reactive transport simulations will be developed and the potential CO2-brine-mineral interactions will be examined. Simulations will focus on identifying potential reactive minerals as well as the corresponding rate and extent of reactions. The spatial distribution and accessibility of minerals to reactive fluids is critical to understanding mineral reaction rates and corresponding changes in the pore structure, including pore connectivity, porosity and permeability. The nature of the pore-mineral interface, and distribution of reactive minerals, will be determined through imaging analysis. Multiple 2D scanning electron microscopy (SEM) backscattered electron (BSE) images and energy dispersive x-ray spectroscopy (EDS) images will be used to create spatial maps of mineral distributions. These maps will be processed to evaluate the accessibility of reactive minerals and the potential for flow-path modifications following CO2 injection. The "Establishing an Early CO2 Storage Complex in Kemper, MS" project is funded by

On the interaction of pure and impure supercritical CO2 with rock forming minerals in saline aquifers: An experimental geochemical approach

International Nuclear Information System (INIS)

Wilke, Franziska D.H.; Vásquez, Mónica; Wiersberg, Thomas; Naumann, Rudolf; Erzinger, Jörg

2012-01-01

The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO 2 on rock forming minerals of possible CO 2 storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO 2 and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO 2 , brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO 2 the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP–MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO 2 (99.5 vol.%) and SO 2 or NO 2 impurities (0.5 vol.%) suggest the formation of H 2 SO 4 and HNO 3 , reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO 2 . For pure CO 2 a pH of around 4 was obtained using silicates and anhydrite, and 7–8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO 2 experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO 2 + NO 2 . Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO 2 . Nonetheless, precipitated secondary carbonates could not be identified.

The Thermodynamics of Selenium Minerals in Near-Surface Environments

Directory of Open Access Journals (Sweden)

Vladimir Krivovichev

2017-10-01

Full Text Available Selenium compounds are relatively rare as minerals; there are presently only 118 known mineral species. This work is intended to codify and systematize the data of mineral systems and the thermodynamics of selenium minerals, which are unstable (selenides or formed in near-surface environments (selenites, where the behavior of selenium is controlled by variations of the redox potential and the acidity of solutions at low temperatures and pressures. These parameters determine the migration of selenium and its precipitation as various solid phases. All selenium minerals are divided into four groups—native selenium, oxide, selenides, and oxysalts—anhydrous selenites (I and hydrous selenites and selenates (II. Within each of the groups, minerals are codified according to the minimum number of independent elements necessary to define the composition of the mineral system. Eh–pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 9.0 software package. The Eh–pH diagrams of the Me–Se–H2O systems (where Me = Co, Ni, Fe, Cu, Pb, Zn, Cd, Hg, Ag, Bi, As, Sb, Al and Ca were plotted for the average contents of these elements in acidic waters in the oxidation zones of sulfide deposits. The possibility of the formation of Zn, Cd, Ag and Hg selenites under natural oxidation conditions in near surface environments is discussed.

Photocatalytic properties of BiVO{sub 4} prepared by the co-precipitation method: Degradation of rhodamine B and possible reaction mechanisms under visible irradiation

Energy Technology Data Exchange (ETDEWEB)

Martinez-de la Cruz, A., E-mail: azael70@yahoo.com.mx [Facultad de Ingenieria Mecanica y Electrica, Universidad Autonoma de Nuevo Leon, Ciudad Universitaria, C.P. 66451, San Nicolas de los Garza, N.L. (Mexico); Perez, U.M. Garcia [Facultad de Ingenieria Mecanica y Electrica, Universidad Autonoma de Nuevo Leon, Ciudad Universitaria, C.P. 66451, San Nicolas de los Garza, N.L. (Mexico)

2010-02-15

Bismuth vanadate (BiVO{sub 4}) was synthesized by the co-precipitation method at 200 {sup o}C. The photocatalytic activity of the oxide was tested for the photodegradation of rhodamine B under visible light irradiation. The analysis of the total organic carbon showed that the mineralization of rhodamine B over a BiVO{sub 4} photocatalyst ({approx}40% after 100 h of irradiation) is feasible. In the same way, a gas chromatography analysis coupled with mass spectroscopy revealed the existence of organic intermediates during the photodegradation process such as ethylbenzene, o-xylene, m-xylene, and phthalic anhydride. The modification of variables such as dispersion pH, amount of dissolved O{sub 2}, and irradiation source was studied in order to know the details about the photodegradation mechanism.

Precipitation of gold by the reaction of aqueous gold(III)-chloride with cyanobacteria at 25-80 C -- Studied by x-ray absorption spectroscopy

International Nuclear Information System (INIS)

Lengke, M. F.; Ravel, B.; Fleet, M. E.; Wanger, G.; Gordon, R. A.; Southam, G.

2007-01-01

The mechanisms of gold precipitation by the interaction of cyanobacteria (Plectonema boryanum UTEX 485) and gold(III) chloride aqueous solutions (7.6 mmol/L final gold) have been studied at 25, 60, and 80 C, using both laboratory and real-time synchrotron radiation absorption spectroscopy experiments. Addition of aqueous gold(III) chloride to the cyanobacterial culture initially promoted the precipitation of amorphous gold(I) sulfide at the cell walls and finally caused the formation of octahedral (111) platelets (<1 to 6 (micro)m) of gold metal near cell surfaces and in solutions. X-ray absorption spectroscopy results confirmed that the reduction mechanism of gold(III) chloride to elemental gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I) sulfide, with sulfur originating from cyanobacterial proteins, presumably cysteine or methionine. Although the bioreduction of gold(III) chloride to gold(I) sulfide was relatively rapid at all temperatures, the reaction rate increased with the increase in temperature. At the completion of the experiments, elemental gold was the major species present at all temperatures

The hydrogeochemical characteristics of the certain uranium deposit and their relationship with uranium mineralization

International Nuclear Information System (INIS)

Li Huanguang

2010-01-01

On the basis of previous work, this paper studies characteristics of the stratum,lithology,structure, ore bodies, ore and wall rocks and the relations between hydrochemical characteristics and uranium mineraliztion are stressed and anaysed.The environmental index of hydrogeochemisty is closely related with the uranium form, migration,and precipitation. According to negative ion, the ground water is classified into HCO3-,SO42-, HCO3--SO42-and HCO3-Cl-. For deposit genesis, uranium source comes from two parts; there are five mineralizations such as leaching, adsorption, hydrogeochemistry, palaeo-climatology and geothermal mineralization. Hydrogeochemical mineralization is the key process.. (authors)

The study on the pH behavior of the HFSC leached solution. The development of model considering the pozzolanic reaction

International Nuclear Information System (INIS)

Yoshida, Yasushi; Mihara, Morihiro

2005-09-01

The development of low alkalinity cement (high fly-ash contained silica-fume cement, HFSC) has been carried out in JNC. Low alkalinity for this cement is achieved by adding pozzolan materials to ordinary portland cement and Ca ion attributed to high alkalinity is consumed by forming CHS gel. This report shows the calculation model to predict the composition for HFSC reacted solution which considers cement mineral dissolution/precipitation as equilibrium reactions and dissolution for pozzolan material as a kinetic reaction. The dissolution kinetic equation for pozzolan material is also derived from leaching experiment. This calculation model is applied to the leaching experiment where powdered HFSC was reacted with distilled water. As a result of comparison between calculation and experimental measurement at the early stage for leaching the tendency for pH, pH decrease from 12.5 to 11.5 drastically, could be interpreted by this calculation model, however, after this drastic pH decreasing pH predicted by calculation model also shows drastic decrease whereas pH for experiment decreased mildly around pH 11.5. It could be thought that this difference between experiment and calculation is caused by inappropriate modelling for CSH gel dissolution/precipitation of C/S value lower than 1.0. For this C/S range thermodynamic data for intermediate and end member for solid solution for CSH gel and in addition the reaction kinetic for CSH gel should be examined in detail. (author)

Trace Elements and Minerals in Fumarolic Sulfur: The Case of Ebeko Volcano, Kuriles

Directory of Open Access Journals (Sweden)

E. P. Shevko

2018-01-01

Full Text Available Native sulfur deposits on fumarolic fields at Ebeko volcano (Northern Kuriles, Russia are enriched in chalcophile elements (As-Sb-Se-Te-Hg-Cu and contain rare heavy metal sulfides (Ag2S, HgS, and CuS, native metal alloys (Au2Pd, and some other low-solubility minerals (CaWO4, BaSO4. Sulfur incrustations are impregnated with numerous particles of fresh and altered andesite groundmass and phenocrysts (pyroxene, magnetite as well as secondary minerals, such as opal, alunite, and abundant octahedral pyrite crystals. The comparison of elemental abundances in sulfur and unaltered rocks (andesite demonstrated that rock-forming elements (Ca, K, Fe, Mn, and Ti and other lithophile and chalcophile elements are mainly transported by fumarolic gas as aerosol particles, whereas semimetals (As, Sb, Se, and Te, halogens (Br and I, and Hg are likely transported as volatile species, even at temperatures slightly above 100°C. The presence of rare sulfides (Ag2S, CuS, and HgS together with abundant FeS2 in low-temperature fumarolic environments can be explained by the hydrochloric leaching of rock particles followed by the precipitation of low-solubility sulfides induced by the reaction of acid solutions with H2S at ambient temperatures. The elemental composition of native sulfur can be used to qualitatively estimate elemental abundances in low-temperature fumarolic gases.

Study On Precipitation Of UO2 Ex-AUC Powder. Part I: Precipitation Of AUC By (NH4)2CO3 From Uranyl Fluoride Solution

International Nuclear Information System (INIS)

Nguyen Trong Hung; Le Ba Thuan; Do Van Khoai; Nguyen Thanh Thuy; Nguyen Van Tung

2011-01-01

In this paper, Ammonium Uranyl Carbonate (AUC) powders were prepared by precipitation method in solution. UO 2 F 2 /HF, ammonium carbonate (AC), and ammonium hydroxide solution were used as precursors for precipitation. The influence of C/U ratio (mol/mol), AC concentration (g/L), reaction temperature ( o C), on characteristics of AUC powders was also investigated. Then, the synthesized AUC powders were analyzed (to define) phase composition (X-ray), fluorine content, morphology (by SEM), and specific surface area (BET). (author)

Organic influences on inorganic patterns of diffusion-controlled precipitation in gels

Science.gov (United States)

Barge, Laura M.; Nealson, Kenneth H.; Petruska, John

2010-06-01

The well-known AgNO 3/K 2CrO 4 reaction-diffusion system produces periodic bands of silver chromate precipitate in gelatin, but only randomly oriented crystals in agarose gel. We show that comparable bands can be produced in agarose gel by adding small amounts of simple organic acids (e.g., acetic acid, N-acetyl glycine, and N-acetyl alanine) that suppress crystal growth and promote formation of rounded particles of precipitate. These results indicate that α-carboxyl groups of amino acids or short peptides in gelatin under mildly acidic conditions can induce periodic band patterns in diffusion-controlled silver chromate precipitates.

Effects of Calcium Source on Biochemical Properties of Microbial CaCO3 Precipitation.

Science.gov (United States)

Xu, Jing; Du, Yali; Jiang, Zhengwu; She, Anming

2015-01-01

The biochemical properties of CaCO3 precipitation induced by Sporosarcina pasteurii, an ureolytic type microorganism, were investigated. Effects of calcium source on the precipitation process were examined, since calcium source plays a key role in microbiologically induced mineralization. Regardless of the calcium source type, three distinct stages in the precipitation process were identified by Ca(2+), NH4 (+), pH and cell density monitoring. Compared with stage 1 and 3, stage 2 was considered as the most critical part since biotic CaCO3 precipitation occurs during this stage. Kinetics studies showed that the microbial CaCO3 precipitation rate for calcium lactate was over twice of that for calcium nitrate, indicating that calcium lactate is more beneficial for the cell activity, which in turn determines urease production and CaCO3 precipitation. X-ray diffraction analysis confirmed the CaCO3 crystal as calcite, although scanning electron microscopy revealed a difference in crystal size and morphology if calcium source was different. The findings of this paper further suggest a promising application of microbiologically induced CaCO3 precipitation in remediation of surface and cracks of porous media, e.g., cement-based composites, particularly by using organic source of calcium lactate.

Dilution physics modeling: Dissolution/precipitation chemistry

International Nuclear Information System (INIS)

Onishi, Y.; Reid, H.C.; Trent, D.S.

1995-09-01

This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affect safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics

Recovery Act: An Integrated Experimental and Numerical Study: Developing a Reaction Transport Model that Couples Chemical Reactions of Mineral Dissolution/Precipitation with Spatial and Temporal Flow Variations.

Energy Technology Data Exchange (ETDEWEB)

Saar, Martin O. [ETH Zurich (Switzerland); Univ. of Minnesota, Minneapolis, MN (United States); Seyfried, Jr., William E. [Univ. of Minnesota, Minneapolis, MN (United States); Longmire, Ellen K. [Univ. of Minnesota, Minneapolis, MN (United States)

2016-06-24

A total of 12 publications and 23 abstracts were produced as a result of this study. In particular, the compilation of a thermodynamic database utilizing consistent, current thermodynamic data is a major step toward accurately modeling multi-phase fluid interactions with solids. Existing databases designed for aqueous fluids did not mesh well with existing solid phase databases. Addition of a second liquid phase (CO2) magnifies the inconsistencies between aqueous and solid thermodynamic databases. Overall, the combination of high temperature and pressure lab studies (task 1), using a purpose built apparatus, and solid characterization (task 2), using XRCT and more developed technologies, allowed observation of dissolution and precipitation processes under CO2 reservoir conditions. These observations were combined with results from PIV experiments on multi-phase fluids (task 3) in typical flow path geometries. The results of the tasks 1, 2, and 3 were compiled and integrated into numerical models utilizing Lattice-Boltzmann simulations (task 4) to realistically model the physical processes and were ultimately folded into TOUGH2 code for reservoir scale modeling (task 5). Compilation of the thermodynamic database assisted comparisons to PIV experiments (Task 3) and greatly improved Lattice Boltzmann (Task 4) and TOUGH2 simulations (Task 5). PIV (Task 3) and experimental apparatus (Task 1) have identified problem areas in TOUGHREACT code. Additional lab experiments and coding work has been integrated into an improved numerical modeling code.

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

Science.gov (United States)

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Linking Global Patterns of Nitrogen Resorption with Nitrogen Mineralization During Litter Decomposition

Science.gov (United States)

Deng, M.; Liu, L.; Jiang, L.

2017-12-01

The nitrogen (N) cycle in terrestrial ecosystems is strongly influenced by resorption prior to litter fall and by mineralization after litter fall. Although both resorption and mineralization make N available to plants and are influenced by climate, their linkage in a changing environment remains largely unknown. Here, we show that, at the global scale, increasing N resorption efficiency has a negative effect on the N mineralization rate. With increasing temperature and precipitation, the increasing rate of the N cycle is closely related to the shift from the more conservative resorption pathway to an acquiring mineralization pathway. Furthermore, systems with faster N-cycle rates support plants with higher foliar N:P ratios and microbes with lower fungi:bacteria ratios. We highlight the importance of considering the geographic pattern and the dynamic interaction between N resorption and N mineralization, which should be incorporated into earth-system models to improve the simulation of nutrient constraints on ecosystem productivity.

Neutron induced autoradiography of some minerals from the Allchar mine

International Nuclear Information System (INIS)

Lazaru, A.; Ilic, R.; Skvarc, J.; Kristof, E.S.; Stafilov, T.

1999-01-01

The mineral lorandite from the Allchar mine (Kavadarci, Macedonia) will be used to estimate the average solar neutrino flux. Here, the amount of 205 Pb isotope induced by the 205 Tl(ν e , e - ) 205 Pb reaction is measured and converted to neutrino flux. To determine the few 205 Pb atoms that are produced by solar neutrinos in the Tl ore it is necessary to know all the interfering reactions and/or impurities producing 205 Pb. The concentration and/or spatial distribution of some impurities such as U in lorandite should be known as accurately as possible. In the present work uranium and boron concentrations in some minerals from the Allchar mine (lorandite, realgar, stibnite, orpiment and dolomite) were measured by neutron induced autoradiography. The tracks of 10 B(n, α) and 235 U(n, f) reaction products were recorded by CR-39 and phosphate glass (PSK-50) etched track detectors, respectively. Results showed that uranium is nonuniformly distributed in some of the minerals (orpiment, realgar and lorandite). Average uranium concentration levels varied from 0.01 to 1 μg g -1 . The highest boron concentration (about 6.7 μg g -1 ) was found in stibnite while its concentration in other minerals was below the detection limit (about 1 μg g -1 ) of the technique

Pyrite formation and mineral transformation pathways upon sulfidation of ferric hydroxides depend on mineral type and sulfide concentration

NARCIS (Netherlands)

Peiffer, Stefan; Behrends, Thilo; Hellige, Katrin; Larese-Casanova, Philip; Wan, Moli; Pollok, Kilian

2015-01-01

The reaction of ferric (hydr)oxides with dissolved sulfide does not lead to the instantaneous production of thermodynamically stable products but can induce a variety of mineral transformations including the formation of metastable intermediates. The importance of the various transformation pathways

Carbonate precipitation under bulk acidic conditions as a potential biosignature for searching life on Mars

NARCIS (Netherlands)

Fernández-Remolar, David C.; Preston, Louisa J.; Sánchez-Román, Mónica; Izawa, Matthew R.M.; Huang, L.; Southam, Gordon; Banerjee, Neil R.; Osinski, Gordon R.; Flemming, Roberta; Gómez-Ortíz, David; Prieto-Ballesteros, Olga; Rodríguez, Nuria; Amils, Ricardo; Darby Dyar, M.

2012-01-01

Recent observations of carbonate minerals in ancient Martian rocks have been interpreted as evidence for the former presence of circumneutral solutions optimal for carbonate precipitation. Sampling from surface and subsurface regions of the low-pH system of Río Tinto has shown, unexpectedly, that

Tannins in Mineral Processing and Extractive Metallurgy

Directory of Open Access Journals (Sweden)

Jordan Rutledge

2015-08-01

Full Text Available This study provides an up to date review of tannins, specifically quebracho, in mineral processing and metallurgical processes. Quebracho is a highly useful reagent in many flotation applications, acting as both a depressant and a dispersant. Three different types of quebracho are mentioned in this study; quebracho “S” or Tupasol ATO, quebracho “O” or Tupafin ATO, and quebracho “A” or Silvafloc. It should be noted that literature often refers simply to “quebracho” without distinguishing a specific type. Quebracho is most commonly used in industry as a method to separate fluorite from calcite, which is traditionally quite challenging as both minerals share a common ion—calcium. Other applications for quebracho in flotation with calcite minerals as the main gangue source include barite and scheelite. In sulfide systems, quebracho is a key reagent in differential flotation of copper, lead, zinc circuits. The use of quebracho in the precipitation of germanium from zinc ores and for the recovery of ultrafine gold is also detailed in this work. This analysis explores the wide range of uses and methodology of quebracho in the extractive metallurgy field and expands on previous research by Iskra and Kitchener at Imperial College entitled, “Quebracho in Mineral Processing”.

The redox properties of the natural iron-bearing clay mineral ferruginous smectite SWA-1: a combined electrochemical and spectroscopic study

International Nuclear Information System (INIS)

Gorski, Christopher A.; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B.

2012-01-01

Document available in extended abstract form only. Iron-bearing clay minerals are ubiquitous in the environment and clay-mineral-based materials have been proposed to be part of backfill material in nuclear waste repositories. Laboratory and field studies have confirmed that structural iron (Fe) in clay minerals participates in redox reactions with organic pollutants, metals, and radionuclides, thus influencing their transport and reactivity. Knowledge of the redox properties of Fe-bearing clay minerals is therefore essential for understanding and predicting the fate, mobility, and bioavailability subsurface contaminants. A quantitative understanding of clay mineral redox behavior remains lacking, however, due to constraints in previous experimental approaches and the complex structural changes that accompany changes in the Fe oxidation state. This work provides a quantitative means for measuring the redox properties of Fe-bearing clay minerals, which can be applied to both field and laboratory studies tracking radionuclide-clay mineral redox reactions. Here we use mediated electrochemical reduction and oxidation to determine the electron accepting and donating capacities of several natural Fe-bearing clay minerals with different structural Fe content (2.3 to 21 wt-%) and varied redox histories. Results indicate that the fraction of redox-active Fe in clay minerals is mineral-dependent, and is linked to the thermodynamics of reduction and oxidation as well as to the ability of clay minerals to conduct electrons and facilitate structural re-arrangements required to maintain charge balance. The reduction potential (E H ) characteristics of a natural ferruginous smectite (SWa-1) were further characterized as a function of solution conditions and repeated Fe reduction and oxidation cycles. SWa-1 samples were analyzed with Moessbauer spectroscopy (MS) and X-ray absorption spectroscopy (XAS) to link observed redox potential behavior to structural properties and changes

Interaction of trivalent actinides and lanthanides with the water/mineral interface

International Nuclear Information System (INIS)

Stumpf, Thorsten

2008-07-01

The behavior of radionuclides in the natural environment (geo-, hydro- and biosphere) is determined by interface reactions like sorption and incorporation processes. In general natural geochemical systems are very complex. This complexity is a result of a combination of several single reactions on the molecular scale. For the understanding of complex systems and for the prediction of radionuclide behavior in the natural environment it is of cardinal importance to clarify the individual reaction mechanisms at the solid/solution interface. The establishment of clarification requires the application of modern spectroscopic and microscopic methods. The presented studies, which are summarized in this professional dissertation, deal with investigations concerning the interaction of lanthanides and trivalent actinides with mineral surfaces. Several single reactions were deduced from these investigations. In particular the combination of time resolved laser fluorescence spectroscopy (TRLFS) with x-ray absorption spectroscopy (XAS) was proven to be very effective for the elucidation of complex geochemical reactions at the water/mineral interface. (orig.)

Dynamic simulation of the in-tank precipitation process

International Nuclear Information System (INIS)

Hang, T.; Shanahan, K.L.; Gregory, M.V.; Walker, D.D.

1993-01-01

As part of the High-Level Waste Tank Farm at the Savannah River Site (SRS), the In-Tank Precipitation (ITP) facility was designed to decontaminate the radioactive waste supernate by removing cesium as precipitated cesium tetraphenylborate. A dynamic computer model of the ITP process was developed using SPEEDUP TM software to provide guidance in the areas of operation and production forecast, production scheduling, safety, air emission, and process improvements. The model performs material balance calculations in all phase (solid, liquid, and gas) for 50 key chemical constituents to account for inventory accumulation, depletion, and dilution. Calculations include precipitation, benzene radiolytic reactions, evaporation, dissolution, adsorption, filtration, and stripping. To control the ITP batch operation a customized FORTRAN program was generated and linked to SPEEDUP TM simulation This paper summarizes the model development and initial results of the simulation study

Mineral-microorganism interactions in Acid Mine Drainage environments: preliminary results

Science.gov (United States)

Carbone, Cristina; Zotti, Mirca; Pozzolini, Marina; Giovine, Marco; Di Piazza, Simone; Mariotti, Mauro; Lucchetti, Gabriella

2014-05-01

Minerals play a key role in controlling the mobility and distribution of metals and metalloids of environmental concern in supergenic environments. These are involved in a variety of processes, spanning the alteration of primary minerals to the formation of secondary authigenic phases and can represent a source or a trap for Potentially Ecotoxic Elements (PTEs). Soil, sediments, and waters heavily polluted with PTEs through AMD processes are a reservoir of a unusual bacteria and fungi well adapted to these toxic environments. Classical studies of biotic weathering have mainly focused on water-mineral interaction and on the ability of microorganism to influence the soil solution chemical composition. In this work, we analyzed two different representative ochreous and greenish-blue AMD colloidal precipitates in order to i) characterize the biota population present in these colloidal minerals and ii) verify the bioaccumulation of PTEs into the fungi and the potential impact of bacteria in the geochemistry of the system. The samples are composed by nanocrystalline goethite which contains high amounts of Fe, Cu, Zn, Pb, and Ni and woodwardite that is characterized by Cu, Zn, Ni, Y, and Ce. These precipitates were examined in order to evaluate the presence of fungal strains and to extract bacteria DNA. The preliminary results of fungi characterization show an interesting and selected mycobiota able to survive under unfavourable environmental conditions. A significant number of fungal strains was isolated in pure culture. Most of them belong to the genus Mucor and Penicillium. It is worth noting the presence of Trametes versicolor, a macrofungal lignicolous species already known for heavy metal biosorption capability from aqueous solution (Gülay et al 2003). The same colloidal precipitates have been processed to extract bacteria DNA, using a specific procedure developed for DNA extraction from sediments. The results gave a good yield of nucleic acids and the positive PCR

New method for the determination of precipitation kinetics using a laminar jet reactor

NARCIS (Netherlands)

Al Tarazi, M.Y.M.; Heesink, Albertus B.M.; Versteeg, Geert

2005-01-01

In this paper a new experimental method for determining the kinetics of fast precipitation reactions is introduced. Use is made of a laminar jet reactor, which is also frequently applied to determine the kinetics of homogeneous gas–liquid reactions. The liquid containing one or more of the

New method for the determination of precipitation kinetics using a laminar jet reactor

NARCIS (Netherlands)

Al-Tarazi, Mousa; Heesink, A. Bert M.; Versteeg, Geert F.

2005-01-01

In this paper a new experimental method for determining the kinetics of fast precipitation reactions is introduced. Use is made of a laminar jet reactor, which is also frequently applied to determine the kinetics of homogeneous gas-liquid reactions. The liquid containing one or more of the

Characterisation of Suspension Precipitated Nanocrystalline Hydroxyapatite Powders

International Nuclear Information System (INIS)

Mallik, P K; Swain, P.K.; Patnaik, S.C

2016-01-01

Hydroxyapatite (HA) is a well-known biomaterial for coating on femoral implants, filling of dental cavity and scaffold for tissue replacement. Hydroxyapatite possess limited load bearing capacity due to their brittleness. In this paper, the synthesis of nanocrystalline hydroxyapatite powders was prepared by dissolving calcium oxide in phosphoric acid, followed by addition of ammonia liquor in a beaker. The prepared solution was stirred by using magnetic stirrer operated at temperature of 80°C for an hour. This leads to the formation of hydroxyapatite precipitate. The precipitate was dried in oven for overnight at 100°C. The dried agglomerated precipitate was calcined at 800°C in conventional furnace for an hour. The influence of calcium oxide concentration and pH on the resulting precipitates was studied using BET, XRD and SEM. As result, a well-defined sub-rounded morphology of powders size of ∼41 nm was obtained with a salt concentration of 0.02 M. Finally, it can be concluded that small changes in the reaction conditions led to large changes in final size, shape and degree of aggregation of the hydroxyapatite particles. (paper)

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Science.gov (United States)

Osten, Julia; Milkereit, Benjamin; Schick, Christoph; Kessler, Olaf

2015-01-01

In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181) in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed) was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC) was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Directory of Open Access Journals (Sweden)

Julia Osten

2015-05-01

Full Text Available In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181 in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Chemical and colloidal aspects of collectorless flotation behavior of sulfide and non-sulfide minerals.

Science.gov (United States)

Aghazadeh, Sajjad; Mousavinezhad, Seyed Kamal; Gharabaghi, Mahdi

2015-11-01

Flotation has been widely used for separation of valuable minerals from gangues based on their surface characterizations and differences in hydrophobicity on mineral surfaces. As hydrophobicity of minerals widely differs from each other, their separation by flotation will become easier. Collectors are chemical materials which are supposed to make selectively valuable minerals hydrophobic. In addition, there are some minerals which based on their surface and structural features are intrinsically hydrophobic. However, their hydrophobicities are not strong enough to be floatable in the flotation cell without collectors such as sulfide minerals, coal, stibnite, and so forth. To float these minerals in a flotation cell, their hydrophobicity should be increased in specific conditions. Various parameters including pH, Eh, size distribution, mill types, mineral types, ore characterization, and type of reaction in flotation cells affect the hydrophobicity of minerals. Surface analysis results show that when sulfide minerals experience specific flotation conditions, the reactions on the surface of these minerals increase the amount of sulfur on the surface. These phenomenons improve the hydrophobicity of these minerals due to strong hydrophobic feature of sulfurs. Collectorless flotation reduces chemical material consumption amount, increases flotation selectivity (grade increases), and affects the equipment quantities; however, it can also have negative effects. Some minerals with poor surface floatability can be increased by adding some ions to the flotation system. Depressing undesirable minerals in flotation is another application of collectorless flotation.

Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1

Science.gov (United States)

Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

2017-11-01

Precipitation of calcium carbobate induced by microbial activities is common occurrence in controlled solution, but the formation mechanism and morphology in precipitation of calcite in solution systems is unclear, and the role of microbes is disputed. Here, culture experiment was performed for 50 days using the Curvibacter lanceolatus strain HJ-1 in a M2 culture medium, and the phase composition and morphology of the precipitates were characterized by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) techniques. We show that the precipitation processes in our experiment lead to unusual morphologies of crystals corresponding to different growth stages, and the morphologies of the precipitated crystal aggregates ranging from the main rod-, cross-, star-, cauliflower-like morphologies to spherulitic structure. The complex and unusual morphologies of the precipitated calcite by strain HJ-1 may provide a reference point for better understanding the biomineralization mechanism of calcite, moreover, morphological transition of minerals revealed that the multi-ply crystals-aggregation mechanism for calcite growth in crystallisation media.

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

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.

Surfactant loss control in chemical flooding spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1993--September 30, 1994

Energy Technology Data Exchange (ETDEWEB)

Somasundaran, P.

1995-06-01

The aim of this project is to elucidate the mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effect of surfactant structure, surfactant combinations, other inorganic and polymeric species is being studied. A multi-pronged approach consisting of micro and nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability is used to achieve the goals. The results of this study should help in controlling surfactant loss in chemical flooding and also in developing optimum structures and conditions for efficient chemical flooding processes. During the second year of this three year contract, adsorption/desorption of single surfactants and select surfactant mixtures on alumina and silica was studied. Surfactants studied include the anionic sodium dodecyl sulfate (SDS), cationic tetradecyl trimethyl ammonium chloride (TTAC), nonionic pentadecylethoxylated nonyl phenol (NP-15) and the nonionic octaethylene glycol n-dodecyl ether (C{sub 12}EO{sub 8}) of varying hydrocarbon chain length. The microstructure of the adsorbed layer in terms of micropolarity and aggregation numbers was probed using fluorescence spectroscopy. Changes of microstructure upon dilution (desorption) were also studied. Presence of the nonionic surfactant in the mixed aggregate led to shielding of the charge of the ionic surfactant which in-turn promoted aggregation but reduced electrostatic attraction between the charged surfactant and the mineral surface. Strong consequences of surfactant interactions in solution upon adsorption as well as correlations between monomer concentrations in mixtures and adsorption were revealed.

Kinetics of oxygen adsorption on ZnS nanoparticles synthesized by precipitation process

Directory of Open Access Journals (Sweden)

Ahmadi Reza

2016-06-01

Full Text Available ZnS nanoparticles were synthesized through a one-step precipitation process. Effect of time and temperature on the formation reaction was investigated. The synthesized samples were characterized by X-ray diffraction (XRD, ultraviolet (UV visible absorption and photoluminescence (PL spectrophotometry. Based on XRD and UV-Vis data, the particles produced at 70 °C had a mean particle size of about 5 nm. Increasing time and temperature of the synthesis reaction resulted in photoluminescence intensification. PL spectroscopy helped understanding the adsorption kinetics of oxygen on ZnS nanoparticles during the precipitation synthesis process. Fabrication of ZnS structures with appropriate oxygen adsorption capacity was suggested as a means of PL emission intensity control.

End point control of an actinide precipitation reactor

International Nuclear Information System (INIS)

Muske, K.R.

1997-01-01

The actinide precipitation reactors in the nuclear materials processing facility at Los Alamos National Laboratory are used to remove actinides and other heavy metals from the effluent streams generated during the purification of plutonium. These effluent streams consist of hydrochloric acid solutions, ranging from one to five molar in concentration, in which actinides and other metals are dissolved. The actinides present are plutonium and americium. Typical actinide loadings range from one to five grams per liter. The most prevalent heavy metals are iron, chromium, and nickel that are due to stainless steel. Removal of these metals from solution is accomplished by hydroxide precipitation during the neutralization of the effluent. An end point control algorithm for the semi-batch actinide precipitation reactors at Los Alamos National Laboratory is described. The algorithm is based on an equilibrium solubility model of the chemical species in solution. This model is used to predict the amount of base hydroxide necessary to reach the end point of the actinide precipitation reaction. The model parameters are updated by on-line pH measurements

The mechanism underlying calcium phosphate precipitation on titanium via ultraviolet, visible, and near infrared laser-assisted biomimetic process

International Nuclear Information System (INIS)

Mahanti, Moumita; Nakamura, Maki; Pyatenko, Alexander; Sakamaki, Ikuko; Koga, Kenji; Oyane, Ayako

2016-01-01

We recently developed a rapid single-step calcium phosphate (CaP) precipitation technique on several substrates using a laser-assisted biomimetic process (LAB process). In this process, ultraviolet (UV, λ   =  355 nm) pulsed laser irradiation has been applied to a substrate that is immersed in a supersaturated CaP solution. In the present study, the LAB process for CaP precipitation on a titanium substrate was successfully expanded to include not only UV but also visible (VIS, λ   =  532 nm) and near infrared (NIR, λ   =  1064 nm) lasers. Surface heating and plasma-mediated surface reactions (micro-deformation, oxidization, photoexcitation, and wetting) generated by UV, VIS, or NIR lasers are considered to be involved in the CaP precipitation on the titanium surface in the LAB process. The kinetics of these reactions and consequently of CaP precipitation were dependent on the laser wavelength and fluence. The higher laser fluence did not always accelerate CaP precipitation on the substrate; rather, it was found that an optimal range of fluence exists for each laser wavelength. These results suggest that for efficient CaP precipitation, a suitable laser wavelength should be selected according to the optical absorption properties of the substrate material and the laser fluence should also be adjusted to induce surface heating and plasma-mediated surface reactions that are favorable for CaP precipitation. (paper)

Precipitation of solid phase calcium carbonates and their effect on application of seawater SA–T–P models

Directory of Open Access Journals (Sweden)

R. Feistel

2009-07-01

Full Text Available At the present time, little is known about how broad salinity and temperature ranges are for seawater thermodynamic models that are functions of absolute salinity (SA, temperature (T and pressure (P. Such models rely on fixed compositional ratios of the major components (e.g., Na/Cl, Mg/Cl, Ca/Cl, SO4/Cl, etc.. As seawater evaporates or freezes, solid phases [e.g., CaCO3(s or CaSO42H2O(s] will eventually precipitate. This will change the compositional ratios, and these salinity models will no longer be applicable. A future complicating factor is the lowering of seawater pH as the atmospheric partial pressures of CO2 increase. A geochemical model (FREZCHEM was used to quantify the SA−T boundaries at P=0.1 MPa and the range of these boundaries for future atmospheric CO2 increases. An omega supersaturation model for CaCO3 minerals based on pseudo-homogeneous nucleation was extended from 25–40°C to 3°C. CaCO3 minerals were the boundary defining minerals (first to precipitate between 3°C (at SA=104 g kg− and 40°C (at SA=66 g kg−. At 2.82°C, calcite(CaCO3 transitioned to ikaite(CaCO36H2O as the dominant boundary defining mineral for colder temperatures, which culminated in a low temperature boundary of −4.93°C. Increasing atmospheric CO2 from 385 μatm (390 MPa (in Year 2008 to 550 μatm (557 MPa (in Year 2100 would increase the SA and t boundaries as much as 11 g kg−1 and 0.66°C, respectively. The model-calculated calcite-ikaite transition temperature of 2.82°C is in excellent agreement with ikaite formation in natural environments that occurs at temperatures of 3°C or lower. Furthermore, these results provide a quantitative theoretical explanation (FREZCHEM model calculation for why ikaite is the solid phase CaCO3 mineral that precipitates during seawater freezing.

Precipitation of solid phase calcium carbonates and their effect on application of seawater SA-T-P models

Science.gov (United States)

Marion, G. M.; Millero, F. J.; Feistel, R.

2009-07-01

At the present time, little is known about how broad salinity and temperature ranges are for seawater thermodynamic models that are functions of absolute salinity (SA), temperature (T) and pressure (P). Such models rely on fixed compositional ratios of the major components (e.g., Na/Cl, Mg/Cl, Ca/Cl, SO4/Cl, etc.). As seawater evaporates or freezes, solid phases [e.g., CaCO3(s) or CaSO42H2O(s)] will eventually precipitate. This will change the compositional ratios, and these salinity models will no longer be applicable. A future complicating factor is the lowering of seawater pH as the atmospheric partial pressures of CO2 increase. A geochemical model (FREZCHEM) was used to quantify the SA-T boundaries at P=0.1 MPa and the range of these boundaries for future atmospheric CO2 increases. An omega supersaturation model for CaCO3 minerals based on pseudo-homogeneous nucleation was extended from 25-40°C to 3°C. CaCO3 minerals were the boundary defining minerals (first to precipitate) between 3°C (at SA=104 g kg-) and 40°C (at SA=66 g kg-). At 2.82°C, calcite(CaCO3) transitioned to ikaite(CaCO36H2O) as the dominant boundary defining mineral for colder temperatures, which culminated in a low temperature boundary of -4.93°C. Increasing atmospheric CO2 from 385 μatm (390 MPa) (in Year 2008) to 550 μatm (557 MPa) (in Year 2100) would increase the SA and t boundaries as much as 11 g kg-1 and 0.66°C, respectively. The model-calculated calcite-ikaite transition temperature of 2.82°C is in excellent agreement with ikaite formation in natural environments that occurs at temperatures of 3°C or lower. Furthermore, these results provide a quantitative theoretical explanation (FREZCHEM model calculation) for why ikaite is the solid phase CaCO3 mineral that precipitates during seawater freezing.

Radial Oxygen Loss in the Rhizosphere of Wild Rice as a Control On Root Surface Mineral Precipitation

Science.gov (United States)

Murphy, K.; Trejo, B.; LaFond-Hudson, S.

2017-12-01

Wild rice (Zizania palustris) is an aquatic plant native to the Great Lakes region that is culturally and nutritionally significant for the Ojibwe people of Northern Minnesota. Concern for the future health of wild rice populations has increased amidst ongoing pressures from proposed mining projects that risk sulfate contamination to natural waters. Although sulfate itself is not toxic to wild rice, bacteria living in anoxic sediments use the sulfate as an electron acceptor, converting it to sulfide, which subsequently precipitates in the form of iron-sulfide on the root surface of wild rice. These precipitates are linked to lowered viability of wild rice. Most wetland plants are able to shield against the harmful accumulation of these precipitates through a process known as radial oxygen loss (ROL), in which oxygen leaches from roots into anoxic sediments to form protective iron-oxide plaques. This mechanism, however, had yet to be experimentally confirmed in wild rice. In this study, we eliminated the potential for ROL to occur in wild rice prior to the reproductive phase, and measured the rates of iron-sulfide accumulation on the roots and in associated sediments. We compared these data with the geochemical composition of roots and sediment from wild rice that accumulated iron-sulfide precipitate during the reproductive phase. In doing so, we demonstrate that ROL is indeed a mechanism by which wild rice protects itself against sulfide exposure, and examine the nuances of ROL as it relates to the life cycle of wild rice. The better we understand the vulnerability of wild rice across its life cycle and comparative rates of both toxic and protective precipitate accumulation, the better we can approach wild rice conservation.

Mass Transfer and Kinetics Study of Heterogeneous Semi-Batch Precipitation of Magnesium Carbonate

DEFF Research Database (Denmark)

Han, B.; Qu, H. Y.; Niemi, H.

2014-01-01

Precipitation kinetics and mass transfer of magnesium carbonate (MgCO3) hydrates from a reaction of magnesium hydroxide (Mg(OH)(2)) and CO2 were analyzed. The effect of CO2 flow rate and mixing intensity on precipitation was investigated under ambient temperature and atmospheric pressure. Raman...... on the dissolution of Mg(OH)(2). In the researched system, the main driver of the precipitation kinetics was the mass transfer of CO2. Nesquehonite (MgCO3 center dot 3H(2)O), as needle-like crystals, was precipitated as the main product. Raman spectroscopy can serve as a potential tool to monitor the carbonation...

Experimental and simulation studies on mineral trapping of CO2 with brine

International Nuclear Information System (INIS)

Soong, Y.; Goodman, A.L.; McCarthy-Jones, J.R.; Baltrus, J.P.

2004-01-01

The reaction of carbon dioxide (CO 2 ) with brine samples collected from the Oriskany Formation in Indiana County, PA, was investigated in an autoclave reactor under various conditions. A geochemical code, PHREEQC, was used as to simulate the reaction in the autoclave reactor. The combined experimental and modeling data suggests that pH (pH > 9) plays a key role in the formation of carbonate minerals. The effects of temperature and CO 2 pressure have a lesser impact on the formation of carbonate minerals

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.

Aerosol impacts on California winter clouds and precipitation during CalWater 2011: local pollution vs. long-range transported dust

OpenAIRE

J. Fan; L. R. Leung; P. J. DeMott; J. M. Comstock; B. Singh; D. Rosenfeld; J. M. Tomlinson; A. White; K. A. Prather; P. Minnis; J. K. Ayers; Q. Min

2013-01-01

Mineral dust aerosols often observed over California in winter/spring, associated with long-range transport from Asia and Sahara, have been linked to enhanced precipitation based on observations. Local anthropogenic pollution, on the other hand, was shown in previous observational and modeling studies to reduce precipitation. Here we incorporate recent developments in ice nucleation parameterizations to link aerosols with ice crystal formation in a spectral-bin cloud microphysical mode...

Aerosol impacts on California winter clouds and precipitation during CalWater 2011: local pollution versus long-range transported dust

OpenAIRE

Fan, J.; Leung, L. R.; DeMott, P. J.; Comstock, J. M.; Singh, B.; Rosenfeld, D.; Tomlinson, J. M.; White, A.; Prather, K. A.; Minnis, P.; Ayers, J. K.; Min, Q.

2014-01-01

Mineral dust aerosols often observed over California in winter and spring, associated with long-range transport from Asia and the Sahara, have been linked to enhanced precipitation based on observations. Local anthropogenic pollution, on the other hand, was shown in previous observational and modeling studies to reduce precipitation. Here we incorporate recent developments in ice nucleation parameterizations to link aerosols with ice crystal formation in a spectral-bin cloud microphysical mod...

Controllable mineral coatings on PCL scaffolds as carriers for growth factor release.

Science.gov (United States)

Suárez-González, Darilis; Barnhart, Kara; Migneco, Francesco; Flanagan, Colleen; Hollister, Scott J; Murphy, William L

2012-01-01

In this study, we have developed mineral coatings on polycaprolactone scaffolds to serve as templates for growth factor binding and release. Mineral coatings were formed using a biomimetic approach that consisted in the incubation of scaffolds in modified simulated body fluids (mSBF). To modulate the properties of the mineral coating, which we hypothesized would dictate growth factor release, we used carbonate (HCO(3)) concentration in mSBF of 4.2 mm, 25 mm, and 100 mm. Analysis of the mineral coatings formed using scanning electron microscopy indicated growth of a continuous layer of mineral with different morphologies. X-ray diffraction analysis showed peaks associated with hydroxyapatite, the major inorganic constituent of human bone tissue in coatings formed in all HCO(3) concentrations. Mineral coatings with increased HCO(3) substitution showed more rapid dissolution kinetics in an environment deficient in calcium and phosphate but showed re-precipitation in an environment with the aforementioned ions. The mineral coating provided an effective mechanism for growth factor binding and release. Peptide versions of vascular endothelial growth factor (VEGF) and bone morphogenetic protein 2 (BMP2) were bound with efficiencies up to 90% to mineral mineral-coated PCL scaffolds. We also demonstrated sustained release of all growth factors with release kinetics that were strongly dependent in the solubility of the mineral coating. Copyright © 2011 Elsevier Ltd. All rights reserved.

Liberation of Adsorbed and Co-Precipitated Arsenic from Jarosite, Schwertmannite, Ferrihydrite, and Goethite in Seawater

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Rodrigo Alarcón

2014-07-01

Full Text Available Sea level rise is able to change the geochemical conditions in coastal systems. In these environments, transport of contaminants can be controlled by the stability and adsorption capacity of iron oxides. The behavior of adsorbed and co-precipitated arsenic in jarosite, schwertmannite, ferrihydrite, and goethite in sea water (common secondary minerals in coastal tailings was investigated. The aim of the investigation was to establish As retention and transport under a marine flood scenario, which may occur due to climate change. Natural and synthetic minerals with co-precipitated and adsorbed As were contacted with seawater for 25 days. During this period As, Fe, Cl, SO4, and pH levels were constantly measured. The larger retention capability of samples with co-precipitated As, in relation with adsorbed As samples, reflects the different kinetics between diffusion, dissolution, and surface exchange processes. Ferrihydrite and schwertmannite showed good results in retaining arsenic, although schwertmannite holding capacity was enhanced due its buffering capacity, which prevented reductive dissolution throughout the experiment. Arsenic desorption from goethite could be understood in terms of ion exchange between oxides and electrolytes, due to the charge difference generated by a low point-of-zero-charge and the change in stability of surface complexes between synthesis conditions and natural media.

Hydrogen-isotopic composition of some hydrous manganese minerals

International Nuclear Information System (INIS)

Hariya, Y.; Tsutsumi, M.

1981-01-01

Initial data on the hydrogen-isotopic compositions in hydrous Mn minerals from various occurrences fall in a wide range from -298 to -84per thousand, relative to SMOW. deltaD-values of todorokite and cryptomelane from Tertiary deposits show -89 and -150per thousand. 10 A-manganite and delta-MnO 2 from deep-sea nodules have relatively restricted deltaD-values ranging from -96 to -84per thousand. The deltaD-values for manganese bog ores from recent hot springs show almost -105per thousand. It is recognized that the isotopic values obtained for the deep-sea nodules and recent bog ores are slightly different ranged. Manganite and groutite are unique in their hydrogen-isotopic compositions, having the most depleted deltaD-values ranging from -298 to -236per thousand. MnO(OH) minerals are more deuterium-depleted hydrous minerals than any other hydrothermal minerals from various ore deposits. Hydrogen-isotope fractionation factors between manganite and water were experimentally determined to be 0.7894, 0.7958 and 0.8078 at 150 0 , 200 0 and 250 0 C respectively. The present experimental results indicate that if manganites were formed at temperatures below 250 0 C, under isotopic equilibrium conditions most of the manganite mineralization in the Tertiary manganese deposits must have precipitated from meteoric hydrothermal solutions. (Auth.)

Waste-rock interactions and bedrock reactions

International Nuclear Information System (INIS)

White, W.B.

1977-01-01

The experimental program is designed to discover possible reactions between shale repository rocks and radioactive wastes. The canister can be regarded in three ways: (a) As a source of heat that modifies the mineralogy and therefore the physical properties of the surrounding rock (dry heat). (b) As a source of heat that activates reactions between minerals in the surrounding rock and slowly percolating ground water. (c) As a source of reaction materials of different composition from the surrounding rock and which therefore may react to form completely new ''minerals'' in a contact aureole around the canister. The matrix of interactions contains two composition axes. The waste compositions are defined by the various prototype waste forms usually investigated: glass, calcine, ''spent fuel'' and the ceramic supercalcine. The temperatures and pressures at which these reactions take place must be investigated. Thus each node on the ''wiring diagram'' is itself a matrix of experiments in which the T and to some extent P are varied. Experiments at higher pressure and temperature allow reactions to take place on a laboratory time scale and thus identify what could happen. These reactions are then followed downward in temperature to determine both phase boundaries and kinetic cut-offs below which equilibrium cannot be achieved on a laboratory time scale

Synthesis and characterization of magnetite nanoparticles from mineral magnetite

Energy Technology Data Exchange (ETDEWEB)

Morel, Mauricio, E-mail: mmorel@ing.uchile.cl [Laboratorio de Síntesis y Polímeros, Departamento de ciencias de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago (Chile); Laboratorio de Materiales a Nanoescala, Departamento de ciencias de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Avenue Tupper 2069, Santiago (Chile); Martínez, Francisco, E-mail: polimart@ing.uchile.cl [Laboratorio de Síntesis y Polímeros, Departamento de ciencias de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago (Chile); Mosquera, Edgar [Laboratorio de Materiales a Nanoescala, Departamento de ciencias de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Avenue Tupper 2069, Santiago (Chile)

2013-10-15

We have synthesized magnetite nanoparticles with sizes that range from 20 to 30 nm from mineral magnetite roughly 45 μm in size. The procedure consists in the dissolution of the mineral in an acidic medium and subsequent precipitation in a basic medium in the presence of oleic acid. Two experiments were conducted in different gaseous environments. The first was carried out in an environment exposed to air (M1) and the second in an N{sub 2} (M2) environment. The x-ray diffraction results showed a slight difference, which corresponds to the surface oxidation of magnetite. The sizes of the modified nanoparticles were determined through the Scherrer equation and transmission electron microscopy. An organic material mass loss corresponding to 18% was observed through a thermogravimetric analysis. The Fourier transform infrared spectroscopic analysis provides information about the type of bond that is formed on the surface of the nanoparticle, which corresponds to a bidentate chelate. The vibrating sample magnetometer results show a superparamagnetic behavior for sample M1. - Highlights: • A new method for synthesis of nanoparticles from mineral microparticles. • Search agreggate value to the mineral by mean nanoscience. • The stoichiometric ratio of the ions Fe{sup 2+} and Fe{sup 3+} from the mineral magnetite is synergistic.

Synthesis and characterization of magnetite nanoparticles from mineral magnetite

International Nuclear Information System (INIS)

Morel, Mauricio; Martínez, Francisco; Mosquera, Edgar

2013-01-01

We have synthesized magnetite nanoparticles with sizes that range from 20 to 30 nm from mineral magnetite roughly 45 μm in size. The procedure consists in the dissolution of the mineral in an acidic medium and subsequent precipitation in a basic medium in the presence of oleic acid. Two experiments were conducted in different gaseous environments. The first was carried out in an environment exposed to air (M1) and the second in an N 2 (M2) environment. The x-ray diffraction results showed a slight difference, which corresponds to the surface oxidation of magnetite. The sizes of the modified nanoparticles were determined through the Scherrer equation and transmission electron microscopy. An organic material mass loss corresponding to 18% was observed through a thermogravimetric analysis. The Fourier transform infrared spectroscopic analysis provides information about the type of bond that is formed on the surface of the nanoparticle, which corresponds to a bidentate chelate. The vibrating sample magnetometer results show a superparamagnetic behavior for sample M1. - Highlights: • A new method for synthesis of nanoparticles from mineral microparticles. • Search agreggate value to the mineral by mean nanoscience. • The stoichiometric ratio of the ions Fe 2+ and Fe 3+ from the mineral magnetite is synergistic

Pore-Scale Study of Transverse Mixing Induced CaCO ₃ Precipitation and Permeability Reduction in a Model Subsurface Sedimentary System

Energy Technology Data Exchange (ETDEWEB)

Zhang, Changyong; Dehoff, Karl; Hess, Nancy; Oostrom, Mart; Wietsma, Thomas W.; Valocchi, Albert J.; Fouke, Bruce W.; Werth, Charles J.

2010-10-15

A microfluidic pore structure etched into a silicon wafer was used as a two-dimensional model subsurface sedimentary system (i.e., a micromodel) to study mineral precipitation and permeability reduction relevant to groundwater remediation and geological carbon sequestration. Solutions containing CaCl₂ and Na₂CO₃ at four different saturation states (Ω = [Ca²⁺] [CO^32-] / KspCaCO₃) were introduced through two separate inlets and they mixed by diffusion transverse to the main flow direction along the center of the micromodel resulting in CaCO₃ precipitation. Precipitation rates increased and the total amount of precipitates decreased with increasing saturation state, and only vaterite and calcite crystals were formed (no aragonite). The relative amount of vaterite increased from 80% at the lowest saturation (Ω_v = 2.8 for vaterite) state to 95% at the highest saturation state (Ω_v = 4.5). Fluorescent tracer tests conducted before and after CaCO₃ precipitation indicate that pore spaces were completely occluded by CaCO₃ precipitates along the transverse mixing zone, thus significantly reducing porosity and permeability, and potentially limiting transformation from vaterite to the more stable calcite. The results suggest that mineral precipitation along plume margins can decrease both reactant mixing during groundwater remediation, and injection and storage efficiency during CO₂ sequestration.

Minerals in deserts

International Nuclear Information System (INIS)

Smith, G.I.

1982-01-01

Almost any kind of mineral deposit can occur in desert areas, and the lack of vegetation and soil cover makes finding them easier. Some kinds of deposits, though, are more likely to occur in deserts than elsewhere. Some of these result from processes genetically related to the present desert climate that improved lower grade deposits of ore. One such process, termed secondary enrichment, is most effective in areas with deep water tables, and many low-grade copper, silver, and uranium deposits have been converted into mineable ore by the downward migration and redeposition of soluble metals. In a desert terrane, placer processes are effective whenever running water flowing over steep slopes erodes outcropping ore bodies and transports and concentrates the heavier ore minerals at lower levels, thus converting low-grade or hard-to-mine bedrock deposits into economically workable concentrations. Other kinds of deposits are better preserved in deserts because the lower rainfall at the surface, and the lower volume of flow and the greater depths to groundwater, result in less destruction of soluble ores; deposits of salines and phosphates are the most notable ores affected by these factors. Still other ore deposits are created as a consequence of the arid climate, mostly because the high evaporation rates operating on standing bodies of water produce brines that can lead directly to concentrations of salts and indirectly to secondary minerals, such as zeolites, that are produced by reaction of silicate minerals with saline waters

Arsenic immobilization by calcium-arsenic precipitates in lime treated soils

International Nuclear Information System (INIS)

Moon, Deok Hyun; Dermatas, Dimitris; Menounou, Nektaria

2004-01-01

Lime-based stabilization/solidification (S/S) can be an effective remediation alternative for the immobilization of arsenic (As) in contaminated soils and sludges. However, the exact immobilization mechanism has not been well established. Based on previous research, As immobilization could be attributed to sorption and/or inclusion in pozzolanic reaction products and/or the formation of calcium-arsenic (Ca-As) precipitates. In this study, suspensions of lime-As and lime-As-kaolinite were studied in an attempt to elucidate the controlling mechanism of As immobilization in lime treated soils. Aqueous lime-As suspensions (slurries) with varying Ca/As molar ratios (1:1, 1.5:1, 2:1, 2.5:1 and 4:1) were prepared and soluble As concentrations were determined. X-Ray diffraction (XRD) analyses were used to establish the resulting mineralogy of crystalline precipitate formation. Depending on the redox state of the As source, different As precipitates were identified. When As (III) was used, the main precipitate formation was Ca-As-O. With As(V) as the source, Ca 4 (OH) 2 (AsO 4 ) 2 ·4H 2 O formed at Ca/As molar ratios greater than 1:1. A significant increase in As (III) immobilization was observed at Ca/As molar ratios greater than 1:1. Similarly, a substantial increase in As (V) immobilization was noted at Ca/As molar ratios greater than or equal to 2.5:1. This observation was also confirmed by XRD. Lime-As-kaolinite slurries were also prepared at different Ca/As molar ratios. These slurries were used to specifically investigate the possibility of forming pozzolanic reaction products. Such products would immobilize As by sorption and/or inclusion along with the formations of different As precipitates. Toxicity Characteristic Leaching Procedure (TCLP) tests were used to evaluate As leachability in these slurries. XRD analyses revealed no pozzolanic reaction product formation. Instead, As immobilization was found to be precipitation controlled. The same Ca-As precipitate, Ca

Reactions the private life of atoms

CERN Document Server

Atkins, Peter

2011-01-01

Through an innovative, closely integrated design of images and text, and his characteristically clear, precise, and economical exposition, Peter Atkins explains the processes involved in chemical reactions. He begins by introducing a 'tool kit' of basic reactions, such as precipitation, corrosion, and catalysis, and concludes by showing how these building blocks are brought together in more complex processes such as photosynthesis.

Coupled processes of fluid flow, solute transport, and geochemical reactions in reactive barriers

Energy Technology Data Exchange (ETDEWEB)

Kim, Jeongkon; Schwartz, Franklin W.; Xu, Tianfu; Choi, Heechul, and Kim, In S.

2004-01-02

A complex pattern of coupling between fluid flow and mass transport develops when heterogeneous reactions occur. For instance, dissolution and precipitation reactions can change a porous medium's physical properties, such as pore geometry and thus permeability. These changes influence fluid flow, which in turn impacts the composition of dissolved constituents and the solid phases, and the rate and direction of advective transport. Two-dimensional modeling studies using TOUGHREACT were conducted to investigate the coupling between flow and transport developed as a consequence of differences in density, dissolution precipitation, and medium heterogeneity. The model includes equilibrium reactions for aqueous species, kinetic reactions between the solid phases and aqueous constituents, and full coupling of porosity and permeability changes resulting from precipitation and dissolution reactions in porous media. In addition, a new permeability relationship is implemented in TOUGHREACT to examine the effects of geochemical reactions and density difference on plume migration in porous media. Generally, the evolutions in the concentrations of the aqueous phase are intimately related to the reaction-front dynamics. Plugging of the medium contributed to significant transients in patterns of flow and mass transport.

Recovery of nickel and cobalt as MHP from limonitic ore leaching solution: Kinetics analysis and precipitate characterization

Science.gov (United States)

Safitri, Nina; Mubarok, M. Zaki; Winarko, Ronny; Tanlega, Zela

2018-05-01

In the present study, precipitation of nickel and cobalt as mixed hydroxide precipitate (MHP) from pregnant leach solution of nickel limonite ore from Soroako after iron removal stage was carried out. A series of MHP precipitation experiments was conducted by using MgO slurry as neutralizing agent and the effects of pH, temperature, duration of precipitation and the addition of MHP seed on the precipitation behavior of nickel, cobalt, as well as iron and manganese was studied. Characterization of MHP product was performed by particle size analyzer (PSA) as well as X-Ray Fluorescence (XRF), X-Ray Diffractometer (XRD) and Scanning Electron Microscope (SEM) analyses. Kinetics analysis was made by using differential-integral method for the rate of homogenous reaction. Precipitation at pH 7, temperature 50°C for 30 minute, without seed addition resulted in nickel and cobalt recoveries of 82.8% and 92%, respectively with co-precipitated iron and manganese of 70% and 24.2%, respectively. The seed addition increases nickel and cobalt precipitations significantly to 99.9% and 99.1%, respectively. However, the addition of seed into led to a significant increase of manganese co-precipitation from 24.2% without seed addition to 39.5% at the addition of 1 g seed per 200 mL of PLS. Kinetics analysis revealed that Ni precipitation to form MHP follows the second-order reaction kinetics with activation energy of 94.6 kJ/mol.

Origin and nature of the aluminium phosphate-sulfate minerals (APS associated with uranium mineralization in triassic red-beds (Iberian Range, Spain

Directory of Open Access Journals (Sweden)

Marfil, R.

2013-06-01

Full Text Available This study focuses on the mineralogical and chemical study of an Aluminium–phosphate–sulphate (APS mineralization that occurs in a clastic sequence from the Triassic (Buntsandstein of the Iberian Range. The deposit is constituted by sandstones, mudstones, and conglomerates with arenaceous matrix, which were deposited in fluvial to shallow-marine environments. In addition to APS minerals, the following diagenetic minerals are present in the clastic sequence: quartz, K-feldspar, kaolinite group minerals, illite, Fe-oxides-hidroxides, carbonate-sulphate cement-replacements and secondary uraniferous minerals. APS minerals were identified and characterized by optical microscopy, X-ray diffraction, scanning electron microscopy, and electron microprobe. Microcrystalline APS crystals occur replacing uraniferous minerals, associated with kaolinite, mica and filling pores, in distal fluvial-to-tidal arkoses-subarkoses. Given their Ca, Sr, and Ba contents, the APS minerals can be defined as a solid solution of crandallite-goyacite-gorceixite (0.53 Ca, 0.46 Sr and 0.01 Ba. The chemical composition, low LREE concentration and Sr > S suggest that the APS mineral were originated during the supergene alteration of the Buntsandstein sandstones due to the presence of the mineralizing fluids which causes the development of U-bearing sandstones in a distal alteration area precipitating from partially dissolved and altered detrital minerals. Besides, the occurrence of dickite associated with APS minerals indicates they were precipitated at diagenetic temperatures (higher than 80ºC, related to the uplifting occurred during the late Cretaceous post-rift thermal stage.Este trabajo se centra en el estudio de los minerales fosfato-sulfato alumínicos (APS que se producenen una secuencia clástica del Triásico (Buntsandstein de la Cordillera Ibérica. El depósito está constituido por areniscas, lutitas y conglomerados con matriz arenosa, que fueron depositados en

Microbe and Mineral Mediated Transformation of Heavy Metals, Radionuclides, and Organic Contaminants

Science.gov (United States)

Gerlach, R.

2011-12-01

Microorganisms influence their surroundings in many ways and humans have utilized microbially catalyzed reactions for benefit for centuries. Over the past few decades, microorganisms have been used for the control of contaminant transport in subsurface environments where many microbe mineral interactions occur. This presentation will discuss microbially influenced mineral formation and transformation as well as their influence on the fate of organic contaminants such as chlorinated aliphatics & 2,4,6-trinitrotoluene (TNT), heavy metals such as chromium, and radionuclides such as uranium & strontium. Both, batch and flow experiments have been performed, which monitor the net effect of microbe mineral interactions on the fate of these contaminants. This invited presentation will place an emphasis on the relative importance of direct microbial (i.e. biotic) transformations, mineral-mediated transformations as well as other abiotic reactions influencing the fate of environmental contaminants. Experiments will be summarized and placed in context of past and future engineered applications for the control of subsurface contaminants.

Summary of United States Geological Survey investigations of fluid-rock-waste reactions in evaporite environments under repository conditions

International Nuclear Information System (INIS)

Stewart, D.B.; Jones, B.F.; Roedder, E.; Potter, R.W. II

1980-01-01

The interstitial and inclusion fluids contained in rock salt and anhydrite, though present in amounts less than 1 weight per cent, are chemically aggressive and may react with canisters or wastes. The three basic types of fluids are: (1) bitterns residual from saline mineral precipitation including later recrystallization reactions; (2) brines containing residual solutes from the formation of evaporite that have been extensively modified by reactions with contiguous carbonate of clastic rocks; and (3) re-solution brines resulting from secondary dehydration of evaporite minerals or solution of saline minerals by undersaturated infiltrating waters. Fluid composition can indicate that meteoric flow systems have contacted evaporites or that fluids from evaporites have migrated into other formations. The movement of fluids trapped in fluid inclusions in salt from southeast New Mexico is most sensitive to ambient temperature and to inclusion size, although several other factors such as thermal gradient and vapour/liquid ratio are also important. There is no evidence of a threshold temperature for movement of inclusions. Empirical data are given for determining the amount of brine reaching the heat source if the temperature, approximate amount of total dissolved solids, and Ca:Mg ratio in the brine are known. SrCl 2 and CsCl can reach high concentrations in saturated NaCl solutions and greatly depress the liquidus. The possibility that such fluids, if generated, could migrate from a high-level waste repository must be minimized because the fluid would contain its own radiogenic energy source in the first decades after repository closure, thus changing the thermal evolution of the repository from designed values. (author)

A new, integrated, approach to mineralization-based CCS

Energy Technology Data Exchange (ETDEWEB)

Hunwick, R.J. [Integrated Carbon Sequestration Pty Ltd., Lindfield, NSW (Australia)

2009-11-15

Mineralization is an attractive concept for carbon capture and storage as it can avoid some of the potential public acceptance problems of geosequestering pressurised CO{sub 2}. But there are major cost and energy penalty concerns. A new integrated approach to mineralisation, avoiding the intermediate step of CO{sub 2} extraction and promising considerable benefits, is outlined here. The ICS process integrates two operation in the first, an ammonia-rich aqueous solution of ammonium bicarbonate is used to scrub carbon dioxide from flue gases to form a solution enriched in carbon dioxide. In the second, pretreated serpentinite or other suitable ultramafic rock is blended directly into this rich solution prior to the mixture being held under controlled conditions in a purpose-built reactor. The silicate minerals react with ammonium carbonate to form magnesium carbonate and silica, thereby directly removing frrm solution the carbon dioxide that was absorbed in the flue gas scrubbers as insoluble precipitates. The capture solution is regenerated for its recycle to the flue gas scrubbers. Trials at Lucas Hights have demonstrated the direct conversion of silicates to magnesite, and work continues to establish optimum conditions for this reaction to allow a continuous pilot plant to be designed. Their thermodynamic modeling has confirmed the energy efficiency of the process. Pre-feasibility studies into retrofitting ICS to major existing coal-fired power stations to capture at least 90% of their carbon dioxide emissions suggest a total cost of US$50 to capture and store each tonne of the gas permanently. Since the tonnage of rock required for this mineralisation process is six times the tonnage of coal to be fired in the host power station logic dictates that any new power station should be nearer the rock deposit than the coal field that furnishes its fuel. 2 figs.

Biomimetic mineralization of recombinant collagen type I derived protein to obtain hybrid matrices for bone regeneration.

Science.gov (United States)

Ramírez-Rodríguez, Gloria Belén; Delgado-López, José Manuel; Iafisco, Michele; Montesi, Monica; Sandri, Monica; Sprio, Simone; Tampieri, Anna

2016-11-01

Understanding the mineralization mechanism of synthetic protein has recently aroused great interest especially in the development of advanced materials for bone regeneration. Herein, we propose the synthesis of composite materials through the mineralization of a recombinant collagen type I derived protein (RCP) enriched with RGD sequences in the presence of magnesium ions (Mg) to closer mimic bone composition. The role of both RCP and Mg ions in controlling the precipitation of the mineral phase is in depth evaluated. TEM and X-ray powder diffraction reveal the crystallization of nanocrystalline apatite (Ap) in all the evaluated conditions. However, Raman spectra point out also the precipitation of amorphous calcium phosphate (ACP). This amorphous phase is more evident when RCP and Mg are at work, indicating the synergistic role of both in stabilizing the amorphous precursor. In addition, hybrid matrices are prepared to tentatively address their effectiveness as scaffolds for bone tissue engineering. SEM and AFM imaging show an homogeneous mineral distribution on the RCP matrix mineralized in presence of Mg, which provides a surface roughness similar to that found in bone. Preliminary in vitro tests with pre-osteoblast cell line show good cell-material interaction on the matrices prepared in the presence of Mg. To the best of our knowledge this work represents the first attempt to mineralize recombinant collagen type I derived protein proving the simultaneous effect of the organic phase (RCP) and Mg on ACP stabilization. This study opens the possibility to engineer, through biomineralization process, advanced hybrid matrices for bone regeneration. Copyright © 2016 Elsevier Inc. All rights reserved.

On dynamics of uranium vein mineralization

International Nuclear Information System (INIS)

Petrosyan, R.V.

1981-01-01

The formation of urnaium vein deposits and the essence of consanguinity of the mineralization and wall metasomatites are considered. The formation of uranium mineralization is analysed from the positions of Korzhinsky D. S. : the formation of metasomatite aureole and associated vein ores take place as a result of the development of one solution flow while the formation of mineral vein associations occurs on the background of contineous filtration of the solution during metasomato is due to a repeated (pulse) half-opening of fractures and their filling with a part of filtrating solution. The analysis of the available information on the example of two different uranium manifestations permits to reveal certain relations both in the character of wall rock alterations and between the metasomatosis and the formation of ore minerals in veins. The conclusion is made that spatial-time correlations of vein formations with wall metasomatites attest that the pulse formation of ores in veinlets occurs on the background and in interrelation with a consecutive precipitation of components in the aureole volume. The analysis of element migration dynamics in wall aureole carried out from the positions of the Korzhinsky hypothesis of the advance wave of acid components that takes into account the interaction of continuous and pulse mechanisms of solution movement permits to avoid contradictions when interpreting the processes of wall rock alterations and vein ore-forming, and permits to make a common scheme of vein ore-genesis [ru

Characterization of glycosaminoglycans during tooth development and mineralization in the axolotl, Ambystoma mexicanum.

Science.gov (United States)

Wistuba, J; Völker, W; Ehmcke, J; Clemen, G

2003-10-01

Glycosaminoglycans (GAGs) involved in the formation of the teeth of Ambystoma mexicanum were located and characterized with the cuprolinic blue (CB) staining method and transmission electron microscopy (TEM). Glycosaminoglycan-cuprolinic blue precipitates (GAGCB) were found in different compartments of the mineralizing tissue. Various populations of elongated GAGCB could be discriminated both according to their size and their preferential distribution in the extracellular matrix (ECM). GAGCB populations that differ in their composition could be attributed not only to the compartments of the ECM but also to different zones and to different tooth types (early-larval and transformed). Larger precipitates were only observed within the dentine matrix of the shaft of the early-larval tooth. The composition of the populations differed significantly between the regions of the transformed tooth: pedicel, shaft and dividing zone. In later stages of tooth formation, small-sized GAGCBs were seen as intracellular deposits in the ameloblasts. It is concluded that the composition of GAGCB populations seems to play a role in the mineralization processes during tooth development in A. mexicanum and influence qualitative characteristics of the mineral in different tooth types and zones, and it is suggested that GAGs might be resorbed by the enamel epithelium during the late phase of enamel formation.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

Science.gov (United States)

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Root-driven Weathering Impacts on Mineral-Organic Associations in Deep Soil

Science.gov (United States)

Keiluweit, M.; Garcia Arredondo, M.; Tfaily, M. M.; Kukkadapu, R. K.; Schulz, M. S.; Lawrence, C. R.

2017-12-01

Plant roots dramatically reshape the soil environments through the release of organic compounds. While root-derived organic compounds are recognized as an important source of soil C, their role in promoting weathering reactions has largely been overlooked. On the one hand, root-driven weathering may generate mineral-organic associations, which can protect soil C for centuries to millennia. On the other hand, root-driven weathering also transforms minerals, potentially disrupting protective mineral-organic associations in the process. Hence root-derived C may not only initiate C accumulation, but also diminish C stocks through disruption of mineral-organic associations. Here we determined the impact of rhizogenic weathering on mineral-organic associations, and associated changes in C storage, across the Santa Cruz Marine Terrace chronosequence (65ka-226ka). Using a combination of high-resolution mass spectrometry, Mössbauer, and X-ray (micro)spectroscopy, we examined mineral-organic associations of deep soil horizons characterized by intense rhizogenic weathering gradients. Initial rhizogenic weathering dramatically increased C stocks, which is directly linked to an increase of microbially-derived C bound to monomeric Fe and Al and nano-goethite. As weathering proceeded, the soil C stocks declined concurrent with an increasingly plant-derived C signature and decreasing crystallinity. X-ray spectromicroscopic analyses revealed strong spatial associations between C and Fe during initial weathering stages, indicative of protective mineral-organic associations. In contrast, later weathering stages showed weaker spatial relationships between C and Fe. We conclude that rhizogenic weathering enhance C storage by creating protective mineral-organic associations in the initial weathering stages. As root-driven weathering proceeds, minerals are transformed into more crystalline phases that retain lower amounts of C. Our results demonstrate that root-induced weathering

Predicting the diagenetic evolution of argillite repositories: application of flow-through reaction cells

International Nuclear Information System (INIS)

Warr, L.; Clatter, N.; Liewig, N.

2005-01-01

In order to successfully predict the diagenetic evolution of argillite repositories we need to know i) which reactions occur under a defined set of conditions, ii) how these reactions modify the material properties of the argillite seal, and iii) how fast these chemical reactions take place. Based on the application of thermodynamics, and the construction of activity diagrams for low temperature mineral phases (e.g. Velde 1992), fair predictions of mineral stability can be made under a given set of physical and chemical conditions. Such predictions are strengthened by examining natural mineral reactions preserved in the geological record, in combination with results obtained from controlled laboratory experiments. Changes in the material behavior can also be reasonably assessed, as the basic physical and chemical properties of argillaceous rocks of varying mineralogy are well documented in the petrophysical and engineering literature (e.g. Bell, 1999). Probably the most difficult task, however, is to assess the rates of the chemical reactions involved. This difficulty reflects our poor knowledge of the reaction kinetics for these low-temperature, fine-grained mineral materials, and apparent differences between rates estimated from natural and experimental systems. A new approach to monitoring the reaction kinetics of fine-grained minerals in percolating solution has been developed using flow-through reaction (wet-cell) chambers. These devices can be routinely mounted onto the X-ray diffractometer for in-situ measurements of the sample. With the aid of a cap to maintain constant volume, the device can be subjected to diagenetic or hydrothermal conditions (<150 C). First results are here presented for the alteration of Callovo-Oxfordian shales in a reactive simple young fluid (strongly alkaline, pH ca. 13) at 90 C, designed to simulate the alteration of concrete at the repository site. (authors)

Mineralization of LCFA associated with anaerobic sludge : kinetics, enhancement of methanogenic activity, and effect of VFA

OpenAIRE

Pereira, M. A.; Sousa, D. Z.; Mota, M.; Alves, M. M.

2004-01-01

Long-chain fatty acids (LCFA) associated with anaerobic sludge by mechanisms of precipitation, adsorption, or entrapment can be biodegraded to methane. The mineralization kinetics of biomass-associated LCFA were established according to an inhibition model based on Haldane’s enzymatic inhibition kinetics. A value around 1,000 mg COD-LCFA g VSS-1 was obtained for the optimal specific LCFA content that allowed the maximal mineralization rate. For sludge with specific LCFA contents of 2838...

Removal of uranium(VI) from the aqueous phase by iron(II) minerals in presence of bicarbonate

Energy Technology Data Exchange (ETDEWEB)

Regenspurg, Simona, E-mail: regens@gfz-potsdam.de [Industrial Ecology, Royal Institute of Technology (KTH), SE 10044 Stockholm (Sweden); Schild, Dieter; Schaefer, Thorsten; Huber, Florian [Institut fuer Nukleare Entsorgung (INE), Forschungszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen (Germany); Malmstroem, Maria E. [Industrial Ecology, Royal Institute of Technology (KTH), SE 10044 Stockholm (Sweden)

2009-09-15

Uranium(VI) mobility in groundwater is strongly affected by sorption of mobile U(VI) species (e.g. uranyl, UO{sub 2}{sup 2+}) to mineral surfaces, precipitation of U(VI) compounds, such as schoepite (UO{sub 2}){sub 4}O(OH){sub 6}.6H{sub 2}O), and by reduction to U(IV), forming sparingly soluble phases (uraninite; UO{sub 2}). The latter pathway, in particular, would be very efficient for long-term immobilization of U. In nature, Fe(II) is an important reducing agent for U(VI) because it frequently occurs either dissolved in natural waters, sorbed to matrix minerals, or structurally bound in many minerals. Redox reactions between U(VI) and Fe(II) depend not only on the availability of Fe(II) in the environment, but also on the chemical conditions in the aqueous solution. Under natural groundwater condition U(VI) forms complexes with many anionic ligands, which strongly affect its speciation. Carbonate, in particular, is known to form stable complexes with U, raising the question, if U(VI), when complexed by carbonate, can be reduced to UO{sub 2}. The goal of this study was to find out if Fe(II) when structurally bound in a mineral (as magnetite, Fe{sub 3}O{sub 4}) or sorbed to a mineral surface (as corundum, Al{sub 2}O{sub 3}) can reduce U(VI) to U(IV) in the presence of HCO{sub 3}{sup -}. Batch experiments were conducted under anaerobic conditions to observe U removal from the aqueous phase by the two minerals depending on HCO{sub 3}{sup -} addition (1 mM), U concentration (0.01-30 {mu}M) and pH value (6-10). Immediately after the experiments, the mineral surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) to obtain information on the redox state of U bound to the solid surfaces. XPS results gave evidence that U(VI) can be reduced both by magnetite and by corundum amended with Fe(II). In the presence of HCO{sub 3}{sup -} the amount of reduced U on the mineral surfaces increased compared to carbonate-free solutions. This can be explained by the formation

Pattern formation and self-organization in a simple precipitation system

NARCIS (Netherlands)

Volford, Andras; Izsak, F.; Ripzam, Matyas; Lagzi, Istvan

Various types of pattern formation and self-organization phenomena can be observed in biological, chemical, and geochemical systems due to the interaction of reaction with diffusion. The appearance of static precipitation patterns was reported first by Liesegang in 1896. Traveling waves and

Geothermal alteration of clay minerals and shales: diagenesis

Energy Technology Data Exchange (ETDEWEB)

Weaver, C.E.

1979-07-01

The objective of this report is to perform a critical review of the data on the mineral and chemical alterations that occur during diagenesis and low-grade metamorphism of shale and other clay-rich rocks - conditions similar to those expected from emplacement of heat-producing radioactive waste in a geologic repository. The conclusions drawn in this document are that the following type of alterations could occur: smectite alteration, ion mobilization, illitic shales, kaolinite reactions, chlorite reactions, organic reactions, paleotemperatures, low temperature shales, high temperature shales, and phase equilibrium changes.

Geothermal alteration of clay minerals and shales: diagenesis

International Nuclear Information System (INIS)

Weaver, C.E.

1979-07-01

The objective of this report is to perform a critical review of the data on the mineral and chemical alterations that occur during diagenesis and low-grade metamorphism of shale and other clay-rich rocks - conditions similar to those expected from emplacement of heat-producing radioactive waste in a geologic repository. The conclusions drawn in this document are that the following type of alterations could occur: smectite alteration, ion mobilization, illitic shales, kaolinite reactions, chlorite reactions, organic reactions, paleotemperatures, low temperature shales, high temperature shales, and phase equilibrium changes

Effect of polydopamine on the biomimetic mineralization of mussel-inspired calcium phosphate cement in vitro

Energy Technology Data Exchange (ETDEWEB)

Liu, Zongguang [Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Qu, Shuxin, E-mail: qushuxin@swjtu.edu.cn [Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Zheng, Xiaotong; Xiong, Xiong [Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China); Fu, Rong; Tang, Kuangyun; Zhong, Zhendong [Department of Plastic Surgery, Academy of Medical Sciences and Sichuan Provincial People' s Hospital, Chengdu 610041 (China); Weng, Jie [Key Lab of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031 (China)

2014-11-01

Inspired by the excellent adhesive property of mussel adhesive protein, we added polydopamine (PDA) to calcium phosphate cement (PDA–CPC) to enhance its compressive strength previously. The mineralization and mechanism on PDA–CPC were investigated by soaking it in simulated body fluid in this study. The results indicated that PDA promoted the conversion of dicalcium phosphate dihydrate and α-tricalcium phosphate to hydroxyapatite (HA) in the early stage but inhibited this conversion subsequently. PDA promoted the rapid mineralization on PDA–CPC to form a layer of nanoscale calcium phosphate (CaP) whereas there was no CaP formation on the control-CPC after 1 d of soaking. This layer of nanoscale CaP was similar to that of natural bone, which was always observed during soaking. X-ray photoelectron spectroscopy showed that the peak of C=O of PDA existed in the newly formed CaP on PDA–CPC, indicating the co-precipitation of CaP with PDA. Furthermore, the newly formed CaP on PDA–CPC was HA confirmed by transmission electron microscopy, which the newly formed HA was in association with PDA. Therefore, PDA increased the capacity of mineralization of CPC and induced the formation of nanoscale bone-like apatite on PDA–CPC. Thus, this provides the feasible route for surface modification on CPC. - Highlights: • Effect of polydopamine (PDA) on the in vitro mineralization of PDA-CPC was studied. • PDA promoted the rapid mineralization on PDA-CPC to form a nanoscale HA layer. • The precipitation of the nanoscale HA layer on PDA-CPC accompanied with PDA. • Polydopamine induced mineralization is feasible for surface modification of CaP.

Studies of some phenomena in control engineering projects - With application to precipitation processes

Energy Technology Data Exchange (ETDEWEB)

Stoele-Hansen, Kjell

1998-12-31

This thesis deals with the life-cycle of a control engineering project and some phenomena encountered in such projects. Different types of control strategies are discussed and an attempt is made to classify them into categories. Some case projects are presented and forms the basis for discussing the individual`s role in a change project. Further conditions for successful implementation of new control strategies are discussed in general, but also conditions for successful implementation of new control strategies at a process section of a nickel work. Procedures for implementing new control strategies are treated and some remarks are made about operation of control strategies. An introduction is given to the modelling of precipitation in pH systems and different model formulations are discused. The modelling of pH controlled precipitations is discussed in general. A variety of dynamic models, ranging from complex to simple, are proposed and discussed. A rigorous dynamic nonlinear mechanistic model of a precipitation reactor is developed. It is based on the theory of reaction invariants and variants. The model is verified against real process data. The dynamics and characteristics of the precipitation reactor are analysed and some remarks are made with respect to controllability. A new strategy for pH control is proposed. A new model based strategy for controlling the precipitation reactions is also proposed. 93 refs., 63 figs., 10 tabs.

Precipitation reactions caused by nitrogen uptake during service at high temperatures of a niobium stabilised austenitic stainless steel

International Nuclear Information System (INIS)

Erneman, J.; Schwind, M.; Liu, P.; Nilsson, J.-O.; Andren, H.-O.; Aagren, J.

2004-01-01

Precipitation phenomena in type 347 austenitic stainless steels have been investigated after long-term heat treatment and creep in air at 700 and 800 deg. C. Nitrogen uptake was observed during long-term creep testing at 800 deg. C. No such effect was observed at 700 deg. C although times up to about 70,000 h were used. The major phases precipitated after long time exposure at 800 deg. C were primary Nb(C,N), Z-phase, Cr 2 N and M 23 C 6 , while primary Nb(C,N), secondary Nb(C,N) and σ-phase were the major phases at 700 deg. C. Z-phase precipitated in both intragranular and intergranular form at 800 deg. C. Large precipitates exhibiting a core/rim structure showed a rim of Z-phase surrounding undissolved primary Nb(C,N). The microstructural evolution during creep deformation in air at 800 deg. C was modelled thermodynamically. The model satisfactorily predicts nitrogen uptake and the essential features of the evolution of the microstructure with time. The precipitation sequence could be qualitatively described, although it was not possible to model the formation of all precipitates

Hydrogeochemical tracing of mineral water in Jingyu County, Northeast China.

Science.gov (United States)

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2016-02-01

The east Jilin Province in China, Jingyu County has been explored as a potential for enriching mineral water. In order to assess the water quality and quantity, it is of crucial importance to investigate the origin of the mineral water and its flow paths. In this study, eighteen mineral springs were sampled in May and September of 2012, May and September of 2013, and May 2014 and the environment, evolvement, and reaction mechanism of mineral water formation were analysed by hydrochemical data analysis, geochemical modelling and multivariate statistical analysis. The results showed that the investigated mineral water was rich in calcium, magnesium, potassium, sodium, bicarbonate, chloride, sulphate, fluoride, nitrate, total iron, silicate, and strontium, and mineral water ages ranged from 11.0 to more than 61.0 years. The U-shape contours of the mineral ages indicate a local and discrete recharge. The mineral compositions of the rocks were olivine, potassium feldspar, pyroxene, albite, and anorthite and were under-saturated in the mineral water. The origin of mineral water was from the hydrolysis of basalt minerals under a neutral to slightly alkaline and CO2-rich environment.

Effect of mineral matter on coal self-heating rate

Energy Technology Data Exchange (ETDEWEB)

B. Basil Beamish; Ahmet Arisoy [University of Queensland, Brisbane, Qld. (Australia). School of Engineering

2008-01-15

Adiabatic self-heating tests have been conducted on subbituminous coal cores from the same seam profile, which cover a mineral matter content range of 11.2-71.1%. In all cases the heat release rate does not conform to an Arrhenius kinetic model, but can best be described by a third order polynomial. Assessment of the theoretical heat sink effect of the mineral matter in each of the tests reveals that the coal is less reactive than predicted using a simple energy conservation equation. There is an additional effect of the mineral matter in these cases that cannot be explained by heat sink alone. The disseminated mineral matter in the coal is therefore inhibiting the oxidation reaction due to physicochemical effects. 14 refs., 5 figs., 5 tabs.

Adaptation Reactions of Siderophilic Cyanobacteria to High and Low Levels Of Environmental Iron: Implications for Biosphere History

Science.gov (United States)

Brown, I. I.; Bryant, D.; Sarkisova, S.; Shen, G.; Garrison, D.; McKay, D. S.

2009-01-01

Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models (Pierson and Parenteau, 2000) for analysis of the ecophysiology of ancient cyanobacteria (CB) which may have emerged in association with hydrothermal activity (Brown et al., 2007) and elevated levels of environmental Fe (Rouxel et al., 2005). Elevated environmental Fe2+ posed a significant challenge to the first oxygenic phototrophs - CB - because reduced Fe2+ induces toxic Fenton reactions (Wiedenheft et al., 2005). Ancient CB could have also been stressed by occasional migrations from the Fe2+-rich Ocean to the basaltic land which was almost devoid of dissolved Fe2+. That is why the study of the adaptation reactions of siderophilic CB, which inhabit iron-depositing hot springs, to up and down shifts in levels of dissolved Fe may shed light on the paleophysiology of ancient oxygenic prokaryotes. Methods. Siderophilic CB (Brown et al., 2007) were cultivated in media with different concentrations of added Fe3+. In some cases basaltic rocks were used as a source of Fe and trace elements. The processes of Fe mineralization and rock dissolution were studied using TEM, SEM and EDS techniques. Fluorescence spectroscopy was used for checking chlorophyll-protein complexes. Results. It was found that five siderophilic isolates Chroogloeocystis siderophila, JSC-1, JSC-3, JSC-11 and JSC-12 precipitated Fe-bearing phases on the exopolymeric sheaths of their cells if [Fe3+] was approx. 400-600 M (high Fe). Same [Fe3+] was most optimal one for the cultures proliferation rate (Brown et al., 2005; Brown et al., 2007). Higher concentrations of Fe3+ repressed the growth of some siderophilic CB (Brown et al., 2005). No mineralized Fe3+ was observed on the sheath of freshwater isolates Synechocystis sp. PCC 6803 and Phormidium aa. Scanning TEM in conjunction with thin-window energy dispersive X-ray spectroscopy (EDS) revealed intracellular Fe-rich phases within all three isolates

Influence of Si concentration on the precipitation in Al-1 at.% Mg alloy

Energy Technology Data Exchange (ETDEWEB)

Afify, N. [Physics Department, Faculty of Science, Assiut University, Assiut 71516 (Egypt)], E-mail: afify@aun.edu.eg; Gaber, A.; Mostafa, M.S.; Abbady, Gh. [Physics Department, Faculty of Science, Assiut University, Assiut 71516 (Egypt)

2008-08-25

The aging processes in Al-Mg-Si alloys have been studied by using differential scanning calorimetry (DSC), microhardness measurements (HV) and X-ray diffraction (XRD). Five processes have been detected by the DSC curves and HV behaviour. In the DSC curves, four exothermic and one endothermic reactions are developed. The sequence of processes are Guinier-Preston (G.P.) zones, dissolution of the G.P. zones, intermediate precipitation of {beta}''-phase, precipitation of {beta}'-phase and precipitation of the stable {beta}-phase + Si particles. The activation energies associated with the processes have been determined by using Kissinger method. Consequently, the nucleation mechanism of the precipitates can be explained. These phases are confirmed by XRD analysis.

Kinetic and analytical study on precipitation reactions with 110AgNO3 of some di(β-chloroethyl)amine derivatives and hydrochlorides with esters of N-(p-aminobenzoyl)-L-aspartic acid as carriers from dimethylformamide - water solution

International Nuclear Information System (INIS)

Cecal, Al.; Sunel, V.; Ghimiciu, L.

1983-01-01

The kinetics of precipitation reactions with 110 AgNO 3 of some di(β-chloroethyl) amine derivates and hydrochlorides with esters of N-(p-aminobenzoyl)-L-aspartic acid as carriers in dimethylformamide-water mixture, were studied. The rate constants of these reactions were of the order of 10 -4 lxmol -1 xmin -1 . The concentrations of the corresponding hydrochloride solutions were measured by radiometric titration with 110 AgNO 3 solution of given concentration. (author)

A Novel Approach to Mineral Carbonation: Enhancing Carbonation While Avoiding Mineral Pretreatment Process Cost