Relationship between pyrite Stability and arsenic mobility during aquifer storage and recovery in southwest central Florida.

Science.gov (United States)

Jones, Gregg W; Pichler, Thomas

2007-02-01

Elevated arsenic concentrations are common in water recovered from aquifer storage and recovery (ASR) systems in west-central Florida that store surface water. Investigations of the Suwannee Limestone of the Upper Floridan aquifer, the storage zone for ASR systems, have shown that arsenic is highest in pyrite in zones of high moldic porosity. Geochemical modeling was employed to examine pyrite stability in limestone during simulated injections of surface water into wells open only to the Suwannee Limestone with known mineralogy and water chemistry. The goal was to determine if aquifer redox conditions could be altered to the degree of pyrite instability. Increasing amounts of injection water were added to native storage-zone water, and resulting reaction paths were plotted on pyrite stability diagrams. Native storage-zone water plotted within the pyrite stability field, indicating that conditions were sufficiently reducing to allow for pyrite stability. Thus, arsenic is immobilized in pyrite, and its groundwater concentration should be low. This was corroborated by analysis of water samples, none of which had arsenic concentrations above 0.036 microg/L. During simulation, however, as injection/native storage-zone water ratios increased, conditions became less reducing and pyrite became unstable. The result would be release of arsenic from limestone into storage-zone water.

Chemical Interactions of Hydraulic Fracturing Biocides with Natural Pyrite

Science.gov (United States)

Consolazio, Nizette A.

significantly. DBNPA is proposed to undergo redox reactions with the pyrite surface, accepting two-electrons from pyrite, and thus becoming reduced. The primary product is the monobrominated analogue of DBNPA, 2-monobromo-3-nitrilopropionamide (or MBNPA). The surface area-normalized first-order initial degradation rate constant was found to be 5.1 L.m-2day-1. It was also determined that the dissolution and oxidation products of pyrite, Fe II, S2O32- and SO4 2- are unlikely to contribute to the reduction of the biocide. Taken together, the results illustrate that a surface reaction with pyrite has the ability to reduce the persistence of DBNPA, and as a consequence change the distribution of its reaction products. The second objective was to quantify the influence of water chemistry and interactions with pyrite on the degradation of the sulfur-containing biocide. Dazomet readily hydrolyzes in water due to the nucleophilic attack of hydroxide (OH-) anions. Thus the half-life of dazomet during the shut-in phase of hydraulic fracturing will decrease with increasing pH: 8.5 hours at pH 4.1 to 3.4 hours at pH 8.2.Dazomet degradation was rapidly accelerated upon exposure to the oxidized pyrite surface, reacting five times faster than hydrolysis in the absence of pyrite at a similar pH. The products measured were identical to those identified on hydrolysis (methyl isothiocyanate and formaldehyde) and no dissolved iron was detected in solutions. This suggests that the dithiocarbamate group in dazomet was able to chemisorb onto the oxidized pyrite surface, shifting the electron density of the molecule which resulted in accelerated hydrolysis of the biocide. The third objective explored the reactivity of various biocide functional groups due to the addition of pyrite. Several elimination mechanisms were identified, and tied to the reactivity of the specific functional group involved. The addition of pyrite led to accelerated degradation of dibromodicyanobutane. This is because the bromine

Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

Energy Technology Data Exchange (ETDEWEB)

Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

1996-10-28

Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

Pyrite oxidation at circumneutral pH

Science.gov (United States)

Moses, Carl O.; Herman, Janet S.

1991-02-01

Previous studies of pyrite oxidation kinetics have concentrated primarily on the reaction at low pH, where Fe(III) has been assumed to be the dominant oxidant. Studies at circumneutral pH, necessitated by effective pH buffering in some pyrite oxidation systems, have often implicitly assumed that the dominant oxidant must be dissolved oxygen (DO), owing to the diminished solubility of Fe(III). In fact, Fe(III)(aq) is an effective pyrite oxidant at circumneutral pH, but the reaction cannot be sustained in the absence of DO. The purpose of this experimental study was to ascertain the relative roles of Fe(III) and DO in pyrite oxidation at circumneutral pH. The rate of pyrite oxidation was first-order with respect to the ratio of surface area to solution volume. Direct determinations of both Fe(II) (aq)> and Fe(III) (aq) demonstrated a dramatic loss of Fe(II) from the solution phase in excess of the loss for which oxidation alone could account. Based on rate data, we have concluded that Fe(II) is adsorbed onto the pyrite surface. Furthermore, Fe(II) is preferred as an adsorbate to Fe(III), which we attribute to both electrostatic and acid-base selectivity. We also found that the rate of pyrite oxidation by either Fe(III) (aq) or DO is reduced in the presence of aqueous Fe(II), which leads us to conclude that, under most natural conditions, neither Fe(III) (aq) nor DO directly attacks the pyrite surface. The present evidence suggests a mechanism for pyrite oxidation that involves adsorbed Fe( II ) giving up electrons to DO and the resulting Fe(III) rapidly accepting electrons from the pyrite. The adsorbed Fe is, thus, cyclically oxidized and reduced, while it acts as a conduit for electrons traveling from pyrite to DO. Oxygen is transferred from the hydration sphere of the adsorbed Fe to pyrite S. The cycle of adsorbed Fe oxidation and reduction and the successive addition of oxygen to pyrite S continues until a stable sulfoxy species dissociates from the surface. Prior

Heterocoagulation of chalcopyrite and pyrite minerals in flotation separation.

Science.gov (United States)

Mitchell, Timothy K; Nguyen, Anh V; Evans, Geoffrey M

2005-06-30

Heterocoagulation between various fine mineral particles contained within a mineral suspension with different structural and surface chemistry can interfere with the ability of the flotation processes to selectively separate the minerals involved. This paper examines the interactions between chalcopyrite (a copper mineral) and pyrite (an iron mineral often bearing gold) as they approach each other in suspensions with added chemicals, and relates the results to the experimental data for the flotation recovery and selectivity. The heterocoagulation was experimentally studied using the electrophoretic light scattering (ELS) technique and was modelled by incorporating colloidal forces, including the van der Waals, electrostatic double layer and hydrophobic forces. The ELS results indicated that pyrite has a positive zeta potential (zeta) up to its isoelectric point (IEP) at approximately pH 2.2, while chalcopyrite has a positive zeta up to its IEP at approximately pH 5.5. This produces heterocoagulation of chalcopyrite with pyrite between pH 2.2 and pH 5.5. The heterocoagulation was confirmed by the ELS spectra measured with a ZetaPlus instrument from Brookhaven and by small-scale flotation experiments.

THE DEPRESSION OF PYRITE FLOTATION BY THIOBACILLUS FERROOXIDANS

Institute of Scientific and Technical Information of China (English)

无

2000-01-01

The experimental studies on the microbial flotation of a pure pyrite sample using Thiobacillus ferrooxidans was conducted in the laboratory. The results indicate that Thiobacillus ferrooaidans has strong depression effect on the flotation of pyrite. Thiobacillus f errooxidans can adsorb on the surface of pyrite in a very short time (a few min. ), changing the surface from hydrophobic into hydrophilic and making the pyrite particles to lose their floatability. Therefore, Thiobacillus ferrooxidans is an effective microbial depressant of pyrite. It has also been pointed out that the depression of pyrite by Thiobacillus ferrooxidans is caused by the adsorption of the microbial colloids, but not by the oxidation effect.

Surface Chemical Characterisation of Pyrite Exposed to Acidithiobacillus ferrooxidans and Associated Extracellular Polymeric Substances

Directory of Open Access Journals (Sweden)

Sian M. La Vars

2018-03-01

Full Text Available A. ferrooxidans and their metabolic products have previously been explored as a viable alternative depressant of pyrite for froth flotation; however, the mechanism by which separation is achieved is not completely understood. Scanning electron microscopy (SEM, photoemission electron microscopy (PEEM, time-of-flight secondary ion mass spectrometry (ToF-SIMS and captive bubble contact angle measurements have been used to examine the surface physicochemical properties of pyrite upon exposure to A. ferrooxidans grown in HH medium at pH 1.8. C K-edge near edge X-ray absorption fine structure (NEXAFS spectra collected from PEEM images indicate hydrophilic lipids, fatty acids and biopolymers are formed at the mineral surface during early exposure. After 168 h, the spectra indicate a shift towards protein and DNA, corresponding to an increase in cell population and biofilm formation on the surface, as observed by SEM. The Fe L-edge NEXAFS show gradual oxidation of the mineral surface from Fe(II sulfide to Fe(III oxyhydroxides. The oxidation of the iron species at the pyrite surface is accelerated in the presence of A. ferrooxidans and extracellular polymeric substances (EPS as compared to HH medium controls. The surface chemical changes induced by the interaction with A. ferrooxidans show a significant decrease in surface hydrophobicity within the first 2 h of exposure. The implications of these findings are the potential use of EPS produced during early attachment of A. ferrooxidans, as a depressant for bioflotation.

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

International Nuclear Information System (INIS)

Tichomirowa, Marion; Junghans, Manuela

2009-01-01

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

Size-Dependent Affinity of Glycine and Its Short Oligomers to Pyrite Surface: A Model for Prebiotic Accumulation of Amino Acid Oligomers on a Mineral Surface

Science.gov (United States)

Afrin, Rehana; Ganbaatar, Narangerel; Aono, Masashi; Cleaves, H. James; Yano, Taka-aki; Hara, Masahiko

2018-01-01

The interaction strength of progressively longer oligomers of glycine, (Gly), di-Gly, tri-Gly, and penta-Gly, with a natural pyrite surface was directly measured using the force mode of an atomic force microscope (AFM). In recent years, selective activation of abiotically formed amino acids on mineral surfaces, especially that of pyrite, has been proposed as an important step in many origins of life scenarios. To investigate such notions, we used AFM-based force measurements to probe possible non-covalent interactions between pyrite and amino acids, starting from the simplest amino acid, Gly. Although Gly itself interacted with the pyrite surface only weakly, progressively larger unbinding forces and binding frequencies were obtained using oligomers from di-Gly to penta-Gly. In addition to an expected increase of the configurational entropy and size-dependent van der Waals force, the increasing number of polar peptide bonds, among others, may be responsible for this observation. The effect of chain length was also investigated by performing similar experiments using l-lysine vs. poly-l-lysine (PLL), and l-glutamic acid vs. poly-l-glutamic acid. The results suggest that longer oligomers/polymers of amino acids can be preferentially adsorbed on pyrite surfaces. PMID:29370126

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

Science.gov (United States)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

Strategies for Reduced Acid and Metalliferous Drainage by Pyrite Surface Passivation

Directory of Open Access Journals (Sweden)

Gujie Qian

2017-03-01

Full Text Available Acid and metalliferous drainage (AMD is broadly accepted to be a major global environmental problem facing the mining industry, requiring expensive management and mitigation. A series of laboratory-scale kinetic leach column (KLC experiments, using both synthetic and natural mine wastes, were carried out to test the efficacy of our pyrite passivation strategy (developed from previous research for robust and sustainable AMD management. For the synthetic waste KLC tests, initial treatment with lime-saturated water was found to be of paramount importance for maintaining long-term circum-neutral pH, favourable for the formation and preservation of the pyrite surface passivating layer and reduced acid generation rate. Following the initial lime-saturated water treatment, minimal additional alkalinity (calcite-saturated water was required to maintain circum-neutral pH for the maintenance of pyrite surface passivation. KLC tests examining natural potentially acid forming (PAF waste, with much greater peak acidity than that of the synthetic waste, blended with lime (≈2 wt % with and without natural non-acid-forming (NAF waste covers, were carried out. The addition of lime and use of NAF covers maintained circum-neutral leachate pH up to 24 weeks. During this time, the net acidity generated was found to be significantly reduced by the overlying NAF cover. If the reduced rate of acidity production from the natural PAF waste is sustained, the addition of smaller (more economically-feasible amounts of lime, together with application of NAF wastes as covers, could be trialled as a potential cost-effective AMD mitigation strategy.

Carbon mineralization and pyrite oxidation in groundwater: Importance for silicate weathering in boreal forest soils and stream base-flow chemistry

International Nuclear Information System (INIS)

Klaminder, J.; Grip, H.; Moerth, C.-M.; Laudon, H.

2011-01-01

Research highlights: → Organic compounds is mineralized during later transport in deep groundwater aquifers. → Carbonic acid generated by this process stimulates dissolution of silicate minerals. → Protons derived from pyrite oxidation also affects weathering in deep groundwater. → The identified weathering mechanisms affect base-flow chemistry in boreal streams. - Abstract: What role does mineralized organic C and sulfide oxidation play in weathering of silicate minerals in deep groundwater aquifers? In this study, how H 2 CO 3 , produced as a result of mineralization of organic matter during groundwater transport, affects silicate weathering in the saturated zone of the mineral soil along a 70 m-long boreal hillslope is demonstrated. Stream water measurements of base cations and δ 18 O are included to determine the importance of the deep groundwater system for downstream surface water. The results suggest that H 2 CO 3 generated from organic compounds being mineralized during the lateral transport stimulates weathering at depths between 0.5 and 3 m in the soil. This finding is indicated by progressively increasing concentrations of base cations-, silica- and inorganic C (IC) in the groundwater along the hillslope that co-occur with decreasing organic C (OC) concentrations. Protons derived from sulfide oxidation appear to be an additional driver of the weathering process as indicated by a build-up of SO 4 2- in the groundwater during lateral transport and a δ 34 S per mille value of +0.26-3.76 per mille in the deep groundwater indicating S inputs from pyrite. The two identified active acids in the deep groundwater are likely to control the base-flow chemistry of streams draining larger catchments (>1 km 2 ) as evident by δ 18 O signatures and base cation concentrations that overlap with that of the groundwater.

Carbon mineralization and pyrite oxidation in groundwater: Importance for silicate weathering in boreal forest soils and stream base-flow chemistry

Energy Technology Data Exchange (ETDEWEB)

Klaminder, J., E-mail: jonatan.klaminder@emg.umu.se [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden)] [Department of Ecology and Environmental Science, Umea University, SE-901 87 (Sweden); Grip, H. [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden); Moerth, C.-M. [Department of Geological Sciences, Stockholm University, 106 91 Stockholm (Sweden); Laudon, H. [Department of Forest Ecology and Management, SLU, SE-901 83 Umea (Sweden)

2011-03-15

Research highlights: {yields} Organic compounds is mineralized during later transport in deep groundwater aquifers. {yields} Carbonic acid generated by this process stimulates dissolution of silicate minerals. {yields} Protons derived from pyrite oxidation also affects weathering in deep groundwater. {yields} The identified weathering mechanisms affect base-flow chemistry in boreal streams. - Abstract: What role does mineralized organic C and sulfide oxidation play in weathering of silicate minerals in deep groundwater aquifers? In this study, how H{sub 2}CO{sub 3}, produced as a result of mineralization of organic matter during groundwater transport, affects silicate weathering in the saturated zone of the mineral soil along a 70 m-long boreal hillslope is demonstrated. Stream water measurements of base cations and {delta}{sup 18}O are included to determine the importance of the deep groundwater system for downstream surface water. The results suggest that H{sub 2}CO{sub 3} generated from organic compounds being mineralized during the lateral transport stimulates weathering at depths between 0.5 and 3 m in the soil. This finding is indicated by progressively increasing concentrations of base cations-, silica- and inorganic C (IC) in the groundwater along the hillslope that co-occur with decreasing organic C (OC) concentrations. Protons derived from sulfide oxidation appear to be an additional driver of the weathering process as indicated by a build-up of SO{sub 4}{sup 2-} in the groundwater during lateral transport and a {delta}{sup 34}S per mille value of +0.26-3.76 per mille in the deep groundwater indicating S inputs from pyrite. The two identified active acids in the deep groundwater are likely to control the base-flow chemistry of streams draining larger catchments (>1 km{sup 2}) as evident by {delta}{sup 18}O signatures and base cation concentrations that overlap with that of the groundwater.

Cu-As Decoupling in Hydrothermal Systems: A Link Between Pyrite Chemistry and Fluid Composition

Science.gov (United States)

Reich, M.; Tardani, D.; Deditius, A.; Chryssoulis, S.; Wrage, J.; Sanchez-Alfaro, P.; Andrea, H.; Cinthia, J.

2016-12-01

Chemical zonations in pyrite have been recognized in most hydrothermal ore deposit types, showing in some cases marked oscillatory alternation of metals and metalloids in pyrite growth zones (e.g., of Cu-rich, As-(Au)-depleted zones and As-(Au)-rich, Cu-depleted zones). This decoupled geochemical behavior of Cu and As has been interpreted as a result of chemical changes in ore-forming fluids, although direct evidence connecting fluctuations in hydrothermal fluid composition with metal partitioning into pyrite growth zones is still lacking. Here we report a comprehensive trace element database of pyrite from an active hydrothermal system, the Tolhuaca Geothermal System (TGS) in southern Chile. We combined high-spatial resolution and X-ray mapping capabilities of electron microprobe analysis (EMPA) with low detection limits and depth-profiling capabilities of secondary-ion mass spectrometry (SIMS) in a suite of pyrite samples retrieved from a 1 km drill hole that crosses the argillic and propylitic alteration zones of the geothermal system. We show that the concentrations of precious metals (e.g., Au, Ag), metalloids (e.g., As, Sb, Se, Te), and base and heavy metals (e.g., Cu, Co, Ni, Pb) in pyrite at the TGS are significant. Among the elements analyzed, arsenic, Cu and Co are the most abundant with concentrations that vary from sub-ppm levels to a few wt. %. Pyrites from the deeper propylitic zone do not show significant zonation and high Cu-(Co)-As concentrations correlate with each other. In contrast, well-developed zonations were detected in pyrite from the shallow argillic alteration zone, where Cu(Co)-rich, As-depleted cores alternate with Cu(Co)-depleted, As-rich rims. These microanalytical data were contrasted with chemical data of fluid inclusion in quartz veins (high Cu/Na and low As/Na) and borehole fluids (low Cu/Na and high As/Na) reported at the TGS, showing a clear correspondence between Cu and As concentrations in pyrite-forming fluids and chemical

Pyrite footprinting of RNA

International Nuclear Information System (INIS)

Schlatterer, Jörg C.; Wieder, Matthew S.; Jones, Christopher D.; Pollack, Lois; Brenowitz, Michael

2012-01-01

Highlights: ► RNA structure is mapped by pyrite mediated · OH footprinting. ► Repetitive experiments can be done in a powdered pyrite filled cartridge. ► High · OH reactivity of nucleotides imply dynamic role in Diels–Alderase catalysis. -- Abstract: In RNA, function follows form. Mapping the surface of RNA molecules with chemical and enzymatic probes has revealed invaluable information about structure and folding. Hydroxyl radicals ( · OH) map the surface of nucleic acids by cutting the backbone where it is accessible to solvent. Recent studies showed that a microfluidic chip containing pyrite (FeS 2 ) can produce sufficient · OH to footprint DNA. The 49-nt Diels–Alder RNA enzyme catalyzes the C–C bond formation between a diene and a dienophile. A crystal structure, molecular dynamics simulation and atomic mutagenesis studies suggest that nucleotides of an asymmetric bulge participate in the dynamic architecture of the ribozyme’s active center. Of note is that residue U42 directly interacts with the product in the crystallized RNA/product complex. Here, we use powdered pyrite held in a commercially available cartridge to footprint the Diels–Alderase ribozyme with single nucleotide resolution. Residues C39 to U42 are more reactive to · OH than predicted by the solvent accessibility calculated from the crystal structure suggesting that this loop is dynamic in solution. The loop’s flexibility may contribute to substrate recruitment and product release. Our implementation of pyrite-mediated · OH footprinting is a readily accessible approach to gleaning information about the architecture of small RNA molecules.

Geochemistry of shale and sedimentary pyrite as a proxy for gold fertility in the Selwyn basin area, Yukon

Science.gov (United States)

Sack, Patrick J.; Large, Ross R.; Gregory, Daniel D.

2018-01-01

Selwyn basin area strata contain sedimentary pyrite with Au above background levels when analyzed by laser ablation-inductively coupled mass spectrometry. Hyland Group rocks contain framboidal pyrite contents of 670 ppb Au, 1223 ppm As, and 5.3 ppm Te; the mean of all types of sedimentary pyrite in the Hyland Group is 391 ppb Au, 1489 ppm As, and 3.8 ppm Te. These levels are similar to sedimentary pyrite in host lithologies from major orogenic gold districts in New Zealand and Australia. Comparison of whole rock and pyrite data show that rocks deposited in continental slope settings with significant terrigenous input contain pyrite that is consistently enriched in Au, As, Te, Co, and Cu. Although data are limited, whole rock samples of stratigraphic units containing Au-rich pyrite also contain high Au, indicating that most of the Au is within sedimentary pyrite. Based on geologic characteristics and comparison of pyrite chemistry data with whole rock chemistry, Selwyn basin area strata have the necessary ingredients to form orogenic gold deposits: Au-enriched source rocks, metamorphic conditions permissive of forming a metamorphic ore fluid, and abundant structural preparation for channeling fluids and depositing ore.

Surface chemistry essentials

CERN Document Server

Birdi, K S

2013-01-01

Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w

Pyrite Iron Sulfide Solar Cells Made from Solution Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Law, Matt [Univ. of California, Irvine, CA (United States)

2017-03-21

This document summarizes research done under the SunShot Next Generation PV II project entitled, “Pyrite Iron Sulfide Solar Cells Made from Solution,” award number DE-EE0005324, at the University of California, Irvine, from 9/1/11 thru 11/30/16. The project goal was to develop iron pyrite (cubic FeS₂) as an absorber layer for solution-processible p-n heterojunction solar cells with a pathway to >20% power conversion efficiency. Project milestones centered around seven main Tasks: (1) make device-quality pyrite thin-films from solar ink; (2) develop an ohmic bottom contact with suitable low resistivity; (3) produce a p-n heterojunction with VOC > 400 mV; (4) make a solar cell with >5% power conversion efficiency; (5) use alloying to increase the pyrite band gap to ~1.2-1.4 eV; (6) produce a p-n heterojunction with VOC > 500 mV; and finally (7) make a solar cell with >10% power conversion efficiency. In response to project findings, the Tasks were amended midway through the project to focus particular effort on passivating the surface of pyrite in order to eliminate excessively-strong surface band bending believed to be responsible for the low VOC of pyrite diodes. Major project achievements include: (1) development and detailed characterization of several new solution syntheses of high-quality thin-film pyrite, including two “molecular ink” routes; (2) demonstration of Mo/MoS₂ bilayers as good ohmic bottom contacts to pyrite films; (3) fabrication of pyrite diodes with a glass/Mo/MoS₂/pyrite/ZnS/ZnO/AZO layer sequence that show VOC values >400 mV and as high as 610 mV at ~1 sun illumination, although these high VOC values ultimately proved irreproducible; (4) established that ZnS is a promising n-type junction partner for pyrite; (5) used density functional theory to show that the band gap of pyrite can be increased from ~1.0 to a more optimal 1.2-1.3 eV by alloying with oxygen; (6) through extensive measurements of ultrahigh

Carrier-microencapsulation using Si-catechol complex for suppressing pyrite floatability

Energy Technology Data Exchange (ETDEWEB)

Jha, R.K.T.; Satur, J.; Hiroyoshi, N.; Ito, M.; Tsunekawa, M. [Hokkaido University, Hokkaido (Japan). Graduate School of Engineering

2008-11-15

Pyrite (FeS{sub 2}) is a common sulfide mineral associated with valuable metal minerals and coal, and it is rejected as a gangue mineral using physical separation techniques such as froth flotation and discharged into tailing pond. In the flotation, pyrite is frequently entrapped in the froth due to its hydrophobic nature. Formation of acid mine drainage due to the air-oxidation of pyrite in the tailing pond is also a serious problem. The authors have proposed carrier-microencapsulation (CME) as a method for suppressing both the floatability and oxidation of pyrite. In this method, pyrite is coated with a thin layer of metal oxide or hydroxide using catechol solution as a carrier combined with metal ions. The layer converts the pyrite surface from hydrophobic to hydrophilic and acts as a protective coating against oxidation. The present study demonstrates the effect of CME using Si-catechol complex to suppress the pyrite floatability: The bubble pick-up experiments showed that attachment of pyrite particles to air bubble is suppressed by the CME treatment at pH 4-10, Si-catechol complex concentration over 0.5 mol m{sup -3} and treatment time within 2 min. The Hallimond tube flotation experiments showed that the pyrite floatability is suppressed by the CME treatment even in the presence of typical flotation collectors such as kerosene and xanthate. SEM-EDX analysis confirmed that Si present on the pyrite surface treated by Si-catechol complex, implying that SiO{sub 2} or SiOH{sub 4} layer formed by the CME treatment convert the pyrite surface hydrophobic to hydrophilic.

Short communication: Adverse effect of surface-active reagents on the bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans.

Science.gov (United States)

Huerta, G; Escobar, B; Rubio, J; Badilla-Ohlbaum, R

1995-09-01

Oxidation of Fe(II) iron and bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans was adversely affected by isopropylxanthate, a flotation agent, and by LIX 984, a solvent-extraction agent, each at ≤ 1 g/l. The reagents/l were adsorbed on the bacterial surface, decreasing the bacteria's development and preventing biooxidation. Both reagents inhibited the bioleaching of pyrite and LIX 984 also inhibited the bioleaching of chalcopyrite.

Action time effect of lime on its depressive ability for pyrite

Institute of Scientific and Technical Information of China (English)

Tichang Sun

2004-01-01

Two sample groups of bulk concentrates consisting mainly of pyrite and chalcopyrite from Daye and Chenghchao Mines in Hubei Province of China were used to investigate the effect of the action time of lime on its depressive ability for pyrite. The experimental results conducted with different samples and collectors showed that the action time between lime and pyrite markedly influences the depressive ability of lime. The depressive ability of lime increased with the action time increasing. It was also proved that the depressive results obtained at a large lime dosage after a shorter action time are similar to those obtained at a small lime dosage after a longer action time. The increase of depressive ability of lime after a longer action time is because that there are different mechanisms in different action time. The composition on the surface of pyrite acted for different time with lime was studied by using ESCA (Electron Spectroscopic Chemical Analysis). The results showed that iron hydroxide and calcium sulphate formed on the pyrite surface at the presence of lime in the pulp but the amounts of iron hydroxide and calcium sulphate were different at different action time. At the beginning action time the compound formed on the pyrite surface was mainly calcium sulphate and almost no iron hydroxide formed; but with the action time increasing, iron hydroxide formed. The longer the action time, the more iron hydroxide and the less calcium sulphate formed. It was considered that the stronger depressive ability of lime after a longer action time is because more iron hydroxide forms on the pyrite surface.

Selective separation of pyrite and chalcopyrite by biomodulation.

Science.gov (United States)

Chandraprabha, M N; Natarajan, K A; Modak, Jayant M

2004-09-01

Selective separation of pyrite from other associated ferrous sulphides at acidic and neutral pH has been a challenging problem. This paper discusses the utility of Acidithiobacillus ferrooxidans for the selective flotation of chalcopyrite from pyrite. Consequent to interaction with bacterial cells, pyrite remained depressed even in the presence of potassium isopropyl xanthate collector while chalcopyrite exhibited significant flotability. However, when the minerals were conditioned together, the selectivity achieved was poor due to the activation of pyrite surface by the copper ions in solution. The selectivity was improved when the sequence of conditioning with bacterial cells and collector was reversed, since the bacterial cells were able to depress collector interacted pyrite effectively, while having negligible effect on chalcopyrite. The observed behaviour is analysed and discussed in detail. The separation obtained was significant both at acidic and alkaline pH. This selectivity achieved was retained when the minerals were interacted with both bacterial cells and collector simultaneously.

Isotopic and elemental chemistry of sedimentary pyrite: A combined analytical and statistical approach to a novel planetary biosignature

Science.gov (United States)

Figueroa, M. C.; Gregory, D. D.; Lyons, T. W.; Williford, K. H.

2017-12-01

Life processes affect trace element abundances in pyrite such that sedimentary and hydrothermal pyrite have significantly different trace element signatures. Thus, we propose that these biogeochemical data could be used to identify pyrite that formed biogenetically either early in our planet's history or on other planets, particularly Mars. The potential for this approach is elevated because pyrite is common in diverse sedimentary settings, and its trace element content can be preserved despite secondary overprints up to greenschist facies, thus minimizing the concerns about remobilization that can plague traditional whole rock studies. We are also including in-situ sulfur isotope analysis to further refine our understanding of the complex signatures of ancient pyrite. Sulfur isotope data can point straightforwardly to the involvement of life, because pyrite in sediments is inextricably linked to bacterial sulfate reduction and its diagnostic isotopic expressions. In addition to analyzing pyrite of known biological origin formed in the modern and ancient oceans under a range of conditions, we are building a data set for pyrite formed by hydrothermal and metamorphic processes to minimize the risk of false positives in life detection. We have used Random Forests (RF), a machine learning statistical technique with proven efficiency for classifying large geological datasets, to classify pyrite into biotic and abiotic end members. Coupling the trace element and sulfur isotope data from our analyses with a large existing dataset from diverse settings has yielded 4500 analyses with 18 different variables. Our initial results reveal the promise of the RF approach, correctly identifying biogenic pyrite 97 percent of the time. We will continue to couple new in-situ S-isotope and trace element analyses of biogenic pyrite grains from modern and ancient environments, using cutting-edge microanalytical techniques, with new data from high temperature settings. Our ultimately goal

Microbial Oxidation of Pyrite Coupled to Nitrate Reduction in Anoxic Groundwater Sediment

DEFF Research Database (Denmark)

Jørgensen, Christian Juncher; Elberling, Bo; Jacobsen, Ole Stig

2009-01-01

denitrification process with pyrite as the primary electron donor. The process demonstrates a temperature dependency (Q10) of 1.8 and could be completely inhibited by addition of a bactericide (NaN3). Experimentally determined denitrification rates show that more than 50% of the observed nitrate reduction can...... be ascribed to pyrite oxidation. The apparent zero-order denitrification rate in anoxic pyrite containing sediment at groundwater temperature has been determined to be 2-3 µmol NO3- kg-1 day-1. The in situ groundwater chemistry at the boundary between the redoxcline and the anoxic zone reveals that between 65......-anoxic boundary in sandy aquifers thus determining the position and downward progression of the redox boundary between nitrate-containing and nitrate-free groundwater....

Effect of Pyrite on Thiosulfate Leaching of Gold and the Role of Ammonium Alcohol Polyvinyl Phosphate (AAPP

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Xiaoliang Liu

2017-07-01

Full Text Available The effect of pyrite and the role of ammonium alcohol polyvinyl phosphate (AAPP during gold leaching in ammoniacal thiosulfate solutions were investigated using pure gold foils. The results showed that pyrite catalyzed the decomposition and also significantly increased the consumption of thiosulfate. This detrimental effect became more severe with increasing pyrite content. Further, the presence of pyrite also substantially slowed the gold leaching kinetics and reduced the overall gold dissolution. The reduction in gold dissolution was found to be caused primarily by the surface passivation of the gold. The negative effects of pyrite, however, can be alleviated by the addition of AAPP. Comparison of zeta potentials of pyrite with and without AAPP suggests that AAPP had adsorbed on the surface of the pyrite and weakened the catalytic effect of pyrite on the thiosulfate decomposition by blocking the contact between the pyrite and thiosulfate anions. AAPP also competed with thiosulfate anions to complex with the cupric ion at the axial coordinate sites, and thus abated the oxidation of thiosulfate by cupric ions. Moreover, the indiscriminate adsorption of AAPP on the surfaces of gold and passivation species prevented the passivation of the gold surface by surface charge and electrostatic repulsion. Therefore, AAPP effectively stabilized the thiosulfate in the solution and facilitated the gold leaching in the presence of pyrite.

Thermal behaviors of mechanically activated pyrites by thermogravimetry (TG)

International Nuclear Information System (INIS)

Hu Huiping; Chen Qiyuan; Yin Zhoulan; Zhang Pingmin

2003-01-01

The thermal decompositions of mechanically activated and non-activated pyrites were studied by thermogravimetry (TG) at the heating rate of 10 K min -1 in argon. Results indicate that the initial temperature of thermal decomposition (T di ) in TG curves for mechanically activated pyrites decreases gradually with increasing the grinding time. The specific granulometric surface area (S G ), the structural disorder of mechanically activated pyrites were analyzed by X-ray diffraction laser particle size analyzer, and X-ray powder diffraction analysis (XRD), respectively. The results show that the S G of mechanically activated pyrites remains almost constant after a certain grinding time, and lattice distortions (ε) rise but the crystallite sizes (D) decrease with increasing the grinding time. All these results imply that the decrease of T di in TG curves of mechanically activated pyrites is mainly caused by the increase of lattice distortions ε and the decrease of the crystallite sizes D of mechanically activated pyrite with increasing the grinding time. The differences in the reactivity between non-activated and mechanically activated pyrites were observed using characterization of the products obtained from 1 h treatment of non-activated and mechanically activated pyrites at 713 K under inert atmosphere and characterization of non-activated and mechanically activated pyrites exposed to ambient air for a certain period

Mechanisms of interaction between arsenian pyrite and aqueous arsenite under anoxic and oxic conditions

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Qiu, Guohong; Gao, Tianyu; Hong, Jun; Luo, Yao; Liu, Lihu; Tan, Wenfeng; Liu, Fan

2018-05-01

Pyrite affects the conversion and migration processes of arsenic in soils and waters. Adsorption and redox reactions of arsenite (As(III)) occur on the surface of pyrite, and the interaction processes are influenced by the arsenic incorporated into pyrite. This work examined the effects of arsenic content, pH and oxygen on the interaction between arsenian pyrite and aqueous As(III) and investigated the underlying mechanisms. The results indicated that arsenic incorporation led to a high content of Fe(III) in pyrite, and that As(III) was mainly adsorbed on pyrite surface and part of As(III) was oxidized to As(V) by the newly formed intermediates including hydroxyl radicals and hydrogen peroxide. The oxidation rate increased with increasing arsenic content in the pyrite and the presence of air (oxygen), and first decreased and then increased with increasing pH from 3.0 to 11.0. Hydroxyl radicals and hydrogen peroxide significantly contributed to the oxidation of pyrite and aqueous As(III) in acidic and alkaline solutions, respectively. Although pyrite oxidation increased with increasing arsenic content as indicated by the elevated concentrations of elemental S and SO42-, the percentage of released arsenic in total arsenic of the arsenian pyrite decreased due to the adsorption of arsenic on the surface of newly formed ferric (hydr)oxides, especially the ferric arsenate precipitate formed in high pH solutions. The present study enables a better understanding of the important interaction process of dissolved arsenite and natural pyrites in the study of groundwater contamination, arsenic migration/sequestration, and acid mine drainage formation.

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

Science.gov (United States)

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; Gault-Ringold, Melanie; George, Ejin; Rijkenberg, Micha J. A.

2018-04-01

The chemical response of the Precambrian oceans to rising atmospheric O2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shift in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the 'Great Oxidation Event' around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise

Influence of the Interaction between Sphalerite and Pyrite on the Copper Activation of Sphalerite

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Bo Yang

2018-01-01

Full Text Available In this paper, the effect of pyrite on the activation of sphalerite was investigated by micro-flotation, copper adsorption experiments, X-ray photoelectron spectroscopy (XPS, and electrochemical measurement. The micro-flotation test results showed that the recovery and flotation rate of sphalerite with copper sulphate as activator and butyl xanthate as collector were significantly decreased with the increasing content of pyrite in pulp. Cu2+ adsorption results indicated that the adsorption of Cu2+ on the sphalerite surface were decreased when pyrite was present in the pulp. XPS surface analysis demonstrated that the proportion of Cu+ species increased in the activation products on the sphalerite surface, but the total atomic concentration of Cu atom was decreased. Linear voltammetry measurement suggested that the current density of Cu+ species oxidizing to Cu2+ species was increased when sphalerite was electrically contacted with pyrite, which confirmed the increased proportion of Cu+ species on Cu-activation sphalerite surface when contacting with pyrite. These results indicated that there is not only a competitive adsorption for cupric ions (Cu2+, but the galvanic interaction between sphalerite and pyrite also has a significant influence on the copper activation of sphalerite.

Silane-based coatings on the pyrite for remediation of acid mine drainage.

Science.gov (United States)

Diao, Zenghui; Shi, Taihong; Wang, Shizhong; Huang, Xiongfei; Zhang, Tao; Tang, Yetao; Zhang, Xiaying; Qiu, Rongliang

2013-09-01

Acid mine drainage (AMD) resulting from the oxidation of pyrite and other metal sulfides has caused significant environmental problems, including acidification of rivers and streams as well as leaching of toxic metals. With the goal of controlling AMD at the source, we evaluated the potential of tetraethylorthosilicate (TEOS) and n-propyltrimethoxysilane (NPS) coatings to suppress pyrite oxidation. The release of total Fe and SO4(-2) from uncoated and coated pyrite in the presence of a chemical oxidizing agent (H2O2) or iron-oxidizing bacteria (Acidithiobacillus ferrooxidans) was measured. Results showed that TEOS- and NPS-based coatings reduced chemical oxidation of pyrite by as much as 59 and 96% (based on Fe release), respectively, while biological oxidation of pyrite was reduced by 69 and 95%, respectively. These results were attributed to the formation of a dense network of Fe-O-Si and Si-O-Si bonds on the pyrite surface that limited permeation of oxygen, water, and bacteria. Compared with results for TEOS-coated pyrite, higher pH and lower concentrations of total Fe and SO4(-2) were observed for oxidation of NPS-coated pyrite, which was attributed to its crack-free morphology and the presence of hydrophobic groups on the NPS-based coating surface. The silane-based NPS coating was shown to be highly effective in suppressing pyrite oxidation, making it a promising alternative for remediation of AMD at its source. Copyright © 2013 Elsevier Ltd. All rights reserved.

Thermal decomposition of pyrite

International Nuclear Information System (INIS)

Music, S.; Ristic, M.; Popovic, S.

1992-01-01

Thermal decomposition of natural pyrite (cubic, FeS 2 ) has been investigated using X-ray diffraction and 57 Fe Moessbauer spectroscopy. X-ray diffraction analysis of pyrite ore from different sources showed the presence of associated minerals, such as quartz, szomolnokite, stilbite or stellerite, micas and hematite. Hematite, maghemite and pyrrhotite were detected as thermal decomposition products of natural pyrite. The phase composition of the thermal decomposition products depends on the terature, time of heating and starting size of pyrite chrystals. Hematite is the end product of the thermal decomposition of natural pyrite. (author) 24 refs.; 6 figs.; 2 tabs

Oxidation of pyrite: Consequences and significance

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Dimitrijević Mile D.

2002-01-01

Full Text Available This paper presents the most important studies on the oxidation of pyrite particularly in aqueous solutions. The consequences of pyrite oxidation was examined, as well as its importance, from both the technical-technological and environmental points of view. The oxidation of pyrite was considered in two parts. The spontaneous oxidation of pyrite in nature was described in the first part, with this part comprising pyrite oxidation in deposits depots and mines. It is explained how way natural electrochemical processes lead to the decomposition of pyrite and other minerals associated with pyrite. The oxidation of pyrite occurring during technological processes such as grinding, flotation and leaching, was shown in the second part. Particular emphasis was placed on the oxidation of pyrite during leaching. This part includes the leaching of sulphide and oxide ores, the leaching of pyrite coal and the leaching of refractory gold-bearing ores (pressure oxidation, bacterial oxidation, oxidation by means of strong oxidants and the electrolysis of pyrite suspensions. Various mechanisms of pyrite oxidation and of the galvanic interaction of pyrite with other sulphide minerals are shown.

Calorimetric investigation on mechanically activated storage energy mechanism of sphalerite and pyrite

International Nuclear Information System (INIS)

Xiao Zhongliang; Chen Qiyuan; Yin Zhoulan; Hu Huiping; Wu Daoxin

2005-01-01

The structural changes of mechanically activated sphalerite and pyrite under different grinding conditions were determined by X-ray powder diffraction (XRD), laser particle size analyzer and elemental analysis. The storage energy of mechanically activated sphalerite and pyrite was measured by a calorimetric method. A thermochemical cycle was designed so that mechanically activated and non-activated minerals reached the same final state when dissolved in the same oxidizing solvent. The results show that the storage energy of mechanically activated sphalerite and pyrite rises with increased in grinding time, and reaches a maximum after a certain grinding period. The storage energy of mechanically activated pyrite decreases when heated under inert atmosphere. The storage energy of mechanically activated sphalerite and pyrite remains constant when treated below 573 K under inert atmosphere. The percentage of the storage energy caused by surface area increase during mechanical activation decreases with increasing grinding time. These results support our opinion that the mechanically activated storage energy of sphalerite is closely related to lattice distortions, and the mechanically activated storage energy of pyrite is mainly caused by the formation of reactive sites on the surface

Oxidation state of gold and arsenic in gold-bearing arsenian pyrite

Energy Technology Data Exchange (ETDEWEB)

Simon, G.; Huang, H.; Penner-Hahn, J.E.; Kesler, S.E.; Kao, L.S. [Univ. of Michigan, Ann Arbor, MI (United States)

1999-07-01

XANES measurements on gold-bearing arsenian pyrite from the Twin Creeks Carlin-type gold deposits show that gold is present as both Au{sup 0} and Au{sup 1+} and arsenic is present as As{sup 1{minus}}. Au{sup 0} is attributed to sub-micrometer size inclusions of free gold, whereas Au{sup 1+} is attributed to gold in the lattice of the arsenian pyrite. STEM observations suggest that As{sup 1{minus}} is probably concentrated in angstrom-scale, randomly distributed layers with a marcasite or arsenopyrite structure. Ionic gold (Au{sup 1+}) could be concentrated in these layers as well, and is present in both twofold- and fourfold-coordinated forms, with fourfold-coordinated Au{sup 1+} more abundant. Twofold-coordinated Au{sup 1+} is similar to gold in Au{sub 2}S in which it is linearly coordinated to two sulfur atoms. The nature of fourfold-coordinated Au{sup 1+} is not well understood, although it might be present as an Au-As-S compound where gold is bonded in fourfold coordination to sulfur and arsenic atoms, or in vacancy positions on a cation site in the arsenian pyrite. Au{sup 1+} was probably incorporated into arsenian pyrite by adsorption onto pyrite surfaces during crystal growth. The most likely compound in the case of twofold-coordinated Au{sup 1+} was probably a tri-atomic surface complex such as S{sub pyrite}-Au{sup 1+}-S{sub bi-sulfide}H or Au{sup 1+}-S-Au{sup 1+}. The correlation between gold and arsenic might be related to the role of arsenic in enhancing the adsorption of gold complexes of this type on pyrite surfaces, possibly through semiconductor effects.

Hydrogeologic and environmental impact of amjhore pyrite mines, India

Science.gov (United States)

Choubey, Vishnu D.; Rawat, Rajendra K.

1991-01-01

Drainage from active and inactive pyrite mines has produced chemical and physical pollution of both ground- and surface water in Amjhore region. In the present case, chemical pollution is caused by exposing pyrite minerals to oxidation or leaching, resulting in undesirable concentrations of dissolved materials. Pyrite mining suddenly exposed large quantities of sulfides to direct contact with oxygen, and oxidation proceeds rapidly, resulting in acidity and release of metal (Fe) and sulfates to the water system, eventually resulting in water pollution in the region. The magnitude and impact of the problem is just being recognized and, as the present and the future projected demand for clean water is of top priority, the present studies were undertaken. Mine drainage includes water flowing from the surface and underground mines and runoff or seepage from the pyrite mines. This article describes the various hydrologic factors that control acid water formation and its transport. The mine drainage is obviously a continuing source of pollution and, therefore, remedial measures mainly consisting of a double-stage limestone-lime treatment technique have been suggested. The present results will be used to develop an alternative and more effective abatement technology to mitigate acid production at the source, namely, the technique of revegetation of the soil cover applied to the waste mine dump material. Water quality change is discussed in detail, with emphasis on acidity formed from exposed pyrite material and on increase in dissolved solids. Preventive and treatment measures are recommended.

Pyrite sulfur isotopes reveal glacial-interglacial environmental changes

Science.gov (United States)

Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina; Revillon, Sidonie; Houghton, Jennifer; Fike, David A.

2017-06-01

The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial-interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial-interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial-interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

Degradation of Diclofenac by sonosynthesis of pyrite nanoparticles.

Science.gov (United States)

Khabbaz, M; Entezari, M H

2017-02-01

The aim of this work is to evaluate the ability of synthesized pyrite nanoparticles (NPs) on the degradation of Diclofenac (DCF) as a model pharmaceutical pollutant. Pyrite NPs were synthesized by sonication with 20 kHz apparatus under optimum conditions. The effects of pyrite loading (0.02-0.20 g/L), DCF concentration (10-50 mg/L) and initial pH (2-10) on the degradation were investigated. The results revealed that the NPs have a great activity in the degradation of DCF with 25 mg/L concentration. A first-order kinetic model was found to match the experimental data. Complete degradation (100%) of DCF was achieved by pyrite within 3 min and 20 min in acidic and natural pH, respectively. To gain an understanding of the degradation mechanism and the role of pyrite, a UV-Vis spectrophotometer was employed to follow the DCF concentration. In addition, the Chemical Oxygen Demand (COD) and the amounts of ammonium and chloride ions verified complete degradation of DCF in both pH values. The results demonstrated that Fe 2+ ions were generated by the pyrite surface and the hydroxyl radical (OH) was formed by Fe 2+ ions through the Fenton reaction. Based on using radical scavengers in the degradation process, OH was mainly responsible for the fast degradation of DCF. COD measurements confirmed that DCF finally degraded to further oxidized forms (NH 4 + , Cl - ). Copyright © 2016 Elsevier Ltd. All rights reserved.

Selective separation of arsenopyrite from pyrite by biomodulation in the presence of Acidithiobacillus ferrooxidans.

Science.gov (United States)

Chandraprabha, M N; Natarajan, K A; Somasundaran, P

2004-08-15

Effective methods for selective separation using flotation or flocculation of arsenopyrite from pyrite by biomodulation using Acidithiobacillus ferrooxidans are presented here. Adhesion of the bacterium to the surface of arsenopyrite was very slow compared to that to pyrite, resulting in a difference in surface modification of the minerals subsequent to interaction with cells. The cells were able to effectively depress pyrite flotation in presence of collectors like potassium isopropyl xanthate and potassium amyl xanthate. On the other hand the flotability of arsenopyrite after conditioning with the cells was not significantly affected. The activation of pyrite by copper sulfate was reduced when the minerals were conditioned together, resulting in better selectivity. Selective separation could also be achieved by flocculation of biomodulated samples.

Effect of capping ligands on the optical properties and electronic energies of iron pyrite FeS2 nanocrystals and solid thin films

International Nuclear Information System (INIS)

Zhai, Guangmei; Xie, Rongwei; Wang, Heng; Zhang, Jitao; Yang, Yongzhen; Wang, Hua; Li, Xuemin; Liu, Xuguang; Xu, Bingshe

2016-01-01

In this work, the optical and electronic properties of iron pyrite FeS 2 nanocrystals and solid thin films with various capping ligands were systematically investigated by UV–Vis–NIR absorption spectroscopy, cyclic voltammetry and current density–voltage characteristic measurements. The iron pyrite nanocrystals with various ligands have an indirect band gap of around 1.05 eV and broad absorption spanning into the near-infrared region, exhibiting favorable optical properties for their photovoltaic applications. The electron affinities and ionization potentials of FeS 2 nanocrystals determined through cyclic voltammetry measurements show strong ligand dependence. An energy level shift of up to 190 meV was obtained among the pyrite nanocrystals capped with the ligands employed in this work. The iron pyrite nanocrystal films capped with iodide and 1,2-ethanedithiol exhibit the largest band edge energy shift and conductivity, respectively. Our results not only provide several useful optical and electronic parameters of pyrite nanocrystals for their further use in optoelectronic devices as active layers and/or infrared optical absorption materials, but also highlight the relationship between their surface chemistry and electronic energies. - Highlights: • The energy levels of FeS 2 nanocrystals with various ligands were determined via electrochemical measurements. • The energy levels of FeS 2 nanocrystals showed strong ligand-dependence. • An energy level shift of up to 190 meV was obtained for the pyrite nanocrystals studied in the work. • The conductivities of FeS 2 nanocrystals with different ligands were obtained by current density–voltage measurements.

A dynamic mathematical model for microbial removal of pyritic sulfur from coal.

Science.gov (United States)

Kargi, F; Weissman, J G

1984-06-01

A dynamic mathematical model has been developed to describe microbial desulfurization of coal by Thiobacillus ferrooxidans. The model considers adsorption and desorption of cells on coal particles and microbial oxidation of pyritic sulfur on particle surfaces. The influence of certain parameters, such as microbial growth rate constants, adsorption-description constants, pulp density, coal particle size, initial cell and solid phase substrate concentration on the maximum rate of pyritic sulfur removal, have been elucidated. The maximum rate of pyritic sulfur removal was strongly dependent upon the number of attached cells per coal particle. At sufficiently high initial cell concentrations, the surfaces of coal particles are nearly saturated by the cells and the maximum leaching rate is limited either by total external surface area of coal particles or by the concentration of pyritic sulfur in the coal phase. The maximum volumetric rate of pyritic sulfur removal (mg S/h cm(3) mixture) increases with the pulp density of coal and reaches a saturation level at high pulp densities (e.g. 45%). The maximum rate also increases with decreasing particle diameter in a hyperbolic form. Increases in adsorption coefficient or decreases in the desorption coefficient also result in considerable improvements in this rate. The model can be applied to other systems consisting of suspended solid substrate particles in liquid medium with microbial oxidation occurring on the particle surfaces (e.g., bacterial ore leaching). The results obtained from this model are in good agreement with published experimental data on microbial desulfurization of coal and bacterial ore leaching.

Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

Science.gov (United States)

Fantauzzi, Marzia; Licheri, Cristina; Atzei, Davide; Loi, Giovanni; Elsener, Bernhard; Rossi, Giovanni; Rossi, Antonella

2011-10-01

In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action. © Springer-Verlag 2011

Effect of capping ligands on the optical properties and electronic energies of iron pyrite FeS{sub 2} nanocrystals and solid thin films

Energy Technology Data Exchange (ETDEWEB)

Zhai, Guangmei, E-mail: zhaiguangmei@tyut.edu.cn [Key Laboratory of Interface Science and Engineering in Advanced Materials of Ministry of Education of the People' s Republic of China, Research Centre of Advanced Materials Science and Technology of Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Jiangsu Key Laboratory for Solar Cell Materials and Technology, Changzhou University, Changzhou, Jiangsu 213164 (China); State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu, Sichuan 610054 (China); Xie, Rongwei; Wang, Heng; Zhang, Jitao; Yang, Yongzhen; Wang, Hua; Li, Xuemin [Key Laboratory of Interface Science and Engineering in Advanced Materials of Ministry of Education of the People' s Republic of China, Research Centre of Advanced Materials Science and Technology of Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Liu, Xuguang [Key Laboratory of Interface Science and Engineering in Advanced Materials of Ministry of Education of the People' s Republic of China, Research Centre of Advanced Materials Science and Technology of Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Xu, Bingshe [Key Laboratory of Interface Science and Engineering in Advanced Materials of Ministry of Education of the People' s Republic of China, Research Centre of Advanced Materials Science and Technology of Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China)

2016-07-25

In this work, the optical and electronic properties of iron pyrite FeS{sub 2} nanocrystals and solid thin films with various capping ligands were systematically investigated by UV–Vis–NIR absorption spectroscopy, cyclic voltammetry and current density–voltage characteristic measurements. The iron pyrite nanocrystals with various ligands have an indirect band gap of around 1.05 eV and broad absorption spanning into the near-infrared region, exhibiting favorable optical properties for their photovoltaic applications. The electron affinities and ionization potentials of FeS{sub 2} nanocrystals determined through cyclic voltammetry measurements show strong ligand dependence. An energy level shift of up to 190 meV was obtained among the pyrite nanocrystals capped with the ligands employed in this work. The iron pyrite nanocrystal films capped with iodide and 1,2-ethanedithiol exhibit the largest band edge energy shift and conductivity, respectively. Our results not only provide several useful optical and electronic parameters of pyrite nanocrystals for their further use in optoelectronic devices as active layers and/or infrared optical absorption materials, but also highlight the relationship between their surface chemistry and electronic energies. - Highlights: • The energy levels of FeS{sub 2} nanocrystals with various ligands were determined via electrochemical measurements. • The energy levels of FeS{sub 2} nanocrystals showed strong ligand-dependence. • An energy level shift of up to 190 meV was obtained for the pyrite nanocrystals studied in the work. • The conductivities of FeS{sub 2} nanocrystals with different ligands were obtained by current density–voltage measurements.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

Science.gov (United States)

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Extreme Ultraviolet (EUV) induced surface chemistry on Ru

NARCIS (Netherlands)

Liu, Feng; Sturm, Jacobus Marinus; Lee, Christopher James; Bijkerk, Frederik

2013-01-01

EUV photon induced surface chemistry can damage multilayer mirrors causing reflectivity loss and faster degradation. EUV photo chemistry involves complex processes including direct photon induced surface chemistry and secondary electron radiation chemistry. Current cleaning techniques include dry

A review of the fundamental studies of the copper activation mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite.

Science.gov (United States)

Chandra, A P; Gerson, A R

2009-01-30

A review of the considerable, but often contradictory, literature examining the specific surface reactions associated with copper adsorption onto the common metal sulfide minerals sphalerite, (Zn,Fe)S, and pyrite (FeS(2)), and the effect of the co-location of the two minerals is presented. Copper "activation", involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the flotation and separation of minerals in an ore. Due to the complexity of metal sulfide mineral containing systems this activation process and the emergence of activation products on the mineral surfaces are not fully understood for most sulfide minerals even after decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Sufficient oxidation potential is also needed (through O(2) conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is sufficiently depressed while sphalerite floats. Good water quality with low concentrations of contaminant ions, such as Pb(2+)and Fe(2+), is also needed to limit inadvertent activation and flotation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial

Attenuation of pyrite oxidation with a fly ash pre-barrier: Reactive transport modelling of column experiments

Energy Technology Data Exchange (ETDEWEB)

Perez-Lopez, R.; Cama, J.; Nieto, J.M.; Ayora, C.; Saaltink, M.W. [University of Huelva, Huelva (Spain). Dept. of Geology

2009-09-15

Conventional permeable reactive barriers (PRBs) for passive treatment of groundwater contaminated by acid mine drainage (AMD) use limestone as reactive material that neutralizes water acidity. However, the limestone-alkalinity potential ceases as inevitable precipitation of secondary metal-phases on grain surfaces occurs, limiting its efficiency. In the present study, fly ash derived from coal combustion is investigated as an alternative alkalinity generating material for the passive treatment of AMD using solution-saturated column experiments. Unlike conventional systems, the utilization of fly ash in a pre-barrier to intercept the non-polluted recharge water before this water reacts with pyrite-rich wastes is proposed. Chemical variation in the columns was interpreted with the reactive transport code RETRASO. In parallel, kinetics of fly ash dissolution at alkaline pH were studied using flow-through experiments and incorporated into the model. In a saturated column filled solely with pyritic sludge-quartz sand (1: 10), oxidation took place at acidic conditions (pH 3.7). According to SO{sub 4}{sup 2-} release and pH, pyrite dissolution occurred favourably in the solution-saturated porous medium until dissolved O{sub 2} was totally consumed. In a second saturated column, pyrite oxidation took place at alkaline conditions (pH 10.45) as acidity was neutralized by fly ash dissolution in a previous level. At this pH Fe release from pyrite dissolution was immediately depleted as Fe-oxy(hydroxide) phases that precipitated on the pyrite grains, forming Fe-coatings (microencapsulation). With time, pyrite microencapsulation inhibited oxidation in practically 97% of the pyritic sludge. Rapid pyrite-surface passivation decreased its reactivity, preventing AMD production in the relatively short term.

Decomposition of pyrite and the interaction of pyrite with coal organic matrix in pyrolysis and hydropyrolysis

Energy Technology Data Exchange (ETDEWEB)

Chen, H.; Li, B.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion, Inst. of Coal Chemistry

2000-10-01

The thermal behaviour of pure pyrite was studied under nitrogen and hydrogen atmospheres in a pressurized thermal balance. The transfer of pyrite in coal during pyrolysis and hydropyrolysis was investigated in a fixed-bed reactor. The results suggest that the indigenous hydro-carbon with hydrogen donor ability in coal can promote the reduction of pyrite in pyrolysis. At low temperatures, organic sulfur removal is almost the same in pyrolysis and hydropyrolysis of two coals. It is likely that indigenous hydrogen in coal is the dominant factor in organic sulfur elimination in the low-temperature stage. An increase of organic sulfur in pyrolysis of Hongmiao coal indicates that the lack of the indigenous hydrogen may be the key factor determining the transformation of pyritic sulfur into organic sulfur. Oxygen affects the conversion of pyrite into organic sulfur through the competitive consumption of hydrogen. 12 refs., 5 figs., 1 tab.

Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

DEFF Research Database (Denmark)

Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

2001-01-01

The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

Flocculation of Pyrite Fines in Aqueous Suspensions with Corn Starch to Eliminate Mechanical Entrainment in Flotation

Directory of Open Access Journals (Sweden)

Wei Ge

2015-10-01

Full Text Available The hydrophilic flocculation of pyrite fines in aqueous suspensions with corn starch was studied by measuring particle size distribution, microscopy observation and micro-flotation. Furthermore, the interaction of corn starch with pyrite was investigated by determining the adsorption density and based on zeta potential measurements and X-ray photoelectron spectrometer (XPS analysis in this work. The results of the particle size distribution measurement show that corn starch can effectively aggregate pyrite fines, and the pyrite floccules (flocs are sensitive to mechanical stirring. The micro-flotation results suggest that the mechanical entrainment of pyrite fines in flotation can be effectively eliminated through the formation of large-size flocs. The zeta potential of pyrite particles decreases with the addition of corn starch. The XPS results prove that carboxyl groups are generated on the digested corn starch, and both iron hydroxyl compounds and ferrous disulfide on the pyrite surface can chemically interact with the corn starch digested by sodium hydroxide.

Pyrite in the Mesoarchean Witwatersrand Supergroup, South Africa

OpenAIRE

2012-01-01

Ph.D. Petrographic, chemical and multiple sulfur isotope analyses were conducted on pyrite from argillaceous, arenaceous and rudaceous sedimentary rocks from the Mesoarchean Witwatersrand Supergroup. Following detailed petrographic analyses, four paragenetic associations of pyrite were identified. These include: 1) Detrital pyrite (derived from an existing rock via weathering and/or erosion). 2) Syngenetic pyrite (formed at the same time as the surrounding sediment). 3) Diagenetic pyrite (...

A Smart Superwetting Surface with Responsivity in Both Surface Chemistry and Microstructure.

Science.gov (United States)

Zhang, Dongjie; Cheng, Zhongjun; Kang, Hongjun; Yu, Jianxin; Liu, Yuyan; Jiang, Lei

2018-03-26

Recently, smart surfaces with switchable wettability have aroused much attention. However, only single surface chemistry or the microstructure can be changed on these surfaces, which significantly limits their wetting performances, controllability, and applications. A new surface with both tunable surface microstructure and chemistry was prepared by grafting poly(N-isopropylacrylamide) onto the pillar-structured shape memory polymer on which multiple wetting states from superhydrophilicity to superhydrophobicity can be reversibly and precisely controlled by synergistically regulating the surface microstructure and chemistry. Meanwhile, based on the excellent controllability, we also showed the application of the surface as a rewritable platform, and various gradient wettings can be obtained. This work presents for the first time a surface with controllability in both surface chemistry and microstructure, which starts some new ideas for the design of novel superwetting materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorção de xantatos sobre pirita Adsorption of xanthate on pyrite

Directory of Open Access Journals (Sweden)

Fábio Garcia Penha

2001-10-01

Full Text Available This paper presents a study of adsorption of xanthate with alkyl chain of two (C2XK, four (C4XK and eight (C8XK atoms of carbon, on pyrite from Santa Catarina, Brazil. The results showed that pyrite surface changes from hydrophilic to hydrophobic when xanthate is adsorbed increasing the contact angle to 35º for C2XK, and to 90º for C4XK and C8XK. The rate of flotation of pyrite particles after adsorption increases with the increase of the number of carbon atoms in the alkyl chain in agreement with the results of contact angle measurements.

Method of synthesizing pyrite nanocrystals

Science.gov (United States)

Wadia, Cyrus; Wu, Yue

2013-04-23

A method of synthesizing pyrite nanocrystals is disclosed which in one embodiment includes forming a solution of iron (III) diethyl dithiophosphate and tetra-alkyl-ammonium halide in water. The solution is heated under pressure. Pyrite nanocrystal particles are then recovered from the solution.

Organometallic chemistry of metal surfaces

International Nuclear Information System (INIS)

Muetterties, E.L.

1981-06-01

The organometallic chemistry of metal surfaces is defined as a function of surface crystallography and of surface composition for a set of cyclic hydrocarbons that include benzene, toluene, cyclohexadienes, cyclohexene, cyclohexane, cyclooctatetraene, cyclooctadienes, cyclooctadiene, cycloheptatriene and cyclobutane. 12 figures

Role of the carbonate impurities on the surface state of pyrite and arsenopyrite under treatment by high power electromagnetic pulses (HPEMP): oxidation of 50-100 μm size particles

International Nuclear Information System (INIS)

Filippova, I; Filippov, L; Ryazantseva, M; Chanturiya, V; Bunin, I

2013-01-01

Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and Transmission Electron Microscopy (TEM) have shown the variation of surface phase compositions of carbonate bearing pyrite and arsenopyrite as a result of the combined action of chemical oxidation and thermal processes after the treatment by high power electromagnetic pulses (HPEMP). The monitoring of the surface phase composition allowed to determine the correlation between the treatment conditions, the surface phase composition, and the flotation yield. Thus, HPEMP treatment may be regarded as a tool controlling the surface composition and the sorption ability of flotation collector onto minerals surface, and therefore, allowing to control the hydrophobic-hydrophilic surface balance. It was confirmed in this study that the flotation of pyrite with xanthate as a result of the influence HPEMP may vary depending on the presence of impurities such as calcite.

Covalent-Bond Formation via On-Surface Chemistry.

Science.gov (United States)

Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

2017-05-02

In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of heterotrophic microbial growth on biological oxidation of pyrite

Energy Technology Data Exchange (ETDEWEB)

Marchand, E.A.; Silverstein, J. [University of Nevada, Reno, NV (United States). Dept. of Civil Engineering

2002-12-15

Experiments were carried out to examine the possibility that enhanced growth of heterotrophic (non-iron-oxidising) bacteria would inhibit pyrite oxidation by Acidithiobacillus ferroxidans by out-competing the more slowly growing autotrophs for oxygen, nutrients or even attachment sites on the mineral surface. Glucose was added to microcosms containing pyrite, acidic mineral solution and cultures of A-ferrooxidans and Acidiphilium acidophilus under various experimental conditions. Results suggest that encouraging the growth of heterotrophic microorganisms under acid mine drainage conditions may be a feasible strategy for decreasing both the rate and the extent of sulfide mineral oxidation. 43 refs., 8 figs., 3 tabs.

Investigating the formation of acid mine drainage of Toledo pyrite concentrate using column cells

Science.gov (United States)

Aguila, Diosa Marie

2018-01-01

Acid mine drainage (AMD) is an inevitable problem in mining and has adverse effects in water quality. Studying AMD formation will be valuable in controlling the composition of mine waters and in planning the rehabilitation method for a mine. In this research, kinetics of AMD formation of Toledo pyrite was studied using two column experiments. The mechanisms of AMD formation and the effects of various factors on pH drop were first studied. Another column test was done for validation and to study the role of Fe2+/Fe3+ ratio in the change of leachate pH. The first experiment revealed that time and particle size are the most significant factors. It was also observed that the sudden pH drop during the starting hours was due to cracks formed from beneficiation, and the formation of Fe(OH)3. The laddered behavior of pH thereafter was due to decrease in formation of Fe(OH)3, and the precipitates in pyrite surface that lowered the surface area available for pyrite oxidation. The results of the second experiment validated the laddered behavior of pH. It was also observed that particle size distribution and pyrite surface were affected by the change in pH. Fe2+/Fe3+ ratio of leachate generally decreased as pH dropped.

The effects of trace element content on pyrite oxidation rates

Science.gov (United States)

Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.

2017-12-01

Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the

Low temperature surface chemistry and nanostructures

Science.gov (United States)

Sergeev, G. B.; Shabatina, T. I.

2002-03-01

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.

Report on assessment of the mechanism of bacterially assisted oxidation of pyritic uranium tailings

International Nuclear Information System (INIS)

Halbert, B.B.; Scharer, J.M.; Knapp, R.A.

1984-07-01

The oxidation of pyritic minerals has been shown to be catalyzed by the presence of iron- and sulphur-oxidizing bacteria. Thiobacillus ferroxidans plays the most significant role in the formation and propagation of acidic conditions. Optimum growth conditions for the T. ferroxidans occurs at a temperature of 35 degrees C and pH of 2 to 3. Bacterially assisted oxidation of pyrite involves both direct and indirect contact mechanisms. The direct contact mechanism entails enzymatic oxidation of the insoluble sulphide moiety. The indirect mechanism involves bacterial oxidation of the dissolved ferrous component to the ferric state. The ferric iron, in turn, acts as the prime oxidant of pyrite and is reduced to ferrous iron. The re-oxidation of the dissolved ferrous component which is catalyzed by bacterial activity, completes the cyclic process. The rate of bacterial oxidation is affected by: the geochemistry and reactivity of the pyritic material; the amount of pyrite present in the waste material and the exposed surface area of the pyritic component; the availability of oxygen and carbon dioxide; the pH and temperature of the leach solution; and the presence (or absence) of organic inhibitors. Of the above factors, oxygen has been frequently identified as the rate limiting reactant in tailings

Decomposition of pyrite and the interaction of pyrite with coal organic matrix in pyrolysis and hydropyrolysis

Energy Technology Data Exchange (ETDEWEB)

Chen, H.; Li, B.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). Institute of Coal Chemistry

1999-07-01

The thermal decomposition and reduction behaviour of pure pyrite crystals were studied under nitrogen and hydrogen atmospheres. Decomposition of pyrite in coal during pyrolysis and hydropyrolysis, and the behaviour of organic sulphur, are discussed. Temperature and pressure effects are considered. 7 refs., 6 figs., 1 tab.

Surface chemistry theory and applications

CERN Document Server

Bikerman, J J

2013-01-01

Surface Chemistry Theory and Applications focuses on liquid-gas, liquid-liquid, solid-gas, solid-liquid, and solid-solid surfaces. The book first offers information on liquid-gas surfaces, including surface tension, measurement of surface tension, rate of capillarity rise, capillary attraction, bubble pressure and pore size, and surface tension and temperature. The text then ponders on liquid-liquid and solid-gas surfaces. Discussions focus on surface energy of solids, surface roughness and cleanness, adsorption of gases and vapors, adsorption hysteresis, interfacial tension, and interfacial t

Moessbauer investigation of gold-bearing pyrite-rich concentrates

International Nuclear Information System (INIS)

Wagner, F.E.; Harris, D.C.

1994-01-01

A gold-bearing pyrite-rich concentrate of a refractory ore from the Golden Bear mine, northwestern British Columbia, and a pyrite-rich concentrate from Newhawk's west zone, Brucejack Lake area, northern British Columbia, containing 38 and 316 ppm Au and 0.57% and 0.19% As, respectively, have been investigated using 197 Au and 57 Fe Moessbauer spectroscopy. In the Golden Bear sample, the gold is mainly chemically bound in the pyrite with minor amounts present as an Au-Ag alloy, whereas in the Newhawk sample, the gold occurs mainly as an Au-Ag alloy with a composition close to Au 0.5 Ag 0.5 and is only partly bound in the pyrite. Having mean isomer shifts of +3.2 and +4.0 mm/s with respect to a Pt metal source, the gold in pyrite exhibits shifts similar to those observed for gold in arsenopyrite. The nature of the lattice sites occupied by the gold in pyrite is discussed. (orig.)

Geochemistry of Early Frasnian (Late Devonian) pyrite-ammonoid level in the Kostomłoty Basin, Poland, and a new proxy parameter for assessing the relative amount of syngenetic and diagenetic pyrite

Science.gov (United States)

Pisarzowska, Agnieszka; Berner, Zsolt A.; Racki, Grzegorz

2014-07-01

Pyrite geochemistry (isotope and trace element composition, degree of pyritization, S/Corg ratio) was used in context of selected lithogeochemical parameters (major and trace elements, including sulphur, organic carbon, and δ13C of carbonate carbon) to constrain fluctuations in depositional conditions during the Early to Middle Frasnian carbon isotopic perturbation (punctata Event) in the Kostomłoty Basin, Poland. Based on the ratio between the sum of oxyanionic elements and transition metals in pyrite, a new proxy parameter (index of syngenetic pyrite, ISYP) is proposed for assessing the relative amount of syngenetic pyrite in a sample. The distribution of the ISYP along the Kostomłoty - Małe Górki section (upper Szydłówek to the basal Kostomłoty beds) is in concert with conclusions inferred from paleoecologic data and other geochemical parameters (degree of pyritization, S/Corg, δ34Spyrite). According to these, the lower segment of the Szydłówek Beds was deposited in a normally oxygenated environment, but undergoing increasing primary productivity in surface water, as indicated by an increase in δ13Ccarb and in Cu/Zr ratio in bulk rock, which triggered the periodic deposition of sediments slightly enriched in organic matter, notably within the pyrite-ammonoid level (= Goniatite Level). Fluctuating, but in general high S/Corg ratios, DOPR values and ISYP values suggest that during this time - against the background of a generally dysoxic environment - shorter or longer lasting episodes of more restricted (anoxic and possibly even euxinic) bottom water conditions developed. Low sedimentation rates enabled a continuous and practically unlimited supply of sulphate during bacterial sulphate reduction (BSR), which in turn led to a strong depletion of pyrite sulphur in 34S in this interval (constantly around -29‰). In contrast, below and above the Goniatite Level, higher δ34S values (up to + 3‰), are compatible with closed system conditions and higher

Pyrite-coated granite cobbles at Lee Bay, Stewart Island

International Nuclear Information System (INIS)

Brathwaite, R.L.; Skinner, D.N.B.; Faure, K.; Edwards, E.

2014-01-01

On the west side of Lee Bay on the northeast coast of Stewart Island, ventifact cobbles of pyrite-coated granite occur on the beach near the high tide mark and appear to be derived from a sand-cemented gravel deposit that forms a low bank at the back of the beach. The pyrite coat (up to 1 mm thick) completely covers the granitic cobbles and is zoned, with an inner zone of fine-grained colloform pyrite and an outer framboidal zone. Framboidal pyrite is typically formed in anoxic sedimentary environments. Subrounded grains of hematite, ilmenite with hematite blebs, magnetite, feldspar, biotite, quartz and zircon are present in the outer framboidal zone, with some ilmenite and hematite grains being partially replaced by pyrite. The assemblage of ilmenite-hematite-magnetite-biotite-zircon is similar both in mineralogy and size range to that found in heavy mineral beach sands. Sulphur isotope values of the pyrite coat are consistent with formation of the pyrite by microbial sulphate reduction of seawater sulphate. The framboidal texture together with the presence of grains of beach sand in the pyrite coating indicate that it was deposited in a low-temperature sedimentary environment. (author)

Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants

Directory of Open Access Journals (Sweden)

Carolina Gil-Lozano

2014-06-01

Full Text Available The Fenton reaction is the most widely used advanced oxidation process (AOP for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2 particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe3+ into Fe2+ and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.

On the mechanism of action of combination of thionocarbamates with xanthate during flotation of copper-molybdenum pyrite contained ores

International Nuclear Information System (INIS)

Nedosekina, T.V.; Glembotskij, A.V.; Bekhtle, G.A.; Novgorodova, Eh.Z.

1985-01-01

Investigation results of action mechanism of thionocarbamates combination with xanthate are described. It is established that these collectors are capable of co-adsorbing on pyrite surface, that is the reason for sharp increase of the floatability and disturbs the selectivity of copper-molybdenum pyrite-containing ore flotation

Acid-base properties of a limed pyritic overburden during simulated weathering

Energy Technology Data Exchange (ETDEWEB)

Doolittle, J.J.; Hossner, L.R. [South Dakota State University, Brookings, SD (United States). Plant Science Dept.

1997-11-01

Surface-mine reclamation is often hindered by the formation of acid mine soil and acid mine drainage from FeS{sub 2} oxidation. Surface soils containing FeS{sub 2} are often treated with crushed limestone (predominately CaCO{sub 3}) to prevent aid minesoil formation. The main objective of this study was to evaluate the long-term effectiveness of liming pyritic minesoil to prevent the formation of acid minesoil and acid mine drainage. Pyritic minesoils that did not receive lime became acidic very rapidly and produced acidic leachate. Almost all of the FeS{sub 2} in this treatment oxidized during the first 200 d. The addition of lime at a rate of 25% of the theoretical acid-base account (ABA) significantly slowed FeS{sub 2} oxidation, but rapid oxidation ensued after the added lime was neutralized. Treatments receiving a liming rate of 50% ABA or greater remained neutral to alkaline throughout the study. Acid-base values and residual FeS{sub 2}-CO{sub 3} data, however, indicate that the lime was dissolving from the system faster than the FeS{sub 2} was oxidizing, and all the treatments would eventually become acidic. The results indicate that the liming of a pyritic overburden to an ABA of 125% is not a sustainable solution to preventing acid minesoil and acid mine drainage. 25 refs., 6 figs., 3 tabs.

Fermi surfaces of the pyrite-type cubic AuSb2 compared with split Fermi surfaces of the ullmannite-type cubic chiral NiSbS and PdBiSe

Science.gov (United States)

Nishimura, K.; Kakihana, M.; Nakamura, A.; Aoki, D.; Harima, H.; Hedo, M.; Nakama, T.; Ōnuki, Y.

2018-05-01

We grew high-quality single crystals of AuSb2 with the pyrite (FeS2)-type cubic structure by the Bridgman method and studied the Fermi surface properties by the de Haas-van Alphen (dHvA) experiment and the full potential LAPW band calculation. The Fermi surfaces of AuSb2 are found to be similar to those of NiSbS and PdBiSe with the ullmannite (NiSbS)-type cubic chiral structure because the crystal structures are similar each other and the number of valence electrons is the same between two different compounds. Note that each Fermi surface splits into two Fermi surfaces in NiSbS and PdBiSe, reflecting the non-centrosymmetric crystal structure.

Spatial Mapping for Managing Oxidized Pyrite (FeS2 in South Sumatra Wetlands, Indonesia

Directory of Open Access Journals (Sweden)

M. Edi Armanto

2016-02-01

Full Text Available The research aimed to analyze spatial mapping for managing oxidized pyrite (FeS2 in South Sumatra wetlands, Indonesia. The field observations are done by exploring several transect on land units. The field description refers to Soil Survey Staff (2014. Water and soil samples were taken from selected key areas for laboratory analysis. The vegetation data was collected by making sample plots (squares method placed on each vegetation type with plot sizes depending on the vegetation type, namely 10 x 10 m for secondary forests and 5 x 5 m for shrubs and grass. The observations of surface water level were done during the river receding with units of m above sea level (m asl. The research results showed that pyrite formation is largely determined by the availability of natural vegetation as Sulfur (S donors, climate and uncontrolled water balance and supporting fauna such as crabs and mud shrimp.  Climate and water balance as well as supporting faunas is the main supporting factors to accelerate the process of pyrite formation. Oxidized pyrite serves to increase soil acidity, becomes toxic to fish ponds and arable soils, plant growth and disturbing the water and soil nutrient balances. Oxidized pyrite is predominantly accelerated by the dynamics of river water and disturbed natural vegetation by human activities.  The pyrite oxidation management approach is divided into three main components of technologies, namely water management, land management and commodity management.

Simulated aerobic pedogenesis in pyritic overburden with a positive acid-base account

Energy Technology Data Exchange (ETDEWEB)

Doolittle, J.J.; Hossner, L.R.; Wilding, L.P. (South Dakota State University, Brookings, SD (United States). Dept. of Plant Science)

Reclamation of surface-mined land is often hindered by the excess salts and acidity produced by the weathering of pyritic overburden. This study was conducted to document the initial transformations that occur when pyritic overburden containing excess acid neutralizing potential is used as parent material in minesoil construction. An overburden containing 0.8% FeS[sub 2] (pyrite) and 1.6% inorganic carbonate (predominantly dolomite) was collected from the highwall of an active lignite surface mine in Panola County, Texas. The overburden was lightly crushed through a 13-mm sieve and packed into three replicate lysimeters (0.75 by 0.75 by 1.2 m). The lysimeters were leached monthly with 63.5 mm of deionized water for 24 mo. The initial material had a pH of 8.3 and an excess acid neutralizing potential. Progressive FeS[sub 2] oxidation released H[sub 2]SO[sub 4], and the pH decreased to 6.8. The dolomite dissolved, neutralizing the acidity, with subsequent release of Ca and Mg ions into solution. Leachate Ca[sup 2+] and SO[sub 4][sup 2-] concentrations exceeded the ion activity product of gypsum in the lower 60 cm of the lysimeters. Thin-section analysis revealed that gypsum crystals precipitated along margins of residual pyrite particles and in conductive vughs and channels. The continued accumulation of gypsum in minesoil development could eventually lead to the formation of a gypsic or a petrogypsic horizon. A restrictive layer such as this would decrease vertical movement of water and O[sub 2] which would reduce vegetative growth, increase runoff and erosion, and thus increase the probability of reclamation failure.

Genesis of uranium-gold pyritic conglomerates

International Nuclear Information System (INIS)

Myers, W.B.

1981-01-01

The ancient pyritic ore conglomerates have a common origin best exemplified by the Witwatersrand deposits. All contain detrital pyrite and uraninite, which are unstable in modern oxygenated environments and were deposited in a reducing atmosphere. The Rand reefs are not similar to modern gold placers. Placers result from the near incapacity of streams and currents to transport coarse gold. Placers as rich as Rand reef occur only in narrow paystreaks within 15 kilometers of a coarse-gold source. The board dispersion of gold in the reefs is due to solution transport of metal complexed as aurous sulfide, leached anoxygenically from crustal rocks, probably from sea-floor basalt, and precipitated by a slow reaction driven by the radioactive decay of detrital uraninite. Radiolysis of water on shallow marine unconformities resulted in diffusion of hydrogen to the atmosphere and a slight excess of hydroxyl free radical in the reef environment. The mild oxidizing tendency slowly dissolved uranium, precipitated gold, and oxygenated thucholite. These actions define a maturing process. A uraninite placer accumulating on an unconformity becomes progressively converted to a gold reef with little residual uraninite. The most mature reefs tend to grade toward the thucholite-seam type, very thin but exceedingly rich in gold. A combination of chemical attack and physical reworking accounts for the general thinness of mature reefs. Pyrite, like uraninite, decreases in abundance with increasing maturity; buffering by pyrite moderated the oxidative depletion of uranium. Where pyrite was scanty or absent, uraninite was completely dissolved by the effects of radiolysis and no ore formed

Enhancement of Biofilm Formation on Pyrite by Sulfobacillus thermosulfidooxidans

Directory of Open Access Journals (Sweden)

Qian Li

2016-07-01

Full Text Available Bioleaching is the mobilization of metal cations from insoluble ores by microorganisms. Biofilms can enhance this process. Since Sulfobacillus often appears in leaching heaps or reactors, this genus has aroused attention. In this study, biofilm formation and subsequent pyrite dissolution by the Gram-positive, moderately thermophilic acidophile Sulfobacillus thermosulfidooxidans were investigated. Five strategies, including adjusting initial pH, supplementing an extra energy source or ferric ions, as well as exchanging exhausted medium with fresh medium, were tested for enhancement of its biofilm formation. The results show that regularly exchanging exhausted medium leads to a continuous biofilm development on pyrite. By this way, multiply layered biofilms were observed on pyrite slices, while only monolayer biofilms were visible on pyrite grains. In addition, biofilms were proven to be responsible for pyrite leaching in the early stages.

Thin film preparation of semiconducting iron pyrite

Science.gov (United States)

Smestad, Greg P.; Ennaoui, Ahmed; Fiechter, Sebastian; Hofmann, Wolfgang; Tributsch, Helmut; Kautek, Wolfgang

1990-08-01

Pyrite (Fe52) has been investigated as a promising new absorber material for thin film solar cell applications because of its high optical absorption coefficient of 1OL cm1, and its bandgap of 0.9 to 1.0 eV. Thin layers have been prepared by Metal Organic Chemical Vapor Deposition, MOCVD, Chemical Spray Pyrolysis, CSP, Chemical Vapor Transport, CVT, and Sulfurization of Iron Oxide films, 510. It is postulated that for the material FeS2, if x is not zero, a high point defect concentration results from replacing 2 dipoles by single S atoms. This causes the observed photovoltages and solar conversion efficiencies to be lower than expected. Using the Fe-O-S ternary phase diagram and the related activity plots, a thermodynamic understanding is formulated for the resulting composition of each of these types of films. It is found that by operating in the oxide portion of the phase diagram, the resulting oxidation state favors pyrite formation over FeS. By proper orientation of the grains relative to the film surface, and by control of pinholes and stoichiometry, an efficient thin film photovolatic solar cell material could be achieved.

Fabrication and characterization of PDLLA/pyrite composite bone ...

Indian Academy of Sciences (India)

Polylactic acid; Chinese herbal medicine; pyrite; scaffold; bone regeneration; cell culture. 1. Introduction ... research focuses on the direct cellular level effect of pyrite on bone cells. ..... optimal scaffold from the results of this paper. Although the.

Distribution of sulfur and pyrite in coal seams from Kutai Basin (East Kalimantan, Indonesia): Implications for paleoenvironmental conditions

Energy Technology Data Exchange (ETDEWEB)

Widodo, Sri [Department of Mining Engineering, Moslem University of Indonesia, Jln. Urip Sumoharjo, Makassar (Indonesia); Oschmann, Wolfgang [Institute of Geosciece, J.W. Goethe-University, Altenhoeferallee 1, D-60438 Frankfurt a.M. (Germany); Bechtel, Achim; Sachsenhofer, Reinhard F. [Department of Applied Geoscience and Geophysics, University of Leoben, Peter-Tunner-Str.5, A-8700 Leoben (Austria); Anggayana, Komang [Department of Mining Engineering, Bandung Institute of Technology, Jln. Ganesa 10, I-40132 Bandung (Indonesia); Puettmann, Wilhelm [Institute of Atmospheric and Environmental Sciences, Dapartment of Analytical Enviromental Chemistry, J.W. Goethe-University, Altenhoeferallee 1, D-60438 Frankfurt a.M. (Germany)

2010-03-01

Thirteen Miocene coal samples from three active open pit and underground coal mines in the Kutai Basin (East Kalimantan, Indonesia) were collected. According to our microscopical and geochemical investigations, coal samples from Sebulu and Centra Busang coal mines yield high sulfur and pyrite contents as compared to the Embalut coal mine. The latter being characterized by very low sulfur (< 1%) and pyrite contents. The ash, mineral, total sulfur, iron (Fe) and pyrite contents of most of the coal samples from the Sebulu and Centra Busang coal mines are high and positively related in these samples. Low contents of ash, mineral, total sulfur, iron (Fe) and pyrite have been found only in sample TNT-32 from Centra Busang coal mine. Pyrite was the only sulfur form that we could recognize under reflected light microscope (oil immersion). Pyrite occurred in the coal as framboidal, euhedral, massive, anhedral and epigenetic pyrite in cleats/fractures. High concentration of pyrite argues for the availability of iron (Fe) in the coal samples. Most coal samples from the Embalut coal mine show lower sulfur (< 1 wt.%) and pyrite contents as found within Centra Busang and Sebulu coals. One exception is the coal sample KTD-38 from Embalut mine with total sulfur content of 1.41 wt.%. The rich ash, mineral, sulfur and pyrite contents of coals in the Kutai Basin (especially Centra Busang and Sebulu coals) can be related to the volcanic activity (Nyaan volcanic) during Tertiary whereby aeolian material was transported to the mire during or after the peatification process. Moreover, the adjacent early Tertiary deep marine sediment, mafic igneous rocks and melange in the center of Kalimantan Island might have provided mineral to the coal by uplift and erosion. The inorganic matter in the mire might also originate from the ground and surface water from the highland of central Kalimantan. (author)

Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

Energy Technology Data Exchange (ETDEWEB)

Mango, Helen, E-mail: helen.mango@castleton.edu [Department of Natural Sciences, Castleton State College, 233 South Street, Castleton, VT 05735 (United States); Ryan, Peter, E-mail: pryan@middlebury.edu [Department of Geology, Middlebury College, 276 Bicentennial Way, Middlebury, VT 05753 (United States)

2015-02-01

Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ{sup 34}S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in {sup 34}S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ{sup 34}S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ{sup 34}S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ{sup 34}S = – 5.2 to 63‰ with higher {sup 34}S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ{sup 34}S.

Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

International Nuclear Information System (INIS)

Mango, Helen; Ryan, Peter

2015-01-01

Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ 34 S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in 34 S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ 34 S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ 34 S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ 34 S = – 5.2 to 63‰ with higher 34 S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ 34 S

Surface chemistry: Key to control and advance myriad technologies

Science.gov (United States)

Yates, John T.; Campbell, Charles T.

2011-01-01

This special issue on surface chemistry is introduced with a brief history of the field, a summary of the importance of surface chemistry in technological applications, a brief overview of some of the most important recent developments in this field, and a look forward to some of its most exciting future directions. This collection of invited articles is intended to provide a snapshot of current developments in the field, exemplify the state of the art in fundamental research in surface chemistry, and highlight some possibilities in the future. Here, we show how those articles fit together in the bigger picture of this field. PMID:21245359

Pyrite oxidation under simulated acid rain weathering conditions.

Science.gov (United States)

Zheng, Kai; Li, Heping; Wang, Luying; Wen, Xiaoying; Liu, Qingyou

2017-09-01

We investigated the electrochemical corrosion behavior of pyrite in simulated acid rain with different acidities and at different temperatures. The cyclic voltammetry, polarization curve, and electrochemical impedance spectroscopy results showed that pyrite has the same electrochemical interaction mechanism under different simulated acid rain conditions, regardless of acidity or environmental temperature. Either stronger acid rain acidity or higher environmental temperature can accelerate pyrite corrosion. Compared with acid rain having a pH of 5.6 at 25 °C, the prompt efficiency of pyrite weathering reached 104.29% as the acid rain pH decreased to 3.6, and it reached 125.31% as environmental temperature increased to 45 °C. Increasing acidity dramatically decreases the charge transfer resistance, and increasing temperature dramatically decreases the passivation film resistance, when other conditions are held constant. Acid rain always causes lower acidity mine drainage, and stronger acidity or high environmental temperatures cause serious acid drainage. The natural parameters of latitude, elevation, and season have considerable influence on pyrite weathering, because temperature is an important influencing factor. These experimental results are of direct significance for the assessment and management of sulfide mineral acid drainage in regions receiving acid rain.

From helical to planar chirality by on-surface chemistry

Czech Academy of Sciences Publication Activity Database

Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Vacek Chocholoušová, Jana; Jančařík, Andrej; Rybáček, Jiří; Kośmider, K.; Stará, Irena G.; Jelínek, Pavel; Starý, Ivo

2017-01-01

Roč. 9, č. 3 (2017), s. 213-218 ISSN 1755-4330 R&D Projects: GA ČR(CZ) GC14-16963J; GA ČR(CZ) GA14-29667S Institutional support: RVO:68378271 ; RVO:61388963 Keywords : chirality * AFM * STM * helicene * on surface chemistry * DFT Subject RIV: CF - Physical ; Theoretical Chemistry; CC - Organic Chemistry (UOCHB-X) OBOR OECD: Physical chemistry; Organic chemistry (UOCHB-X) Impact factor: 25.870, year: 2016

Comparison Analysis of Coal Biodesulfurization and Coal's Pyrite Bioleaching with Acidithiobacillus ferrooxidans

Science.gov (United States)

Hong, Fen-Fen; He, Huan; Liu, Jin-Yan; Tao, Xiu-Xiang; Zheng, Lei; Zhao, Yi-Dong

2013-01-01

Acidithiobacillus ferrooxidans (A. ferrooxidans) was applied in coal biodesulfurization and coal's pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal's pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal's pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32%) and jarosite (18.99%) were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34%) and elemental sulfur (50.72%) but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process. PMID:24288464

Water at surfaces with tunable surface chemistries

Science.gov (United States)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Characterisation of the inorganic chemistry of surface waters in ...

African Journals Online (AJOL)

The main purpose of this study was to determine a simple inorganic chemistry index that can be used for all surface waters in South Africa, in order to characterise the inorganic chemistry of surface waters. Water quality data collected up until 1999 from all sample monitoring stations (2 068 monitoring stations, 364 659 ...

Pyritic ash-flow tuff, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Castor, S.B.; Tingley, J.V.; Bonham, H.F. Jr.

1994-01-01

The Yucca Mountain site is underlain by a 1,500-m-thick Miocene volcanic sequence that comprises part of the southwestern Nevada volcanic field. Rocks of this sequence, which consists mainly of ash-flow tuff sheets with minor flows and bedded tuff, host precious metal mineralization in several areas as near as 10 km from the site. In two such areas, the Bullfrog and Bare Mountain mining districts, production and reserves total over 60 t gold and 150 t silver. Evidence of similar precious metal mineralization at the Yucca Mountain site may lead to mining or exploratory drilling in the future, compromising the security of the repository. The authors believe that most of the pyrite encountered by drilling at Yucca Mountain was introduced as pyroclastic ejecta, rather than by in situ hydrothermal activity. Pyritic ejecta in ash-flow tuff are not reported in the literature, but there is no reason to believe that the Yucca Mountain occurrence is unique. The pyritic ejecta are considered by us to be part of a preexisting hydrothermal system that was partially or wholly destroyed during eruption of the tuff units. Because it was introduced as ejecta in tuff units that occur at depths of about 1,000 m, such pyrite does not constitute evidence of shallow mineralization at the proposed repository site; however, the pyrite may be evidence for mineralization deep beneath Yucca Mountain or as much as tens of kilometers from it

Quantification of air plasma chemistry for surface disinfection

International Nuclear Information System (INIS)

Pavlovich, Matthew J; Clark, Douglas S; Graves, David B

2014-01-01

Atmospheric-pressure air plasmas, created by a variety of discharges, are promising sources of reactive species for the emerging field of plasma biotechnology because of their convenience and ability to operate at ambient conditions. One biological application of ambient-air plasma is microbial disinfection, and the ability of air plasmas to decontaminate both solid surfaces and liquid volumes has been thoroughly established in the literature. However, the mechanism of disinfection and which reactive species most strongly correlate with antimicrobial effects are still not well understood. We describe quantitative gas-phase measurements of plasma chemistry via infrared spectroscopy in confined volumes, focusing on air plasma generated via surface micro-discharge (SMD). Previously, it has been shown that gaseous chemistry is highly sensitive to operating conditions, and the measurements we describe here extend those findings. We quantify the gaseous concentrations of ozone (O 3 ) and nitrogen oxides (NO and NO 2 , or NO x ) throughout the established ‘regimes’ for SMD air plasma chemistry: the low-power, ozone-dominated mode; the high-power, nitrogen oxides-dominated mode; and the intermediate, unstable transition region. The results presented here are in good agreement with previously published experimental studies of aqueous chemistry and parameterized models of gaseous chemistry. The principal finding of the present study is the correlation of bacterial inactivation on dry surfaces with gaseous chemistry across these time and power regimes. Bacterial decontamination is most effective in ‘NO x mode’ and less effective in ‘ozone mode’, with the weakest antibacterial effects in the transition region. Our results underscore the dynamic nature of air plasma chemistry and the importance of careful chemical characterization of plasma devices intended for biological applications. (paper)

Quantification of air plasma chemistry for surface disinfection

Science.gov (United States)

Pavlovich, Matthew J.; Clark, Douglas S.; Graves, David B.

2014-12-01

Atmospheric-pressure air plasmas, created by a variety of discharges, are promising sources of reactive species for the emerging field of plasma biotechnology because of their convenience and ability to operate at ambient conditions. One biological application of ambient-air plasma is microbial disinfection, and the ability of air plasmas to decontaminate both solid surfaces and liquid volumes has been thoroughly established in the literature. However, the mechanism of disinfection and which reactive species most strongly correlate with antimicrobial effects are still not well understood. We describe quantitative gas-phase measurements of plasma chemistry via infrared spectroscopy in confined volumes, focusing on air plasma generated via surface micro-discharge (SMD). Previously, it has been shown that gaseous chemistry is highly sensitive to operating conditions, and the measurements we describe here extend those findings. We quantify the gaseous concentrations of ozone (O3) and nitrogen oxides (NO and NO2, or NOx) throughout the established ‘regimes’ for SMD air plasma chemistry: the low-power, ozone-dominated mode; the high-power, nitrogen oxides-dominated mode; and the intermediate, unstable transition region. The results presented here are in good agreement with previously published experimental studies of aqueous chemistry and parameterized models of gaseous chemistry. The principal finding of the present study is the correlation of bacterial inactivation on dry surfaces with gaseous chemistry across these time and power regimes. Bacterial decontamination is most effective in ‘NOx mode’ and less effective in ‘ozone mode’, with the weakest antibacterial effects in the transition region. Our results underscore the dynamic nature of air plasma chemistry and the importance of careful chemical characterization of plasma devices intended for biological applications.

Greigite: a true intermediate on the polysulfide pathway to pyrite

Directory of Open Access Journals (Sweden)

Benning Liane G

2007-03-01

Full Text Available Abstract The formation of pyrite (FeS2 from iron monosulfide precursors in anoxic sediments has been suggested to proceed via mackinawite (FeS and greigite (Fe3S4. Despite decades of research, the mechanisms of pyrite formation are not sufficiently understood because solid and dissolved intermediates are oxygen-sensitive and poorly crystalline and therefore notoriously difficult to characterize and quantify. In this study, hydrothermal synchrotron-based energy dispersive X-ray diffraction (ED-XRD methods were used to investigate in situ and in real-time the transformation of mackinawite to greigite and pyrite via the polysulfide pathway. The rate of formation and disappearance of specific Bragg peaks during the reaction and the changes in morphology of the solid phases as observed with high resolution microscopy were used to derive kinetic parameters and to determine the mechanisms of the reaction from mackinawite to greigite and pyrite. The results clearly show that greigite is formed as an intermediate on the pathway from mackinawite to pyrite. The kinetics of the transformation of mackinawite to greigite and pyrite follow a zero-order rate law indicating a solid-state mechanism. The morphology of greigite and pyrite crystals formed under hydrothermal conditions supports this conclusion and furthermore implies growth of greigite and pyrite by oriented aggregation of nanoparticulate mackinawite and greigite, respectively. The activation enthalpies and entropies of the transformation of mackinawite to greigite, and of greigite to pyrite were determined from the temperature dependence of the rate constants according to the Eyring equation. Although the activation enthalpies are uncharacteristic of a solid-state mechanism, the activation entropies indicate a large increase of order in the transition state, commensurate with a solid-state mechanism.

Gas-grain chemistry in cold interstellar cloud cores with a microscopic Monte Carlo approach to surface chemistry

Science.gov (United States)

Chang, Q.; Cuppen, H. M.; Herbst, E.

2007-07-01

Aims:We have recently developed a microscopic Monte Carlo approach to study surface chemistry on interstellar grains and the morphology of ice mantles. The method is designed to eliminate the problems inherent in the rate-equation formalism to surface chemistry. Here we report the first use of this method in a chemical model of cold interstellar cloud cores that includes both gas-phase and surface chemistry. The surface chemical network consists of a small number of diffusive reactions that can produce molecular oxygen, water, carbon dioxide, formaldehyde, methanol and assorted radicals. Methods: The simulation is started by running a gas-phase model including accretion onto grains but no surface chemistry or evaporation. The starting surface consists of either flat or rough olivine. We introduce the surface chemistry of the three species H, O and CO in an iterative manner using our stochastic technique. Under the conditions of the simulation, only atomic hydrogen can evaporate to a significant extent. Although it has little effect on other gas-phase species, the evaporation of atomic hydrogen changes its gas-phase abundance, which in turn changes the flux of atomic hydrogen onto grains. The effect on the surface chemistry is treated until convergence occurs. We neglect all non-thermal desorptive processes. Results: We determine the mantle abundances of assorted molecules as a function of time through 2 × 105 yr. Our method also allows determination of the abundance of each molecule in specific monolayers. The mantle results can be compared with observations of water, carbon dioxide, carbon monoxide, and methanol ices in the sources W33A and Elias 16. Other than a slight underproduction of mantle CO, our results are in very good agreement with observations.

Abiotic pyrite reactivity versus nitrate, selenate and selenite using chemical and electrochemical methods

International Nuclear Information System (INIS)

Ignatiadis, I.; Betelu, S.; Gaucher, E.; Tournassat, C.; Chainet, F.

2010-01-01

Document available in extended abstract form only. This work is part of ReCosy European project (www.recosy.eu), whose main objectives are the sound understanding of redox phenomena controlling the long-term release/retention of radionuclides in nuclear waste disposal and providing tools to apply the results to performance assessment/safety case. Redox is one of the main factor affecting speciation and mobility of redox-sensitive radionuclides. Thus, it is of a great importance to investigate the redox reactivity of the host radioactive waste formations, particularly when exposed to redox perturbations. Callovo-Oxfordian formation (COx), a clay rock known as an anoxic and reducing system, was selected in France as the most suitable location to store nuclear waste. Iron (II) sulfide, mostly constituted of pyrite (FeS 2 ), iron (II) carbonate, iron(II) bearing clays and organic matter are considered to account almost entirely for the total reducing capacity of the rock. We report here the redox reactivity of pyrite upon exposure to nitrate (N(V)), selenate (Se(VI)) and selenite (Se(IV)) that possibly occur in the nuclear storage. Both, chemical and electrochemical kinetic approaches were simultaneously conducted such as to (i) determine the kinetics parameters of the reactions and (ii) understand the kinetic mechanisms. In order to reach similar conditions that are encountered in the storage system, all experiments were realised in NaCl 0.1 M, near neutral pH solutions, and an abiotic glove box (O 2 less than 10 -8 M). Chemical approach has consisted to set in contact pyrite in grains with solutions containing respectively nitrate, selenate and selenite. Reactants and products chemical analyses, conducted at different contact times, allowed us to assess the kinetics of oxidant reduction. Electrochemical approach has consisted in the continuous or semi-continuous analysis of large surface pyrite electrodes immersed in solutions with or without oxidant (nitrate

Effects of pyrite and sphalerite on population compositions, dynamics and copper extraction efficiency in chalcopyrite bioleaching process.

Science.gov (United States)

Xiao, Yunhua; Liu, Xueduan; Dong, Weiling; Liang, Yili; Niu, Jiaojiao; Gu, Yabing; Ma, Liyuan; Hao, Xiaodong; Zhang, Xian; Xu, Zhen; Yin, Huaqun

2017-07-01

This study used an artificial microbial community with four known moderately thermophilic acidophiles (three bacteria including Acidithiobacillus caldus S1, Sulfobacillus thermosulfidooxidans ST and Leptospirillum ferriphilum YSK, and one archaea, Ferroplasma thermophilum L1) to explore the variation of microbial community structure, composition, dynamics and function (e.g., copper extraction efficiency) in chalcopyrite bioleaching (C) systems with additions of pyrite (CP) or sphalerite (CS). The community compositions and dynamics in the solution and on the ore surface were investigated by real-time quantitative PCR (qPCR). The results showed that the addition of pyrite or sphalerite changed the microbial community composition and dynamics dramatically during the chalcopyrite bioleaching process. For example, A. caldus (above 60%) was the dominant species at the initial stage in three groups, and at the middle stage, still dominated C group (above 70%), but it was replaced by L. ferriphilum (above 60%) in CP and CS groups; at the final stage, L. ferriphilum dominated C group, while F. thermophilum dominated CP group on the ore surface. Furthermore, the additions of pyrite or sphalerite both made the increase of redox potential (ORP) and the concentrations of Fe 3+ and H + , which would affect the microbial community compositions and copper extraction efficiency. Additionally, pyrite could enhance copper extraction efficiency (e.g., improving around 13.2% on day 6) during chalcopyrite bioleaching; on the contrary, sphalerite restrained it.

Liquid flow along a solid surface reversibly alters interfacial chemistry.

Science.gov (United States)

Lis, Dan; Backus, Ellen H G; Hunger, Johannes; Parekh, Sapun H; Bonn, Mischa

2014-06-06

In nature, aqueous solutions often move collectively along solid surfaces (for example, raindrops falling on the ground and rivers flowing through riverbeds). However, the influence of such motion on water-surface interfacial chemistry is unclear. In this work, we combine surface-specific sum frequency generation spectroscopy and microfluidics to show that at immersed calcium fluoride and fused silica surfaces, flow leads to a reversible modification of the surface charge and subsequent realignment of the interfacial water molecules. Obtaining equivalent effects under static conditions requires a substantial change in bulk solution pH (up to 2 pH units), demonstrating the coupling between flow and chemistry. These marked flow-induced variations in interfacial chemistry should substantially affect our understanding and modeling of chemical processes at immersed surfaces. Copyright © 2014, American Association for the Advancement of Science.

Smart Surface Chemistries of Conducting Polymers

DEFF Research Database (Denmark)

Lind, Johan Ulrik

In this thesis we investigate post-polymerization covalent modifications of poly(3,4-dioxythiophene (PEDOT)-type conducting polymers. The aim of the modifications is to gain specific control of the interaction between the material and living mammalian cells. The use of “click-chemistry” to modify...... a straightforward and in-expensive method for patterning conducting polymer thin films into microelectrodes, without losing control of the surface chemistry of the samples. On the contrary, the method provides direct control of the surface chemistry of both the fabricated micro-electrodes and the gaps between them....... The method is based on locally removing PEDOTtype polymers to expose underlying non-conducting functional polymer substrates. Thereby, multifunctional substrates are obtained. By applying this method, we are able to fabricate allpolymer micro-systems with multiple types of localized functional (bio...

Fabrication and characterization of PDLLA/pyrite composite bone ...

Indian Academy of Sciences (India)

Keywords. Polylactic acid; Chinese herbal medicine; pyrite; scaffold; bone regeneration; cell culture. ... Pyrite (FeS2, named as Zi-Ran-Tong in Chinese medicine), as a traditional Chinesemedicine, has been used in the Chinese population to treat bone diseases and to promote bone healing. The mechanical properties of ...

Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

CERN Document Server

Busca, Guido

2014-01-01

Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

Comparison Analysis of Coal Biodesulfurization and Coal’s Pyrite Bioleaching with Acidithiobacillus ferrooxidans

Directory of Open Access Journals (Sweden)

Fen-Fen Hong

2013-01-01

Full Text Available Acidithiobacillus ferrooxidans (A. ferrooxidans was applied in coal biodesulfurization and coal’s pyrite bioleaching. The result showed that A. ferrooxidans had significantly promoted the biodesulfurization of coal and bioleaching of coal’s pyrite. After 16 days of processing, the total sulfur removal rate of coal was 50.6%, and among them the removal of pyritic sulfur was up to 69.9%. On the contrary, after 12 days of processing, the coal’s pyrite bioleaching rate was 72.0%. SEM micrographs showed that the major pyrite forms in coal were massive and veinlets. It seems that the bacteria took priority to remove the massive pyrite. The sulfur relative contents analysis from XANES showed that the elemental sulfur (28.32% and jarosite (18.99% were accumulated in the biotreated residual coal. However, XRD and XANES spectra of residual pyrite indicated that the sulfur components were mainly composed of pyrite (49.34% and elemental sulfur (50.72% but no other sulfur contents were detected. Based on the present results, we speculated that the pyrite forms in coal might affect sulfur biooxidation process.

Models of gas-grain chemistry in interstellar cloud cores with a stochastic approach to surface chemistry

Science.gov (United States)

Stantcheva, T.; Herbst, E.

2004-08-01

We present a gas-grain model of homogeneous cold cloud cores with time-independent physical conditions. In the model, the gas-phase chemistry is treated via rate equations while the diffusive granular chemistry is treated stochastically. The two phases are coupled through accretion and evaporation. A small network of surface reactions accounts for the surface production of the stable molecules water, formaldehyde, methanol, carbon dioxide, ammonia, and methane. The calculations are run for a time of 107 years at three different temperatures: 10 K, 15 K, and 20 K. The results are compared with those produced in a totally deterministic gas-grain model that utilizes the rate equation method for both the gas-phase and surface chemistry. The results of the different models are in agreement for the abundances of the gaseous species except for later times when the surface chemistry begins to affect the gas. The agreement for the surface species, however, is somewhat mixed. The average abundances of highly reactive surface species can be orders of magnitude larger in the stochastic-deterministic model than in the purely deterministic one. For non-reactive species, the results of the models can disagree strongly at early times, but agree to well within an order of magnitude at later times for most molecules. Strong exceptions occur for CO and H2CO at 10 K, and for CO2 at 20 K. The agreement seems to be best at a temperature of 15 K. As opposed to the use of the normal rate equation method of surface chemistry, the modified rate method is in significantly better agreement with the stochastic-deterministic approach. Comparison with observations of molecular ices in dense clouds shows mixed agreement.

Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

Energy Technology Data Exchange (ETDEWEB)

Osseo-Asare, K.; Wei, Dawei

1996-01-01

This project seeks to advance the fundamental understanding of the physico-chemical processes occurring at the pyrite/aqueous interface, in the context of coal cleaning, coal desulfurization, and acid mine drainage. Central to this research is the use of synthetic microsize particles of pyrite as model microelectrodes to investigate the semiconductor electrochemistry of pyrite. The research focuses on: (a) the synthesis of microsize particles of pyrite in aqueous solution at room temperature, (b) the formation of iron sulfide complex, the precursor of FeS or FeS{sub 2}, and (c) the relationship between the semiconductor properties of pyrite and its interfacial electrochemical behavior in the dissolution process. In Chapter 2, 3 and 4, a suitable protocol for preparing microsize particles of pyrite in aqueous solution is given, and the essential roles of the precursors elemental sulfur and ``FeS`` in pyrite formation are investigated. In Chapter 5, the formation of iron sulfide complex prior to the precipitation of FeS or FeS{sub 2} is investigated using a fast kinetics technique based on a stopped-flow spectrophotometer. The stoichiometry of the iron sulfide complex is determined, and the rate and formation constants are also evaluated. Chapter 6 provides a summary of the semiconductor properties of pyrite relevant to the present study. In Chapters 7 and 8, the effects of the semiconductor properties on pyrite dissolution are investigated experimentally and the mechanism of pyrite dissolution in acidic aqueous solution is examined. Finally, a summary of the conclusions from this study and suggestions for future research are presented in Chapter 9.

Spectral Induced Polarization of Disseminated Pyrite Particles in Soil

Science.gov (United States)

Slater, L. D.; Kessouri, P.; Seleznev, N. V.

2017-12-01

Disseminated metallic particles in soil, particularly pyrite, occur naturally or are enhanced by anthropogenic activities. Detecting their presence and quantifying their concentration and location is of interest for numerous applications such as remediation of hydrocarbon contamination, mine tailings assessment, detection of oil traps, and archaeological studies. Because pyrite is a semiconductor, spectral induced polarization (SIP) is a promising geophysical method for sensing it in porous media. Previous studies have identified relations between pyrite properties (e.g., volumetric content, grain size) and SIP parameters (e.g., chargeability, relaxation time). However, the effect of pyrite grains in porous media on the SIP response is not fully understood over the entire low-frequency range. We tested the relationship between the presence of pyrite grains and the change in electrical properties of the medium through an extended series of laboratory measurements: (1) variation of grain size, (2) variation of grain concentration, (3) variation of electrolyte conductivity, (4) change in the diffusion properties of the host medium. For the fourth set of measurements, we compared sand columns to agar gel columns. Our experimental design included more than 20 different samples with multiple repeats to ensure representative results. We confirm the strong relation between grain size and relaxation time and that between grain concentration and chargeability in both the sand and agar gel samples. Furthermore, our results shed light on the significance of the diffusion coefficient and the recently hypothesized role of pyrite grains as resistors at frequencies lower than the relaxation frequency.

Introduction to Applied Colloid and Surface Chemistry

DEFF Research Database (Denmark)

Kontogeorgis, Georgios; Kiil, Søren

Colloid and Surface Chemistry is a subject of immense importance and implications both to our everyday life and numerous industrial sectors, ranging from coatings and materials to medicine and biotechnology. How do detergents really clean? (Why can’t we just use water ?) Why is milk “milky” Why do......, to the benefit of both the environment and our pocket. Cosmetics is also big business! Creams, lotions and other personal care products are really just complex emulsions. All of the above can be explained by the principles and methods of colloid and surface chemistry. A course on this topic is truly valuable...... to chemists, chemical engineers, biologists, material and food scientists and many more....

Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

Science.gov (United States)

Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

2018-03-07

Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

Semiconductor electrochemistry of coal pyrite. Final technical report, September 1990--September 1995

Energy Technology Data Exchange (ETDEWEB)

Osseo-Asare, K.; Wei, D.

1996-01-01

This project is concerned with the physiochemical processes occuring at the pyrite/aqueous interface, in the context of coal cleaning, desulfurization, and acid mine drainage. The use of synthetic particles of pyrite as model electrodes to investigate the semiconductor electrochemistry of pyrite is employed.

Modelling the reactive-path between pyrite and radioactive nuclides

International Nuclear Information System (INIS)

Kang Mingliang; Wu Shijun; Dou Shunmei; Chen Fanrong; Yang Yongqiang

2008-01-01

The mobility of redox sensitive nuclides is largely dependent on their valence state. The radionuclides that make the dominant contributions to final dose calculations are redox sensitive. Almost all the radionuclides (except 129 I) have higher mobility at high valence state, and correspond to immobilization at low valence state due to the much lower solubility. Pyrite is an ubiquitous and stable mineral in geological environment, and would be used as a low-cost long time reductant for the immobilization of radionuclides. However, pyrite oxidation is supposed to generate acid, which will enhance the mobility of nuclides. In this paper, the reaction path of the reactions between radionuclides (U, Se and Tc) and pyrite in the groundwater from Wuyi well in Beishan area of China has been simulated using geochemical modeling software. According to the results, pyrite can reduce high valence nuclides to a dinky-level effectively, with the pH slightly increasing under anaerobic condition that is common in deep nuclear waste repositories. (authors)

Practical considerations of pyrite oxidation control in uranium tailings

International Nuclear Information System (INIS)

1984-05-01

The problems posed by the oxidation of pyrite in uranium tailings include the generation of sulfuric acid and acid sulfate metal salts. These have substantial negative impacts on watercourse biota by themselves, and the lowered pH levels tend to mobilize heavy metals present in the tailings the rate of oxidation of pyrite at lower pH levels is catalyzed by sulfur and iron oxidizing bacteria present in soils. No single clear solution to the problems came from this study. Exclusion of air is a most important preventative of bacterial catalysis of oxidation. Bactericides, chemically breaking the chain of integrated oxidation reactions, maintaining anaerobic conditions, or maintaining a neutral or alkaline pH all reduce the oxidation rate. Removal of pyrite by flotation will reduce but not eliminate the impact of pyrite oxidation. Controlled oxidation of the remaining sulfide in the flotation tails would provide an innocuous tailing so far as acidity generation is concerned

Recrystallization Experiments of Pyrite From Circulating Hydrothermal Solution by Thermal Convection

Science.gov (United States)

Tanaka, K.; Isobe, H.

2005-12-01

Pyrite is one of the most common accessory minerals in many rocks and generally occurs in hydrothermal deposit. However, pyrite morphology and association with other sulfide minerals is not well known with respect to the solution condition, especially with the hydrothermal solution under circulation. In this study, recrystallization experiments of pyrite from circulating hydrothermal solution by thermal convection were carried out. A rectangular circuit (42.6 cm by 17.3 cm) of SUS316 pressure tubing with 5 mm in inner diameter was used as a reaction vessel. The volume of the circuit is approximately 24 ml. Long sides of the rectangular circuit were held to be 20 degrees inclination. One of the long sides was heated by an electric furnace. Solution in the circuit evaporates in the high temperature tubing and the vapor condenses in room temperature tubing. The solution backs to the bottom of the high temperature tubing. Thus, thermal convection of the solution produces circulation in the circuit. Starting material was filled in the high temperature tubing. The lower half was filled with mixture of 2 g of powdered natural pyrite and 4 g of quartz grains. The upper half was filled with quartz grains only. 9 ml of 5 mol/l NH4Cl solution was sealed in the circuit with the starting material. Temperature gradient of the sample was monitored by 6 thermocouples. Maximum temperature was controlled at 350°C. Experimental durations are 3, 5, 10 and 30 days. After the experiments, the run products are fixed with resin and cut every 2 cm. Thin sections of vertical cross-sections are made and observed by microscope and SEM. Tiny pyrite crystals occurred at the upper outside of the furnace, where temperature should be much lower than 200°C. In the lower half of the starting material, pyrite decomposed and pyrrhotite formed around pyrite grains. At higher temperature area, pyrite decomposition and pyrrhotite formation is remarkable. Circulating sulfur-bearing solution provided by

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

International Nuclear Information System (INIS)

Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; Ostrikov, Kostya; Vasilev, Krasimir

2016-01-01

The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces. (paper)

Particulate Pyrite Autotrophic Denitrification (PPAD) for Remediation of Nitrate-contaminated Groundwater

Science.gov (United States)

Tong, S.; Rodriguez-Gonzalez, L. C.; Henderson, M.; Feng, C.; Ergas, S. J.

2015-12-01

The rapid movement of human civilization towards urbanization, industrialization, and increased agricultural activities has introduced a large amount of nitrate into groundwater. Nitrate is a toxic substance discharged from groundwater to rivers and leads to decreased dissolved oxygen and eutrophication. For this experiment, an electron donor is needed to convert nitrate into non-toxic nitrogen gas. Pyrite is one of the most abundant minerals in the earth's crust making it an ideal candidate as an electron donor. The overall goal of this research was to investigate the potential for pyrite to be utilized as an electron donor for autotrophic denitrification of nitrate-contaminated groundwater. Batch studies of particulate pyrite autotrophic denitrification (PPAD) of synthetic groundwater (100 mg NO3--N L-1) were set up with varying biomass concentration, pyrite dose, and pyrite particle size. Reactors were seeded with mixed liquor volatile suspended solids (VSS) from a biological nitrogen removal wastewater treatment facility. PPAD using small pyrite particles (exhibited substantial nitrate removal rate, lower sulfate accumulation (5.46 mg SO42-/mg NO3--N) and lower alkalinity consumption (1.70 mg CaCO3/mg NO3--N) when compared to SOD (7.54 mg SO42-/mg NO3--N, 4.57 mg CaCO3/mg NO3--N based on stoichiometric calculation). This research revealed that the PPAD process is a promising technique for nitrate-contaminated groundwater treatment and promoted the utilization of pyrite in the field of environmental remediation.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials.

Science.gov (United States)

Dick, Susan; Konrad, Magdalena P; Lee, Wendy W Y; McCabe, Hannah; McCracken, John N; Rahman, Taifur M D; Stewart, Alan; Xu, Yikai; Bell, Steven E J

2016-07-01

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of perfluoroalkyl acids by carbonaceous adsorbents: Effect of carbon surface chemistry

International Nuclear Information System (INIS)

Zhi, Yue; Liu, Jinxia

2015-01-01

Adsorption by carbonaceous sorbents is among the most feasible processes to remove perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) from drinking and ground waters. However, carbon surface chemistry, which has long been recognized essential for dictating performance of such sorbents, has never been considered for PFOS and PFOA adsorption. Thus, the role of surface chemistry was systematically investigated using sorbents with a wide range in precursor material, pore structure, and surface chemistry. Sorbent surface chemistry overwhelmed physical properties in controlling the extent of uptake. The adsorption affinity was positively correlated carbon surface basicity, suggesting that high acid neutralizing or anion exchange capacity was critical for substantial uptake of PFOS and PFOA. Carbon polarity or hydrophobicity had insignificant impact on the extent of adsorption. Synthetic polymer-based Ambersorb and activated carbon fibers were more effective than activated carbon made of natural materials in removing PFOS and PFOA from aqueous solutions. - Highlights: • Adsorption of PFOS and PFOA by ten carbonaceous adsorbents were compared. • Surface chemistry of the adsorbents controlled adsorption affinity. • Carbon surface basicity was positively correlated with the extent of PFOS and PFOA uptake. • Carbon polarity or hydrophobicity was not correlated with adsorption affinity. • Synthetic polymer-based adsorbents were more effective in removing PFOS and PFOA. - Carbon surface basicity is the primary factor that influences adsorption affinity of the carbonaceous sorbents for perfluorooctane sulfonic and carboxylic acids

Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

NARCIS (Netherlands)

Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

1996-01-01

Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

The role of sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering

International Nuclear Information System (INIS)

Sasaki, K.; Tsunekawa, M.; Ohtsuka, T.; Konno, H.

1998-01-01

The paper investigates the role of the sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering in order to clarify the effects of the bacteria on the dissolution behavior of pyrite and the formation of secondary minerals using Raman spectroscopy and powder X-ray diffraction (XRD) in addition to solution analysis. It was found that T. thiooxidans, when present with the iron-oxidizing bacteria Thiobacillus ferrooxidans, enhanced the dissolution of Fe and S species for pyrite, whereas T. thiooxidans alone did not oxidize pyrite. Enhancement of the consumption of elemental sulfur and regeneration of Fe(II) ions were also observed with T. thiooxidans together with T. ferrooxidans, while this did not occur with T. ferrooxidans alone

Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite

International Nuclear Information System (INIS)

Xu, Zhi-Xiang; Wang, Qian; Fu, Xiao-Qi

2015-01-01

Highlights: • An exothermic reaction occurs at about 200 °C between pyrite and ammonium nitrate (emulsion explosives). • The essence of reaction between emulsion explosives and pyrite is reaction between ammonium nitrate and pyrite. • The excellent thermal stability of emulsion explosives does not mean it was also showed when pyrite was added. • A new overall reaction has been proposed as: • 14FeS_2(s) + 91NH_4NO_3(s) → 52NO(g) + 26SO_2(g) + 6Fe_2O_3(s) + 78NH_3(g) + 26N_2O(g) + 2FeSO_4(s) + 65H_2O(g). - Abstract: The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG–DSC–MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10 K/min from room temperature to 350 °C, exothermic reactions occurred at about 200 °C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO_2, NH_3, SO_2 and N_2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite

Energy Technology Data Exchange (ETDEWEB)

Xu, Zhi-Xiang; Wang, Qian [School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013 (China); Fu, Xiao-Qi, E-mail: xzx19820708@163.com [School of Chemistry and Chemical Engineering, Jiangsu University Zhenjiang 212013 (China)

2015-12-30

Highlights: • An exothermic reaction occurs at about 200 °C between pyrite and ammonium nitrate (emulsion explosives). • The essence of reaction between emulsion explosives and pyrite is reaction between ammonium nitrate and pyrite. • The excellent thermal stability of emulsion explosives does not mean it was also showed when pyrite was added. • A new overall reaction has been proposed as: • 14FeS{sub 2}(s) + 91NH{sub 4}NO{sub 3}(s) → 52NO(g) + 26SO{sub 2}(g) + 6Fe{sub 2}O{sub 3}(s) + 78NH{sub 3}(g) + 26N{sub 2}O(g) + 2FeSO{sub 4}(s) + 65H{sub 2}O(g). - Abstract: The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG–DSC–MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10 K/min from room temperature to 350 °C, exothermic reactions occurred at about 200 °C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO{sub 2}, NH{sub 3}, SO{sub 2} and N{sub 2}O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

The determination of uranium in pyrite samples

International Nuclear Information System (INIS)

Jacobs, J.J.

1979-01-01

An existing method for the determination of uranium in rocks and minerals is examined for the determination of uranium in materials containing pyrite. The results are comparable with those obtained by a spectrophotometric method, the precision (relative standard deviation) of the method for standards with U 3 O 8 contents of 1500 and 300 p.p.m. being 0,03 and 0,08 respectively when prepared in pyrite, and 0,15 and 0,06 respectively when made up with inert diluent. Full details of the procedure are given in accompanying appendices [af

Magmatic and fragmentation controls on volcanic ash surface chemistry

Science.gov (United States)

Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

2016-04-01

The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that

Sulfur isotope evidence for the contemporary formation of pyrite in a coastal acid sulfate soil

International Nuclear Information System (INIS)

Bush, R.T.; Sullivan, L.A.; Prince, K.; White, I.

2000-01-01

The sulfur isotopic composition of pyrite (FeS 2 ), greigite (Fe 3 S 4 ) and pore-water sulfate was determined for a typical coastal acid sulfate soil (ASS). Greigite occurs only in the partially oxidised upper-most pyrite sediments as blackish clusters within vertical fissures and other macro-pores. The concentration of pyrite was an order of magnitude greater than greigite in this layer, continuing through the underlying reduced estuarine sediments. δ 34 S of pyrite (0.45 per mil) associated with greigite accumulations were distinctly different to the bulk average for pyrite (-3.7 per mil), but similar to greigite (0.9 per mil). Greigite is meta-stable under reducing conditions, readily transforming to pyrite. The transformation of iron monosulfides (including greigite) to pyrite is a sulfur-isotope conservative process and therefore, these observations indicate that pyrite is forming from greigite at the oxic/anoxic boundary

Electrical conductivity of conductive carbon blacks: influence of surface chemistry and topology

International Nuclear Information System (INIS)

Pantea, Dana; Darmstadt, Hans; Kaliaguine, Serge; Roy, Christian

2003-01-01

Conductive carbon blacks from different manufacturers were studied in order to obtain some insight into the relation between their electrical conductivity and their surface properties. The surface chemistry was studied by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS), whereas the topology of the carbon black surface was investigated using low-pressure nitrogen adsorption. All these techniques yield information on the graphitic character of the surface. In general, the electrical conductivity of the conductive blacks increases with the graphitic character of the surface. For low surface area conductive blacks, the electrical conductivity correlates well with the surface chemistry. In the case of the XPS and SIMS data, this correlation is also valid when other types of carbon blacks such as thermal and furnace blacks are included, confirming the determining influence of the carbon black surface chemistry on the electrical conductivity

New improvements in the characterization of refractory gold in pyrites: an electron microprobe, Moessbauer spectrometry and ion microprobe study

International Nuclear Information System (INIS)

Marion, P.; Holliger, P.; Boiron, M.C.; Cathelineau, M.; Wagner, F.E.

1991-01-01

Studies of pyrites by Moessbauer spectroscopy have shown the presence of gold in a combined state probably inserted within the lattice. In order to enhance detection limits for in-situ quantitative gold analyses, new SIMS investigations have been made thanks to a Resistive Anode Encorder record of the ion emissions, which provides digital images or scans of any part of the analyzed volume. Quantitative analysis of gold have been carried out thanks to 2 MeV ion implantation of gold in reference sulfide crystals, and the bulk composition of a pyrite grain has been determined. Some strong enrichments in gold and arsenic at the crystal margin attest fluctuations in the fluid chemistry and may be interpreted as a final growth zone, which is similar to that observed on arsenopyrite crystals. This multidisciplinary approach constitutes a powerful tool for the investigation of the insertion and distribution of trace elements within crystals, especially gold in sulfides at low contents down to a few ppm. (author)

Microprobe channeling analysis of pyrite crystals

International Nuclear Information System (INIS)

Jamieson, D.N.; Ryan, C.G.

1992-01-01

Nuclear microprobe analysis has provided much useful information about the composition of microscopic inclusions in minerals, mainly through the use of Particle Induced X-ray Emission (PIXE). However this technique, while powerful, does not provide any direct information about the chemical state, in particular the lattice location, of the elements in the mineral. This information is often of crucial importance in understanding the ore genesis. The technique of ion channeling may be used to identify lattice location, but many minerals occur as microscopic crystals. Therefore it is necessary to utilize a nuclear microprobe with the technique of Channeling Contrast Microscopy (CCM). As many minerals contain interesting trace elements, it is necessary to measure both the yield of backscattered particles and the induced x-rays to get a clear picture of the lattice location of the elements in the crystal. CCM with PIXE was used to analyse natural pyrite crystals containing a variety of substitutional and non-substitutional elements and natural pyrite crystals from a gold bearing ore. In the latter case, evidence was obtained for two habits for Au in the 400 μm crystals: one as inclusions of Au rich minerals, the other substituted on the pyrite lattice sites. 31 refs., 3 tabs., 6 figs

Bacterial leaching of pyritic gold ores

International Nuclear Information System (INIS)

Gagliardi, F.M.; Cashion, J.D.; Brown, J.; Jay, W.H.

1998-01-01

Full text: Pyritic ores (pyrite and arsenopyrite) containing gold concentrations in excess of 50g Au/t can be processed to recover the gold by the removal of the sulphur from the ore. This may be achieved by roasting (producing sulphur dioxide emissions), pressure oxidation (expensive and suitable for large high grade deposits), pressure leaching (still currently being developed) or bacterial oxidation. The bacterial oxidation process is a well known process in nature but has only recently come under investigation as a economically viable and relatively clean method of gold recovery from deep low grade sulphidic ores. Samples were obtained from the Wiluna Gold Mine in Western Australia consisting of the original ore, six successive bacterial reactors and the final products. Moessbauer experiments have been performed at room temperature, liquid nitrogen and liquid helium temperatures, and in applied magnetic fields. The main components of the iron phases which were present during the bacterial treatment were pyrite and arsenopyrite which were readily oxidised by the bacteria. Ferric sulfates and ferric arsenates were identified as by-products of the process with a small amount of the oxyhydroxide goethite. These results are in contrast to the similar study of the Fairview Mine in South Africa where principally Fe(II) species were observed

XAS studies on selenite reduction by pyrite

International Nuclear Information System (INIS)

Kang Mingliang; Liu Chunli; Chen Fanrong; Charlet, Laurnet

2012-01-01

The interaction of aqueous Se (IV) with pyrite were systematically investigated in light of thermodynamic calculations and X-ray Absorption Spectroscopy (XAS). The results from the speciation study reveal that the reduction product is Se (O) when natural pyrite reacts with Se (N) at pH≤5.65, while small amount of FeSeO 3 or iron selenides may be formed at pH 6.1. At pH≥6.94, due to the precipitation of Fe (Ⅲ) -oxyhydroxide, the formation of the thermodynamically most stable species, FeSe 2 , is inhibited. However, when the reactive nanopyrite-greigite was used for reaction, the thermodynamically most stable species, FeSe 2 , was found for the first time as the predominant product in the present study, suggesting that 79 Se can be immobilized in its most insoluble form, FeSe 2 , in Fe (Ⅱ) -sulfide containing environment. This study confirms that pyrite can significantly attenuate the mobility of Se by reductive precipitation, and that the reaction process does not produce protons under acidic or neutral condition when Se (O) is formed. (authors)

Chalcopyrite Dissolution at 650 mV and 750 mV in the Presence of Pyrite

Directory of Open Access Journals (Sweden)

Yubiao Li

2015-08-01

Full Text Available The dissolution of chalcopyrite in association with pyrite in mine waste results in the severe environmental issue of acid and metalliferous drainage (AMD. To better understand chalcopyrite dissolution, and the impact of chalcopyrite’s galvanic interaction with pyrite, chalcopyrite dissolution has been examined at 75 °C, pH 1.0, in the presence of quartz (as an inert mineral and pyrite. The presence of pyrite increased the chalcopyrite dissolution rate by more than five times at Eh of 650 mV (SHE (Cu recovery 2.5 cf. 12% over 132 days due to galvanic interaction between chalcopyrite and pyrite. Dissolution of Cu and Fe was stoichiometric and no pyrite dissolved. Although the chalcopyrite dissolution rate at 750 mV (SHE was approximately four-fold greater (Cu recovery of 45% within 132 days as compared to at 650 mV in the presence of pyrite, the galvanic interaction between chalcopyrite and pyrite was negligible. Approximately all of the sulfur from the leached chalcopyrite was converted to S0 at 750 mV, regardless of the presence of pyrite. At this Eh approximately 60% of the sulfur associated with pyrite dissolution was oxidised to S0 and the remaining 40% was released in soluble forms, e.g., SO42−.

Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

Science.gov (United States)

Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

2014-02-15

The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.

Science.gov (United States)

Xu, Zhi-Xiang; Wang, Qian; Fu, Xiao-Qi

2015-12-30

The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG-DSC-MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10K/min from room temperature to 350°C, exothermic reactions occurred at about 200°C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO2, NH3, SO2 and N2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals. Copyright © 2015 Elsevier B.V. All rights reserved.

Presentation on mechanisms and applications of chalcopyrite and pyrite bioleaching in biohydrometallurgy - a presentation.

Science.gov (United States)

Tao, Huang; Dongwei, Li

2014-12-01

This review outlines classic and current research, scientific documents and research achievements in bioleaching, particularly in respect of the bioleaching of chalcopyrite and pyrite. The diversity and commonality of the microbial leaching process can be easily studied through comparing the bioleaching mechanism and the application of these two metal sulfides. The crystal, electronic and surface structures of chalcopyrite and pyrite are summarized in detail in this paper. It determines the specific and complicated interaction pathways, kinetics of the atmospheric/aqueous oxidation, and the control process of bioleaching of the minerals as the precondition. Bioleaching of metal sulfides is performed by a diverse group of microorganisms and microbial communities. The species of the bacteria which have a significant effect on leaching ores are miraculously diverse. The newly identified acidophilic microorganisms with unique characteristics for efficient bioleaching of sulfidic minerals are increasing sharply. The cell-to-cell communication mechanisms, which are still implicit, elusive and intangible at present day, have gradually become a research hotspot. The different mineralogy characteristics and the acid solubility of the metal sulfides (e.g., chalcopyrite and pyrite) cause two different dissolution pathways, the thiosulfate and the polysulfide pathways. The bioleaching mechanisms are categorized by contact (an electrostatic attachment) and noncontact (planktonic) process, with emphasis on the produce of extracellular polymeric substances and formation of biofilm on the surface of the metal sulfides in this paper. The division of the direct and indirect effect are not adopted due to the redox chain, the reduction of the ferric iron and oxidation of the ferrous iron. The molecular oxygen is reduced by the electrons extracted from the specific metal sulfide, via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner

Waste pyritic coal as a raw material for energetic industry

Energy Technology Data Exchange (ETDEWEB)

Gasiorek, J. [Institute of Inorganic Chemistry, Poznan (Poland). Dept. of Research and Technology

1997-11-01

Results are presented of large laboratory studies on coal desulphurisation with foam flotation method improved by application of bioadsorption of Thiobacillus ferrooxidans bacteria to the modification of superficial properties of pyrite particulates from hydrophobic to hydrophillic ones. Results of coal desulfurization with and without bioadsorption have been compared. Bioadsorption improved pyritic sulfur removal by 30% (for coal from `Sierza mine`, coal size 0.3 to 0.102 mm, S pyritic content 1.69%) after 6-week adaptation of bacteria and 30 min of bioadsorption. Bacteria concentration in 5% water suspension of coal reached 22 {mu}g of biomass cm{sup -3}. 12 refs., 4 figs., 1 tab.

Application of fuel cell for pyrite and heavy metal containing mining waste

Science.gov (United States)

Keum, H.; Ju, W. J.; Jho, E. H.; Nam, K.

2015-12-01

Once pyrite and heavy metal containing mining waste reacts with water and air it produces acid mine drainage (AMD) and leads to the other environmental problems such as contamination of surrounding soils. Pyrite is the major source of AMD and it can be controlled using a biological-electrochemical dissolution method. By enhancing the dissolution of pyrite using fuel cell technology, not only mining waste be beneficially utilized but also be treated at the same time by. As pyrite-containing mining waste is oxidized in the anode of the fuel cell, electrons and protons are generated, and electrons moves through an external load to cathode reducing oxygen to water while protons migrate to cathode through a proton exchange membrane. Iron-oxidizing bacteria such as Acidithiobacillus ferrooxidans, which can utilize Fe as an electron donor promotes pyrite dissolution and hence enhances electrochemical dissolution of pyrite from mining waste. In this study mining waste from a zinc mine in Korea containing 17 wt% pyrite and 9% As was utilized as a fuel for the fuel cell inoculated with A. ferrooxidans. Electrochemically dissolved As content and chemically dissolved As content was compared. With the initial pH of 3.5 at 23℃, the dissolved As concentration increased (from 4.0 to 13 mg/L after 20 d) in the fuel cell, while it kept decreased in the chemical reactor (from 12 to 0.43 mg/L after 20 d). The fuel cell produced 0.09 V of open circuit voltage with the maximum power density of 0.84 mW/m2. Dissolution of As from mining waste was enhanced through electrochemical reaction. Application of fuel cell technology is a novel treatment method for pyrite and heavy metals containing mining waste, and this method is beneficial for mining environment as well as local community of mining areas.

NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2013-03-01

NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

Science.gov (United States)

Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

1991-01-01

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

Science.gov (United States)

Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

2014-10-01

An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

Unraveling the Reaction Chemistry of Icy Ocean World Surfaces

Science.gov (United States)

Hudson, R.; Loeffler, M. J.; Gerakines, P.

2017-12-01

The diverse endogenic chemistry of ocean worlds can be divided among interior, surface, and above-surface process, with contributions from exogenic agents such as solar, cosmic, and magnetospheric radiation. Bombardment from micrometeorites to comets also can influence chemistry by both delivering new materials and altering pre-existing ones, and providing energy to drive reactions. Geological processes further complicate the chemistry by transporting materials from one environment to another. In this presentation the focus will be on some of the thermally driven and radiation-induced changes expected from icy materials, primarily covalent and ionic compounds. Low-temperature conversions of a few relatively simple molecules into ions possessing distinct infrared (IR) features will be covered, with an emphasis on such features as might be identified through either orbiting spacecraft or landers. The low-temperature degradation of a few bioorganic molecules, such as DNA nucleobases and some common amino acids, will be used as examples of the more complex, and potentially misleading, chemistry expected for icy moons of the outer solar system. This work was supported by NASA's Emerging Worlds and Outer Planets Research programs, as well as the NASA Astrobiology Institute's Goddard Center for Astrobiology.

Trace element chemistry and textures of low-temperature pyrites associated with shallow fossil subsurface geothermal discharge in the Eger Graben, northwestern Bohemia

Czech Academy of Sciences Publication Activity Database

Zachariáš, J.; Adamovič, Jiří; Langrová, Anna

2006-01-01

Roč. 37, 29 (2006), s. 237-239 ISSN 0032-6267 R&D Projects: GA AV ČR IAA3013302 Institutional research plan: CEZ:AV0Z30130516 Keywords : pyrite * geothermal fluids * Eger Graben Subject RIV: DB - Geology ; Mineralogy

Variability in chemistry of surface and soil waters of an ...

African Journals Online (AJOL)

Water chemistry is important for the maintenance of wetland structure and function. Interpreting ecological patterns in a wetland system therefore requires an in-depth understanding of the water chemistry of that system. We investigated the spatial distribution of chemical solutes both in soil pore water and surface water, ...

Technological procedure for chemical cleaning prior to re-pyritization of H2O-H2S isotopic exchange installations

International Nuclear Information System (INIS)

Stefanescu, I.; Smaranda, D.; Titescu, Gh.

1996-01-01

In normal operation the anti-corrosive shielding of the GS installations undergo a slow, irreversible degradation in time so that after 6 - 8 years their protection characteristics break down. In order to put them back in operation the regeneration of anti-corrosive is required. The procedure achieved at ICIS - Rm.Valcea consists in chemical cleaning of the impaired layers and re-pyritization of the interior surface of installations. Chemical cleaning include the following operations: - mechanical cleaning; - water washing; - alkaline washing with sodium hydroxide, tri-sodium phosphate and sodium tri-polyphosphate; - final mechanical cleaning; - neutralizing washing; - chemical cleaning with phosphoric acid solution; - neutralizing washing. After applying this procedure, the surface is prepared for the pyritization regeneration of the anti-corrosive shielding which ensures the prolongation of the equipment service lifetime with another six year period

Deconvoluting the effects of surface chemistry and nanoscale topography: Pseudomonas aeruginosa biofilm nucleation on Si-based substrates.

Science.gov (United States)

Zhang, Jing; Huang, Jinglin; Say, Carmen; Dorit, Robert L; Queeney, K T

2018-06-01

The nucleation of biofilms is known to be affected by both the chemistry and topography of the underlying substrate, particularly when topography includes nanoscale (topography vs. chemistry is complicated by concomitant variation in both as a result of typical surface modification techniques. Analyzing the behavior of biofilm-forming bacteria exposed to surfaces with systematic, independent variation of both topography and surface chemistry should allow differentiation of the two effects. Silicon surfaces with reproducible nanotopography were created by anisotropic etching in deoxygenated water. Surface chemistry was varied independently to create hydrophilic (OH-terminated) and hydrophobic (alkyl-terminated) surfaces. The attachment and proliferation of Psuedomonas aeruginosa to these surfaces was characterized over a period of 12 h using fluorescence and confocal microscopy. The number of attached bacteria as well as the structural characteristics of the nucleating biofilm were influenced by both surface nanotopography and surface chemistry. In general terms, the presence of both nanoscale features and hydrophobic surface chemistry enhance bacterial attachment and colonization. However, the structural details of the resulting biofilms suggest that surface chemistry and topography interact differently on each of the four surface types we studied. Copyright © 2018 Elsevier Inc. All rights reserved.

Grain surface chemistry in protoplanetary disks

International Nuclear Information System (INIS)

Reboussin, Laura

2015-01-01

Planetary formation occurs in the protoplanetary disks of gas and dust. Although dust represents only 1% of the total disk mass, it plays a fundamental role in disk chemical evolution since it acts as a catalyst for the formation of molecules. Understanding this chemistry is therefore essential to determine the initial conditions from which planets form. During my thesis, I studied grain-surface chemistry and its impact on the chemical evolution of molecular cloud, initial condition for disk formation, and protoplanetary disk. Thanks to numerical simulations, using the gas-grain code Nautilus, I showed the importance of diffusion reactions and gas-grain interactions for the abundances of gas-phase species. Model results combined with observations also showed the effects of the physical structure (in temperature, density, AV) on the molecular distribution in disks. (author)

The composition of pyrite in volcanogenic massive sulfide deposits as determined with the proton microprobe

International Nuclear Information System (INIS)

Huston, D.L.; Sie, S.H.; Suter, G.F.; Ryan, C.G.

1993-01-01

Pixeprobe analysis of pyrite from Australian volcanogenic massive sulfide (VMS) deposits indicate significant levels of Cu, Zn, Pb, Ba, Ag, Sb, Bi (from inclusions), As, Tl, Mo, Au, In, Cd (from nonstoichiometric substitution), Co, Ni, Se and Te (from stoichiometric substitution). Pyrite in massive sulfide lenses is enriched in trace elements compared to that in the stringer zone owing to hydrothermal recrystallization. Metamorphic recrystallization also 'cleans' pyrite of trace elements. High Au values occur in pyrite with high As content. Pyrite in stringer zones is enriched in Se relative to the overlying massive sulfide lenses and the surrounding alteration zones. (orig.)

Complete removal of AHPS synthetic dye from water using new electro-fenton oxidation catalyzed by natural pyrite as heterogeneous catalyst.

Science.gov (United States)

Labiadh, Lazhar; Oturan, Mehmet A; Panizza, Marco; Hamadi, Nawfel Ben; Ammar, Salah

2015-10-30

The mineralization of a new azo dye - the (4-amino-3-hydroxy-2-p-tolylazo-naphthalene-1-sulfonic acid) (AHPS) - has been studied by a novel electrochemical advanced oxidation process (EAOP), consisting in electro-Fenton (EF) oxidation, catalyzed by pyrite as the heterogeneous catalyst - the so-called 'pyrite-EF'. This solid pyrite used as heterogeneous catalyst instead of a soluble iron salt, is the catalyst the system needs for production of hydroxyl radicals. Experiments were performed in an undivided cell equipped with a BDD anode and a commercial carbon felt cathode to electrogenerate in situ H2O2 and regenerate ferrous ions as catalyst. The effects on operating parameters, such as applied current, pyrite concentration and initial dye content, were investigated. AHPS decay and mineralization efficiencies were monitored by HPLC analyses and TOC measurements, respectively. Experimental results showed that AHPS was quickly oxidized by hydroxyl radicals (OH) produced simultaneously both on BDD surface by water discharge and in solution bulk from electrochemically assisted Fenton's reaction with a pseudo-first-order reaction. AHPS solutions with 175 mg L(-1) (100 mg L(-1) initial TOC) content were then almost completely mineralized in 8h. Moreover, the results demonstrated that, under the same conditions, AHPS degradation by pyrite electro-Fenton process was more powerful than the conventional electro-Fenton process. Copyright © 2015 Elsevier B.V. All rights reserved.

Lattice location of gold in natural pyrite crystals

International Nuclear Information System (INIS)

Besten, Jacinta den; Jamieson, David N.; Ryan, Chris G.

1999-01-01

The lattice location of gold atoms in naturally occurring Au-doped pyrite crystals has been investigated with a nuclear microprobe using ion channeling. The specimens consisted of 300-μm diameter pyrite crystals in veins embedded in a quartz matrix from the Emperor mine in Fiji. The specimens were prepared by standard geological specimen preparation techniques and the pyrite crystals were analysed in situ in the quartz matrix. Significant trace elements in the crystals, determined by Proton Induced X-ray Emission with a 3 MeV H + microprobe, were Cu, As, Mo, Zn, Te, Au and Pb. The Au concentration was about 0.2 wt%. By the use of 2 MeV He + ion channeling, the Miller indices of the lowest order crystal axes nearest to the normal were determined from backscattering yield maps from two-dimensional angular scanning and comparison of the resulting patterns with published gnomonic projections. Channeling angular yield curves were obtained from Fe, S, As and Au signals. The results indicate that at least 35% of the Au is substituted onto lattice sites

Pyrite deformation and connections to gold mobility: Insight from micro-structural analysis and trace element mapping

Science.gov (United States)

Dubosq, R.; Lawley, C. J. M.; Rogowitz, A.; Schneider, D. A.; Jackson, S.

2018-06-01

The metamorphic transition of pyrite to pyrrhotite results in the liberation of lattice-bound and nano-particulate metals initially hosted within early sulphide minerals. This process forms the basis for the metamorphic-driven Au-upgrading model applied to many orogenic Au deposits, however the role of syn-metamorphic pyrite deformation in controlling the retention and release of Au and related pathfinder elements is poorly understood. The lower amphibolite facies metamorphic mineral assemblage (Act-Bt-Pl-Ep-Alm ± Cal ± Qz ± Ilm; 550 °C) of Canada's giant Detour Lake deposit falls within the range of pressure-temperature conditions (450 °C) for crystal plastic deformation of pyrite. We have applied a complementary approach of electron backscatter diffraction (EBSD) mapping and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) 2D element mapping on pyrite from the Detour Lake deposit. Chemical element maps document an early generation of Au-rich sieve textured pyrite domains and a later stage of syn-metamorphic oscillatory-zoned Au-poor pyrite. Both pyrite types are cut by Au-rich fractures as a consequence of remobilization of Au with trace element enrichment of first-row transition elements, post-transition metals, chalcogens and metalloids during a late brittle deformation stage. However, similar enrichment in trace elements and Au can be observed along low-angle grain boundaries within otherwise Au-poor pyrite, indicating that heterogeneous microstructural misorientation patterns and higher strain domains are also relatively Au-rich. We therefore propose that the close spatial relationship between pyrite and Au at the microscale, features typical of orogenic Au deposits, reflects the entrapment of Au within deformation-induced microstructures in pyrite rather than the release of Au during the metamorphic transition from pyrite to pyrrhotite. Moreover, mass balance calculations at the deposit scale suggest that only a small percentage

Thermoluminescence kinetics of pyrite (FeS2)

International Nuclear Information System (INIS)

Silverman, A.N; Levy, P.W.; Kierstead, J.A.

1990-01-01

Thermoluminescence of pyrite (FeS 2 ) has been investigated to study the kinetics of single peak glow curves. The material used normally exhibits one large and four small peaks. However a glow curve can be obtained with only the large single peak that is suitable for testing thermoluminescence kinetics. Glow curves from aliquots of a single natural pyrite crystal studied in detail contain two low intensity thermoluminescence (TL) peaks at ∼90 degree and ∼250 degree C, and two chemiluminescence (CL) peaks at ∼350 degree and ∼430 degree C. The CL peaks are largely removable by initially heating the sample chamber under vacuum, pumping through liquid nitrogen traps, and recording glow curves immediately after helium is introduced, procedures which reduce system contaminants that react with pyrite. The shape, the variation of the temperature of the peak maximum (T max ) with dose, and the retrapping to recombination cross section ratio σ of the large 250 degree C peak are better described by the general one trap (GOT) kinetic equation, the basic equation from which the 1st and 2nd order kinetic equations are obtained as special cases (see text), than by the 1st and 2nd order equations. 12 refs., 7 figs

Study of the pyritized surfaces of the carbon steel components in heavy water production facilities

International Nuclear Information System (INIS)

Radulescu, Maria; Parvan, Ioana; Lucan, Dumitra; Fulger, Manuela; Dinu, Alice; Blanatui, A.

1998-01-01

The components used in the Girldler Sulfide (GS) process of heavy water production are made of carbon steel covered by iron sulfide layers of different compositions (mackinawite, troilite, pyrrhotite or pyrite) of variable thicknesses. The most protective layers which provide an acceptable corrosion resistance of the subjacent metal are the mixtures of pyrrhotite and pyrite. In the present work, the corrosion resistance of carbon steel samples covered by different types of sulfides was investigated by the following methods: X ray diffraction, metallography and electrochemical methods (potential-dynamical and electrochemical impedance). In order to carry out the electrochemical measurements in the same conditions as those of the operation of carbon steel components in D 2 O production facilities, the experiments were performed with Na 2 S solutions, at pH=4 - 13 and S 2- concentration value between 1 and 1000 mg/l. The dependence of corrosion rate kinetics on pH and S 2- concentration of the testing solution was investigated for sulfide covered samples comparatively with the uncovered ones. Corrosion rates determined gravimetrically were compared with those determined by electrochemical measurements. The uniformity and thickness of the sulfide layers were checked by metallographic methods. The composition of the sulfides formed in various environment conditions was established by X-ray diffraction. Reaction mechanisms specific for sulfide formation environments have been proposed. (authors)

Drainage from coal mines: Chemistry and environmental problems

International Nuclear Information System (INIS)

Wildeman, T.

1991-01-01

Much of the research on coal-mine drainage chemistry was conducted a decade ago, and now increased environmental awareness has brought about renewed interest in the findings. Consideration of the trace minerals and elements in coal points to the possible generation of acidic waters upon weathering, especially when pyrite is present. When pyrite weathers, it produces H + and Fe 3+ which catalyze the incongruent weathering of other carbonates and sulfides. In this weathering mechanism, catalysis by bacteria is important. Of the environmental problems in coal mine drainage, the mineral acidity of the water is the most serious. This is caused not only by the H + , but also by Mn 4+ , Fe 3+ , and Al 3+ that are found or generated within the drainage. Case studies in Kentucky, Pennsylvania, Illinois, and Colorado show that the abundance and form of pyrite in the deposit and in the overburden determines the level of acidity and the concentration of heavy metal pollutants in the drainage. Recent trends in environmental enforcement that emphasize integrated stream water standards and biotoxicity assays point to the possibility that the concentrations of heavy metals in coal mine drainages may cause environmental concern

Recent advances in study of uranium surface chemistry in China

International Nuclear Information System (INIS)

Luo, Lizhu; Lai, Xinchun; Wang, Xiaolin

2014-01-01

Uranium is very important in nuclear energy industry; however, uranium and its alloys corrode seriously in various atmospheres because of their chemical reactivities. In China, continuous investigations focused on surface chemistry have been carried out for a thorough understanding of uranium in order to provide technical support for its engineering applications. Oxidation kinetics of uranium and its alloys in oxidizing atmospheres are in good agreement with those in the literature. In addition to the traditional techniques, non-traditional methods have been applied for oxidation kinetics of uranium, and it has been verified that spectroscopic ellipsometry and X-ray diffraction are effective and nondestructive tools for in situ kinetic studies. The inhibition efficiency of oxidizing gas impurities on uranium hydrogenation is found to follow the order CO 2 > CO > O 2 , and the broadening of XPS shoulders with temperature in depth profile of hydrogenated uranium surface is discussed, which is not mentioned in the literature. Significant progress on surface chemistry of alloyed uranium (U-Nb and U-Ti) in hydrogen atmosphere is reported, and it is revealed that the hydrating nucleation and subsequent growth of alloyed uranium are closely connected with the surface states, underlying metal matrix, and it is microstructure-dependent. In this review, the recent advances in uranium surface chemistry in China, published so far mostly in Chinese language, are briefly summarized. Suggestions for further study are made. (orig.)

Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite

International Nuclear Information System (INIS)

Gunawan, Richard; Zhang Dongke

2009-01-01

The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol -1 and 4.55 x 10 7 s -1 without the presence of pyrite and 101.8 kJ mol -1 and 2.57 x 10 9 s -1 with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.

Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.

Science.gov (United States)

Gunawan, Richard; Zhang, Dongke

2009-06-15

The interaction between ammonium nitrate based industrial explosives and pyrite-rich minerals in mining operations can lead to the occurrence of spontaneous explosion of the explosives. In an effort to provide a scientific basis for safe applications of industrial explosives in reactive mining grounds containing pyrite, ammonium nitrate decomposition, with and without the presence of pyrite, was studied using a simultaneous Differential Scanning Calorimetry and Thermogravimetric Analyser (DSC-TGA) and a gas-sealed isothermal reactor, respectively. The activation energy and the pre-exponential factor of ammonium nitrate decomposition were determined to be 102.6 kJ mol(-1) and 4.55 x 10(7)s(-1) without the presence of pyrite and 101.8 kJ mol(-1) and 2.57 x 10(9)s(-1) with the presence of pyrite. The kinetics of ammonium nitrate decomposition was then used to calculate the critical temperatures for ammonium nitrate decomposition with and without the presence of pyrite, based on the Frank-Kamenetskii model of thermal explosion. It was shown that the presence of pyrite reduces the temperature for, and accelerates the rate of, decomposition of ammonium nitrate. It was further shown that pyrite can significantly reduce the critical temperature of ammonium nitrate decomposition, causing undesired premature detonation of the explosives. The critical temperature also decreases with increasing diameter of the blast holes charged with the explosive. The concept of using the critical temperature as indication of the thermal stability of the explosives to evaluate the risk of spontaneous explosion was verified in the gas-sealed isothermal reactor experiments.

Reactivity of Dazomet, a Hydraulic Fracturing Additive: Hydrolysis and Interaction with Pyrite

Science.gov (United States)

Consolazio, N.; Lowry, G. V.; Karamalidis, A.; Hakala, A.

2015-12-01

The Marcellus Shale is currently the largest shale gas formation in play across the world. The low-permeability formation requires hydraulic fracturing to be produced. In this process, millions of gallons of water are blended with chemical additives and pumped into each well to fracture the reservoir rock. Although additives account for less than 2% of the fracking fluid mixture, they amount to hundreds of tons per frack job. The environmental properties of some of these additives have been studied, but their behavior under downhole conditions is not widely reported in the peer-reviewed literature. These compounds and their reaction products may return to the surface as produced or waste water. In the event of a spill or release, this water has the potential to contaminate surface soil and water. Of these additives, biocides may present a formidable challenge to water quality. Biocides are toxic compounds (by design), typically added to the Marcellus Shale to control bacteria in the well. An assessment of the most frequently used biocides indicated a need to study the chemical dazomet under reservoir conditions. The Marcellus Shale contains significant deposits of pyrite. This is a ubiquitous mineral within black shales that is known to react with organic compounds in both oxic and anoxic settings. Thus, the objective of our study was to determine the effect of pyrite on the hydrolysis of dazomet. Liquid chromatography-triple quadrupole mass spectrometry (LC-QQQ) was used to calculate the loss rate of aqueous dazomet. Gas chromatography-mass spectrometry (GC-MS) was used to identify the reaction products. Our experiments show that in water, dazomet rapidly hydrolyses in water to form organic and inorganic transformation products. This reaction rate was unaffected when performed under anoxic conditions. However, with pyrite we found an appreciable increase in the removal rate of dazomet. This was accompanied by a corresponding change in the distribution of observed

The flotation of gold, uranium, and pyrite from Witwatersrand ores

International Nuclear Information System (INIS)

Lloyd, P.J.D.

1981-01-01

The Witwatersrand reefs contain gold, uranium, and pyrite in the following average concentrations: 0,001 per cent, 0,02 per cent, and 1,7 per cent respectively. The paper discusses the flotation of pyrite to produce a sulphide concentrate, reviews work done on the production of gold concentrates, discusses attempts to produce maximum concentrates, and closes with a review of processes for the simultaneous flotation of these three species. It is concluded that high recoveries of all three species can be achieved only if a rougher concentrate of perhaps 20 per cent of the feed (by mass) is produced, and it is suggested that reverse leaching (leaching before cyanidation) of this concentrate, followed by a cleaning flotation step for the recovery of the pyrite, would be more efficient than the routes employed at present [af

Preparation of Authigenic Pyrite from Methane-bearing Sediments for In Situ Sulfur Isotope Analysis Using SIMS.

Science.gov (United States)

Lin, Zhiyong; Sun, Xiaoming; Peckmann, Jörn; Lu, Yang; Strauss, Harald; Xu, Li; Lu, Hongfeng; Teichert, Barbara M A

2017-08-31

Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ 34 S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ 34 S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ 34 S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34 S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ 34 S values than the framboids. Such 34 S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.

Effect of Phospholipid on Pyrite Oxidation and Microbial Communities under Simulated Acid Mine Drainage (AMD) Conditions.

Science.gov (United States)

Pierre Louis, Andro-Marc; Yu, Hui; Shumlas, Samantha L; Van Aken, Benoit; Schoonen, Martin A A; Strongin, Daniel R

2015-07-07

The effect of phospholipid on the biogeochemistry of pyrite oxidation, which leads to acid mine drainage (AMD) chemistry in the environment, was investigated. Metagenomic analyses were carried out to understand how the microbial community structure, which developed during the oxidation of pyrite-containing coal mining overburden/waste rock (OWR), was affected by the presence of adsorbed phospholipid. Using columns packed with OWR (with and without lipid adsorption), the release of sulfate (SO4(2-)) and soluble iron (FeTot) was investigated. Exposure of lipid-free OWR to flowing pH-neutral water resulted in an acidic effluent with a pH range of 2-4.5 over a 3-year period. The average concentration of FeTot and SO4(2-) in the effluent was ≥20 and ≥30 mg/L, respectively. In contrast, in packed-column experiments where OWR was first treated with phospholipid, the effluent pH remained at ∼6.5 and the average concentrations of FeTot and SO4(2-) were ≤2 and l.6 mg/L, respectively. 16S rDNA metagenomic pyrosequencing analysis of the microbial communities associated with OWR samples revealed the development of AMD-like communities dominated by acidophilic sulfide-oxidizing bacteria on untreated OWR samples, but not on refuse pretreated with phospholipid.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

Science.gov (United States)

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

2016-03-14

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

Directory of Open Access Journals (Sweden)

Wei Zheng

2016-03-01

Full Text Available Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Pyrite as a proxy for the identification of former coastal lagoons in semiarid NE Brazil

Science.gov (United States)

Ferreira, Tiago O.; Nóbrega, Gabriel N.; Albuquerque, Antonia G. B. M.; Sartor, Lucas R.; Gomes, Irlene S.; Artur, Adriana G.; Otero, Xosé L.

2015-10-01

This work aimed to test the suitability of pyrite (FeS2) as a proxy for reconstructing past marine environmental conditions along the semiarid coast of Brazil. Morphological description combined with physicochemical analyses including Fe partitioning were conducted for soil depth profiles (30 and 60 cm depths) at three sites in two contrasting lagoons of the state of Ceará: a suspected former lagoon that would have been transformed into a freshwater "lake" at a site vegetated by Juncus effusus (site P1), and another lagoon with connection to the sea at sites vegetated by J. effusus (site P2) or Portulaca oleracea (site P3). Soil samples were collected in September 2010. Site P3 had more reducing conditions, reaching Eh values of -132 mV in the surface layer (0-10 cm), whereas minimum values for the P1 and P2 sites were +219 and +85 mV, respectively. Lower pyritic Fe values were found at site P1, with a degree of pyritization (DOP) ranging from 10 to 13%. At sites P2 and P3, DOP ranged from 9 to 67% and from 55 to 72%, respectively. These results are consistent with an interruption of tidal channels by eolian dune migration inducing strong changes in the hydrodynamics and physicochemical characteristics (lower salinity, oxidizing conditions) of these sites, causing the dieback of suspected former mangroves and a succession to freshwater marshes with an intermediate salt marsh stage. Together with other physicochemical signatures, pyrite can evidently serve as a useful proxy in tracking environmental changes in such ecotones, with implications for coastal management.

Recent advances in study of uranium surface chemistry in China

Energy Technology Data Exchange (ETDEWEB)

Luo, Lizhu; Lai, Xinchun [Science and Technology on Surface Physics and Chemistry Laboratory, Sichuan (China); Wang, Xiaolin [China Academy of Engineering Physics, Sichuan (China)

2014-04-01

Uranium is very important in nuclear energy industry; however, uranium and its alloys corrode seriously in various atmospheres because of their chemical reactivities. In China, continuous investigations focused on surface chemistry have been carried out for a thorough understanding of uranium in order to provide technical support for its engineering applications. Oxidation kinetics of uranium and its alloys in oxidizing atmospheres are in good agreement with those in the literature. In addition to the traditional techniques, non-traditional methods have been applied for oxidation kinetics of uranium, and it has been verified that spectroscopic ellipsometry and X-ray diffraction are effective and nondestructive tools for in situ kinetic studies. The inhibition efficiency of oxidizing gas impurities on uranium hydrogenation is found to follow the order CO{sub 2} > CO > O{sub 2}, and the broadening of XPS shoulders with temperature in depth profile of hydrogenated uranium surface is discussed, which is not mentioned in the literature. Significant progress on surface chemistry of alloyed uranium (U-Nb and U-Ti) in hydrogen atmosphere is reported, and it is revealed that the hydrating nucleation and subsequent growth of alloyed uranium are closely connected with the surface states, underlying metal matrix, and it is microstructure-dependent. In this review, the recent advances in uranium surface chemistry in China, published so far mostly in Chinese language, are briefly summarized. Suggestions for further study are made. (orig.)

Isotopic and microbiological signatures of pyrite-driven denitrification in a sandy aquifer

NARCIS (Netherlands)

Zhang, Y.-C.; Slomp, C.P.; Broers, H.P.; Bostick, B.; Passier, H.F.; Böttcher, M.E.; Omoregie, E.O.; Lloyd, J.R.; Polya, D.A.; Van Cappellen, P.

2012-01-01

Denitrificationdriven by pyrite oxidation can play a major role in the removal of nitrate from groundwater systems. As yet, limited information is available on the interactions between the micro-organisms and aqueous and mineral phases in aquifers where pyrite oxidation is occurring. In this study,

A model of pyritic oxidation in waste rock dumps

International Nuclear Information System (INIS)

Davis, G.B.; Ritchie, A.I.M.

1983-01-01

The oxidation of pyrite can lead to high acid levels and high concentrations of trace metals in the water that runs off and percolates through pyritic material. This is the situation at the abandoned uranium mine at Rum Jungle in the Northern Territory of Australia, where pyritic oxidation in the waste rock dumps resulting from open cut mining of the uranium orebody has led to pollution of the nearby East Branch of the Finniss River, with trace metals such as copper, manganese and zinc. Mathematical equations are formulated which describe a model of pyritic oxidation within a waste rock dump, where it is assumed that oxygen transport is the rate limiting step in the oxidation process and that oxygen is transported by gaseous diffusion through the pore space of the dump, followed by diffusion into oxidation sites within the particles that comprise the dump. The equations have been solved numerically assuming values for such parameters as porosity, sulphur density and oxygen diffusion coefficients which are applicable to the waste rock dumps at Rum Jungle. An approximate solution to the equations is also presented. Calculations of the heat source distribution and the total SO 4 production rate are presented for both single size particles and for a range of particle sizes in the dump. The usefulness of the approximate solution, and of calculations based on single size particles in the dump in assessing the effectiveness of strategies to reduce pollution from such waste rock dumps are discussed

Copper-arsenic decoupling in an active geothermal system: A link between pyrite and fluid composition

Science.gov (United States)

Tardani, Daniele; Reich, Martin; Deditius, Artur P.; Chryssoulis, Stephen; Sánchez-Alfaro, Pablo; Wrage, Jackie; Roberts, Malcolm P.

2017-05-01

Over the past few decades several studies have reported that pyrite hosts appreciable amounts of trace elements which commonly occur forming complex zoning patterns within a single mineral grain. These chemical zonations in pyrite have been recognized in a variety of hydrothermal ore deposit types (e.g., porphyry Cu-Mo-Au, epithermal Au deposits, iron oxide-copper-gold, Carlin-type and Archean lode Au deposits, among others), showing, in some cases, marked oscillatory alternation of metals and metalloids in pyrite growth zones (e.g., of Cu-rich, As-(Au, Ag)-depleted zones and As-(Au, Ag)-rich, Cu-depleted zones). This decoupled geochemical behavior of Cu and As has been interpreted as a result of chemical changes in ore-forming fluids, although direct evidence connecting fluctuations in hydrothermal fluid composition with metal partitioning into pyrite growth zones is still lacking. In this study, we report a comprehensive trace element database of pyrite from the Tolhuaca Geothermal System (TGS) in southern Chile, a young and active hydrothermal system where fewer pyrite growth rims and mineralization events are present and the reservoir fluid (i.e. ore-forming fluid) is accessible. We combined the high-spatial resolution and X-ray mapping capabilities of electron microprobe analysis (EMPA) with low detection limits and depth-profiling capacity of secondary-ion mass spectrometry (SIMS) in a suite of pyrite samples retrieved from a ∼1 km drill hole that crosses the argillic (20-450 m) and propylitic (650-1000 m) alteration zones of the geothermal system. We show that the concentrations of precious metals (e.g., Au, Ag), metalloids (e.g., As, Sb, Se, Te), and base and heavy metals (e.g., Cu, Co, Ni, Pb) in pyrite at the TGS are significant. Among the elements analyzed, As and Cu are the most abundant with concentrations that vary from sub-ppm levels to a few wt.% (i.e., up to ∼5 wt.% As, ∼1.5 wt.% Cu). Detailed wavelength-dispersive spectrometry (WDS) X

Isotopic and microbiological signatures of pyrite-driven denitrification in a sandy aquifer

NARCIS (Netherlands)

Zhang, Y.C.; Slomp, C.P.; Broers, H.P.; Bostick, B.; Passier, H.F.; Böttcher, M.E.; Omoregie, E.O.; Lloyd, J.R.; Polya, D.A.; Cappellen, P. van

2012-01-01

Denitrification driven by pyrite oxidation can play a major role in the removal of nitrate from groundwater systems. As yet, limited information is available on the interactions between the micro-organisms and aqueous and mineral phases in aquifers where pyrite oxidation is occurring. In this study,

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

Science.gov (United States)

Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

2016-07-08

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

Pyrite Passivation by Triethylenetetramine: An Electrochemical Study

Directory of Open Access Journals (Sweden)

Yun Liu

2013-01-01

Full Text Available The potential of triethylenetetramine (TETA to inhibit the oxidation of pyrite in H2SO4 solution had been investigated by using the open-circuit potential (OCP, cyclic voltammetry (CV, potentiodynamic polarization, and electrochemical impedance (EIS, respectively. Experimental results indicate that TETA is an efficient coating agent in preventing the oxidation of pyrite and that the inhibition efficiency is more pronounced with the increase of TETA. The data from potentiodynamic polarization show that the inhibition efficiency (η% increases from 42.08% to 80.98% with the concentration of TETA increasing from 1% to 5%. These results are consistent with the measurement of EIS (43.09% to 82.55%. The information obtained from potentiodynamic polarization also displays that the TETA is a kind of mixed type inhibitor.

Density functional theory in surface chemistry and catalysis

DEFF Research Database (Denmark)

Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

2011-01-01

Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future...

Production of ferric sulphate from pyrite by thiobacillus ferrooxidans. Application to uranium ore leaching

International Nuclear Information System (INIS)

Rouas, C.

1988-12-01

A process for uranium extraction by oxidizing solutions of ferric sulphate produced by T. ferrooxidans from pyrite is developed. A new counting method specific of T. ferrooxidans is designed. An uranium resistant wild strain, with oxidizing properties as high as the strain ATCC 19859, is isolated. Optimal conditions for ferric sulphate production from pyrite are defined (pH 1.8, density of the medium 1.2%, pyrite granulometry [fr

Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

Science.gov (United States)

Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

2017-03-01

Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

The role of "inert" surface chemistry in marine biofouling prevention.

Science.gov (United States)

Rosenhahn, Axel; Schilp, Sören; Kreuzer, Hans Jürgen; Grunze, Michael

2010-05-07

The settlement and colonization of marine organisms on submerged man-made surfaces is a major economic problem for many marine industries. The most apparent detrimental effects of biofouling are increased fuel consumption of ships, clogging of membranes and heat exchangers, disabled underwater sensors, and growth of biofoulers in aquaculture systems. The presently common-but environmentally very problematic-way to deal with marine biofouling is to incorporate biocides, which use biocidal products in the surface coatings to kill the colonizing organisms, into the surface coatings. Since the implementation of the International Maritime Organization Treaty on biocides in 2008, the use of tributyltin (TBT) is restricted and thus environmentally benign but effective surface coatings are required. In this short review, we summarize the different strategies which are pursued in academia and industry to better understand the mechanisms of biofouling and to develop strategies which can be used for industrial products. Our focus will be on chemically "inert" model surface coatings, in particular oligo- and poly(ethylene glycol) (OEG and PEG) functionalized surface films. The reasons for choosing this class of chemistry as an example are three-fold: Firstly, experiments on spore settlement on OEG and PEG coatings help to understand the mechanism of non-fouling of highly hydrated interfaces; secondly, these studies defy the common assumption that surface hydrophilicity-as measured by water contact angles-is an unambiguous and predictive tool to determine the fouling behavior on the surface; and thirdly, choosing this system is a good example for "interfacial systems chemistry": it connects the behavior of unicellular marine organisms with the antifouling properties of a hydrated surface coating with structural and electronic properties as derived from ab initio quantum mechanical calculations using the electronic wave functions of oxygen, hydrogen, and carbon. This short

Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

Energy Technology Data Exchange (ETDEWEB)

Bonten, Luc T.C., E-mail: luc.bonten@wur.nl [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands); Groenenberg, Jan E. [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands); Meesenburg, Henning [Northwest German Forest Research Station, Abt. Umweltkontrolle, Sachgebiet Intensives Umweltmonitoring, Goettingen (Germany); Vries, Wim de [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands)

2011-10-15

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: > Surface complexation models can be well applied in field studies. > Soil chemistry under a forest site is adequately modelled using generic parameters. > The model is easily extended with extra elements within the existing framework. > Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

International Nuclear Information System (INIS)

Bonten, Luc T.C.; Groenenberg, Jan E.; Meesenburg, Henning; Vries, Wim de

2011-01-01

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: → Surface complexation models can be well applied in field studies. → Soil chemistry under a forest site is adequately modelled using generic parameters. → The model is easily extended with extra elements within the existing framework. → Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

Mineralization and trace element distribution in pyrite using EMPA in exploration drill holes from Cheshmeh Zard gold district, Khorasan Razavi Province, Iran

Directory of Open Access Journals (Sweden)

Zahra Alaminia

2015-10-01

systems were recognized east of Arghash. The estimated resources are about 2 million metric tons of potential ore with an average of 1.9 g/t Au (Samadi, 2001;Ashrafpour et al., 2012. Multiple intrusive events are recognized in the region including Precambrian to post-Oligocene-Miocene igneous rocks (Alaminia et al., 2013a. This includes the Arghash diorite pluton, upper Cretaceous granitoids (minor diorite, mainly quartz monzodiorite and granodiorite, early Eocene granite and several lamprophyre and small intrusions of quartz monzodiorite porphyries. Volcanicsinclude andesite, dacite, pillow basalt and tuffs. Sedimentary rocks are conglomerate and minor limestone. Gold veins are hosted by intermediate to silicic volcanic rocks, tuffs, granite, granodiorite, and conglomerate. Veins consist of calcite and quartz. The main alteration zones mapped at the surface and underground are sericite-quartz-pyrite-calcite, withsilicified, propylitic, argillic, and carbonate zones. The mineralization associated with sericiticalteration and silicificationoccurs asveinlets and disseminated in the propylitic zone. Gangue minerals are quartz, chalcedony, calcite, adularia, illite, and kaolinite. Mineralization occurs as veinlets, breccia filling and disseminated. The veinlets are comprised of pyrite, arsenopyrite, minor chalcopyrite, sphalerite, galena, magnetite and hematite. Pyrite is the main sulfide mineral in the hypogene ore. Samples were collected with the objective of studying the pyrite in the Au (III vein systems. All samples were therefore pyrite rich. The paragenesiswas determined to show four stages of mineralization based on the following microscopic observations: 1. an initial pyrite veinlet stage with associated quartz, chlorite, epidote. Pyrite is fine to medium grained, anhedral and gold-poor. 2. a second pyritic stage (polymetallic sulfide stage contains pyrite, chalcopyrite, galena, sphalerite, quartz and chalcedony, minor adularia and arsenopyrite. 3. An As

On the genesis of pyrite-polymetallic deposits of the Rudnyi Altai

International Nuclear Information System (INIS)

Puchkov, E.V.; Najdenov, B.M.

1986-01-01

Results of lead isotope composition measurements in pyrite-polymetallic deposits of the Rudnyi Altai are presented. Porphyr dating by zirconium has shown isochronous age of 552 million years. Lead of galenites of various generations and galenite form of lead of pyrit provide similar lead-isotope values with model age of 370 million years. The isotopic-geochemical data obtained are interpreted as applied to the deposit genesis

The influence of pyrite on the solubility of minjingu and panda ...

African Journals Online (AJOL)

A laboratory study was conducted to investigate the effect of pyrite rock on the solubility of Minjingu and Panda phosphate rocks. The rocks were ground to 100 mesh (0.045 mm) after which each phosphate rock was mixed with pyrite at P:S ratios of 1:4, 1 :3, 1:2, 1:1, 2:1, and 3: 1. The mixtures were moistened and incubated ...

Evaluation of pyrite and pyrrhotite in concretes

Directory of Open Access Journals (Sweden)

A. P. Marcelino

Full Text Available ABSTRACT It is well known that aggregate characteristics can intensively interfere in concrete behavior especially when sulfides are presented in the aggregates. The lack of consensus to content limit value of these deleterious sulfur compounds in concrete structures for dams has motivated several investigations worldwide. Within this scenario, this work presents a methodology to evaluate the presence of pyrite and pyrrhotite in concretes produced with aggregates containing sulfides. For the study, rock samples from the Irapé hydroelectric power plant area in Minas Gerais (Brazil were used. This plant was built in a geological site where the rock presented sulfide levels of at least 3%. These rock samples were first ground and then used as aggregates in mortars, which were, during almost one year, subjected to three different exposed conditions: temperature of 23° ± 2°C and relative humidity of 95 to 100%; calcium hydroxide solution diluted in water kept at two different temperatures: room temperature and 50° C. The presence and amount of pyrrhotite were obtained from a leaching process of the material (aggregate or mortar in a solution of hydrochloric acid. This procedure allowed also the evaluation of the pyrite content. The results showed that the amount of pyrite has remained virtually constant over time in the three exposure situations. This finding indicates that sulfur limits in aggregates should be set according to the type of iron sulfide presented and not solely by the total amount of sulfur.

Uranium(VI) sorption onto magnetite. Increasing confidence in surface complexation models using chemically evident surface chemistry

Energy Technology Data Exchange (ETDEWEB)

Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

2017-06-01

Surface complexation models have made great efforts in describing the sorption of various radionuclides on naturally occurring mineral phases. Unfortunately, many of the published sorption parameter sets are built upon unrealistic or even wrong surface chemistry. This work describes the benefit of combining spectroscopic and batch sorption experimental data to create a reliable and consistent surface complexation parameter set.

Pyrite-enhanced methylene blue degradation in non-thermal plasma water treatment reactor

Energy Technology Data Exchange (ETDEWEB)

Benetoli, Luis Otavio de Brito, E-mail: luskywalcker@yahoo.com.br [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Cadorin, Bruno Mena; Baldissarelli, Vanessa Zanon [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Geremias, Reginaldo [Departamento de Ciencias Rurais, Universidade Federal de Santa Catarina (UFSC), Curitibanos, SC (Brazil); Goncalvez de Souza, Ivan [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Debacher, Nito Angelo, E-mail: debacher@qmc.ufsc.br [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)

2012-10-30

Highlights: Black-Right-Pointing-Pointer We use O{sub 2} as the feed gas and pyrite was added to the non-thermal plasma reactor. Black-Right-Pointing-Pointer The methylene blue removal by NTP increased in the presence of pyrite. Black-Right-Pointing-Pointer The total organic carbon content decreased substantially. Black-Right-Pointing-Pointer The acute toxicity test showed that the treated solution is not toxic. Black-Right-Pointing-Pointer The dye degradation occurs via electron impact as well as successive hydroxylation. - Abstract: In this study, methylene blue (MB) removal from an aqueous phase by electrical discharge non-thermal plasma (NTP) over water was investigated using three different feed gases: N{sub 2}, Ar, and O{sub 2}. The results showed that the dye removal rate was not strongly dependent on the feed gas when the electrical current was kept the same for all gases. The hydrogen peroxide generation in the water varied according to the feed gas (N{sub 2} < Ar < O{sub 2}). Using O{sub 2} as the feed gas, pyrite was added to the reactor in acid medium resulting in an accentuated increase in the dye removal, which suggests that pyrite acts as a Fenton-like catalyst. The total organic carbon (TOC) content of the dye solution decreased slightly as the plasma treatment time increased, but in the presence of the pyrite catalyst the TOC removal increased substantially. The acute toxicity test using Artemia sp. microcrustaceans showed that the treated solution is not toxic when Ar, O{sub 2} or O{sub 2}-pyrite is employed. Electrospray ionization mass spectrometry analysis (ESI-MS) of the treated samples indicated that the dye degradation occurs via high energy electron impact as well as successive hydroxylation in the benzene rings of the dye molecules.

Pyrite-pyrrhotite intergrowths in calcite marble from Bistriški Vintgar, Slovenia

International Nuclear Information System (INIS)

Zavašnik, J

2016-01-01

Roman marble quarry in Bistrica gorge in southern Pohorje Mt. (north-eastern Slovenia) is situated in a 20 m thick lens of layered marble, at the contact zone between granodiorite and metamorphites. Grey and yellowish non-homogenous calcite marble is heavily included by mica, quartz, feldspars, zoisite, pyrite and amphiboles. In the present research, we have studied numerous pyrite (FeS 2 ) crystals associated with yellowish-bronze non-stoichiometric pyrrhotite (Fe 1−x S), not previously reported from this locality. SEM investigation revealed unusual sequence of crystallisation: primary skeletal pyrrhotite matrix is sparsely overgrown by well-crystalline pyrite, both being overgrown by smaller, well-developed hexagonal pyrrhotite crystals of the second generation. With TEM we identify the pyrrhotite as 5T-Fe 1-x S phase, where x is about 0.1 and is equivalent to Fe 9 S 10 . The pyrite-pyrrhotite coexistence allows us a construction of fO 2 -pH diagram of stability fields, which reflects geochemical conditions at the time of marble re-crystallisation. (paper)

Pyritized ooids from the Arabian Sea basin

Digital Repository Service at National Institute of Oceanography (India)

Rao, P.S.; Rao, Ch.M.; Reddy, N.P.C.

Pyritized ooids in association with turbidites were observed in a box core collected at a depth of 3627 m from the Arabian Sea Basin. Ooids having a shallow water origin were transported to the present depth by turbidity currents or slumping...

In situ characterization of natural pyrite bioleaching using electrochemical noise technique

Science.gov (United States)

Chen, Guo-bao; Yang, Hong-ying; Li, Hai-jun

2016-02-01

An in situ characterization technique called electrochemical noise (ECN) was used to investigate the bioleaching of natural pyrite. ECN experiments were conducted in four active systems (sulfuric acid, ferric-ion, 9k culture medium, and bioleaching solutions). The ECN data were analyzed in both the time and frequency domains. Spectral noise impedance spectra obtained from power spectral density (PSD) plots for different systems were compared. A reaction mechanism was also proposed on the basis of the experimental data analysis. The bioleaching system exhibits the lowest noise resistance of 0.101 MΩ. The bioleaching of natural pyrite is considered to be a bio-battery reaction, which distinguishes it from chemical oxidation reactions in ferric-ion and culture-medium (9k) solutions. The corrosion of pyrite becomes more severe over time after the long-term testing of bioleaching.

Ferroelectrics: A pathway to switchable surface chemistry and catalysis

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab; Altman, Eric I.

2016-08-01

It has been known for more than six decades that ferroelectricity can affect a material's surface physics and chemistry thereby potentially enhancing its catalytic properties. Ferroelectrics are a class of materials with a switchable electrical polarization that can affect surface stoichiometry and electronic structure and thus adsorption energies and modes; e.g., molecular versus dissociative. Therefore, ferroelectrics may be utilized to achieve switchable surface chemistry whereby surface properties are not fixed but can be dynamically controlled by, for example, applying an external electric field or modulating the temperature. Several important examples of applications of ferroelectric and polar materials in photocatalysis and heterogeneous catalysis are discussed. In photocatalysis, the polarization direction can control band bending at water/ferroelectric and ferroelectric/semiconductor interfaces, thereby facilitating charge separation and transfer to the electrolyte and enhancing photocatalytic activity. For gas-surface interactions, available results suggest that using ferroelectrics to support catalytically active transition metals and oxides is another way to enhance catalytic activity. Finally, the possibility of incorporating ferroelectric switching into the catalytic cycle itself is described. In this scenario, a dynamic collaboration of two polarization states can be used to drive reactions that have been historically challenging to achieve on surfaces with fixed chemical properties (e.g., direct NOx decomposition and the selective partial oxidation of methane). These predictions show that dynamic modulation of the polarization can help overcome some of the fundamental limitations on catalytic activity imposed by the Sabatier principle.

Surface chemistry and bonding configuration of ultrananocrystalline diamond surfaces and their effects on nanotribological properties

International Nuclear Information System (INIS)

Sumant, A. V.; Grierson, D. S.; Carpick, R. W.; Gerbi, J. E.; Carlisle, J. A.; Auciello, O.

2007-01-01

We present a comprehensive study of surface composition and nanotribology for ultrananocrystalline diamond (UNCD) surfaces, including the influence of film nucleation on these properties. We describe a methodology to characterize the underside of the films as revealed by sacrificial etching of the underlying substrate. This enables the study of the morphology and composition resulting from the nucleation and initial growth of the films, as well as the characterization of nanotribological properties which are relevant for applications including micro-/nanoelectromechanical systems. We study the surface chemistry, bonding configuration, and nanotribological properties of both the topside and the underside of the film with synchrotron-based x-ray absorption near-edge structure spectroscopy to identify the bonding state of the carbon atoms, x-ray photoelectron spectroscopy to determine the surface chemical composition, Auger electron spectroscopy to further verify the composition and bonding configuration, and quantitative atomic force microscopy to study the nanoscale topography and nanotribological properties. The films were grown on SiO 2 after mechanically polishing the surface with detonation synthesized nanodiamond powder, followed by ultrasonication in a methanol solution containing additional nanodiamond powder. The sp 2 fraction, morphology, and chemistry of the as-etched underside are distinct from the topside, exhibiting a higher sp 2 fraction, some oxidized carbon, and a smoother morphology. The nanoscale single-asperity work of adhesion between a diamond nanotip and the as-etched UNCD underside is far lower than for a silicon-silicon interface (59.2±2 vs 826±186 mJ/m 2 , respectively). Exposure to atomic hydrogen dramatically reduces nanoscale adhesion to 10.2±0.4 mJ/m 2 , at the level of van der Waals' interactions and consistent with recent ab initio calculations. Friction is substantially reduced as well, demonstrating a direct link between the

Use of the Moessbauer effect for determining pyritic sulfur content in coal

Energy Technology Data Exchange (ETDEWEB)

Czerw, B; Sikora, T

1986-10-01

This paper discusses investigations into resonance absorption of gamma radiation. Standard equipment for measuring the Moessbauer effect in black coal consisting of a measuring head, the SM-4T spectrometer, a multichannel analyzer, the Standard electronic unit and a printer is evaluated. The MSP measuring system developed jointly by the EMAG Mine Automation Company and the Nuclear Research Institute in Swierk is described. The MSP equipment is used for measuring content of pyritic sulfur in coal. Its accuracy is satisfactory. Results of measuring pyritic and total sulfur content by means of quantitative chemical analysis and by the MSP resonance absorption method (Moessbauer effect) are compared. The mean standard deviation for pyritic sulfur is 0.14% and for total sulfur content 0.21%. 11 refs.

Pyrite: A blender plugin for visualizing molecular dynamics simulations using industry-standard rendering techniques.

Science.gov (United States)

Rajendiran, Nivedita; Durrant, Jacob D

2018-05-05

Molecular dynamics (MD) simulations provide critical insights into many biological mechanisms. Programs such as VMD, Chimera, and PyMOL can produce impressive simulation visualizations, but they lack many advanced rendering algorithms common in the film and video-game industries. In contrast, the modeling program Blender includes such algorithms but cannot import MD-simulation data. MD trajectories often require many gigabytes of memory/disk space, complicating Blender import. We present Pyrite, a Blender plugin that overcomes these limitations. Pyrite allows researchers to visualize MD simulations within Blender, with full access to Blender's cutting-edge rendering techniques. We expect Pyrite-generated images to appeal to students and non-specialists alike. A copy of the plugin is available at http://durrantlab.com/pyrite/, released under the terms of the GNU General Public License Version 3. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia

Science.gov (United States)

Ingham, Edwina S.; Cook, Nigel J.; Cliff, John; Ciobanu, Cristiana L.; Huddleston, Adam

2014-01-01

The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S = -43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into

Low temperature anaerobic bacterial diagenesis of ferrous monosulfide to pyrite

Science.gov (United States)

Donald, Ravin; Southam, Gordon

1999-07-01

In vitro enrichment cultures of dissimilatory sulfate-reducing bacteria precipitated FeS and catalyzed its transformation into FeS 2 at ambient temperature and pressure under anaerobic conditions. When compared to purely abiotic processes, the bacterially mediated transformation was shown to be more efficient in transforming FeS into FeS 2. This occurred due to the large, reactive surface area available for bacterially catalyzed diagenesis, where the biogenic FeS precursor was immobilized as a thin film (˜25 nm thick) on the μm-scale bacteria. The bacteria also contained the source(s) of sulfur for diagenesis to occur. Using a radiolabeled organic-sulfur tracer study, sulfur was released during cell autolysis and was immobilized at the bacterial cell surface forming FeS 2. The formation of FeS 2 occurred on both the inner and outer surfaces of the cell envelope and represented the first step of bacterial mineral diagenesis. Pyrite crystals, having linear dimensions of ˜1 μm, grew outward from the bacterial cell surfaces. These minerals were several orders of magnitude larger in volume than those originating abiotically.

Preparation of natural pyrite nanoparticles by high energy planetary ball milling as a nanocatalyst for heterogeneous Fenton process

Energy Technology Data Exchange (ETDEWEB)

Fathinia, Siavash [Department of Mining Engineering, Faculty of Engineering and Technology, Imam Khomeini International University, Qazvin (Iran, Islamic Republic of); Research Laboratory of Advanced Water and Wastewater Treatment Processes, Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of); Fathinia, Mehrangiz [Research Laboratory of Advanced Water and Wastewater Treatment Processes, Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of); Rahmani, Ali Akbar [Department of Mining Engineering, Faculty of Engineering and Technology, Imam Khomeini International University, Qazvin (Iran, Islamic Republic of); Khataee, Alireza, E-mail: a_khataee@tabrizu.ac.ir [Research Laboratory of Advanced Water and Wastewater Treatment Processes, Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of)

2015-02-01

Graphical abstract: - Highlights: • Pyrite nanoparticles were successfully produced by planetary ball milling process. • The physical and chemical properties of pyrite nanoparticles were fully examined. • The degradation of AO7 was notably enhanced by pyrite nanoparticles Fenton system. • The influences of basic operational parameters were investigated using CCD. - Abstract: In the present study pyrite nanoparticles were prepared by high energy mechanical ball milling utilizing a planetary ball mill. Various pyrite samples were produced by changing the milling time from 2 h to 6 h, in the constant milling speed of 320 rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) linked with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer–Emmett–Teller (BET) were performed to explain the characteristics of primary (unmilled) and milled pyrite samples. The average particle size distribution of the produced pyrite during 6 h milling was found to be between 20 nm and 100 nm. The catalytic performance of the different pyrite samples was examined in the heterogeneous Fenton process for degradation of C.I. Acid Orange 7 (AO7) solution. Results showed that the decolorization efficiency of AO7 in the presence of 6 h-milled pyrite sample was the highest. The impact of key parameters on the degradation efficiency of AO7 by pyrite nanoparticles catalyzed Fenton process was modeled using central composite design (CCD). Accordingly, the maximum removal efficiency of 96.30% was achieved at initial AO7 concentration of 16 mg/L, H{sub 2}O{sub 2} concentration of 5 mmol/L, catalyst amount of 0.5 g/L and reaction time of 25 min.

Seventh BES [Basic Energy Sciences] catalysis and surface chemistry research conference

International Nuclear Information System (INIS)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases

Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

Energy Technology Data Exchange (ETDEWEB)

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

Thallium-rich pyrite ores from the Apuan Alps, Tuscany, Italy:constraints for their origin and environmental concerns

Science.gov (United States)

D'Orazio, Massimo; Biagioni, Cristian; Dini, Andrea; Vezzoni, Simone

2017-06-01

The southern sector of the Apuan Alps (AA) massif, Tuscany, Italy, is characterized by the occurrence of a series of baryte-pyrite-iron oxide orebodies whose Tl-rich nature was recognized only recently. The geochemistry of the pyrite ore was investigated through inductively coupled plasma mass spectrometry. In addition, lead isotope data for selected pyrite ores from AA were collected. Pyrite ores are characterized by a complex geochemistry, with high concentrations of Tl (up to 1100 μg/g) coupled with high As and Sb contents; the Co/Ni ratio is always <1. Geochemical data of pyrite and marcasite ore samples from other mining districts of Tuscany have been collected in order to compare them with those from the AA. These samples usually have very low Tl content (less than 2 μg/g) and high to very high Co/Ni and As/Sb ratios. Only some samples from the Sb-Hg ore deposits showed very high Tl concentrations (up to 3900 μg/g). Another difference is related to the lead isotope composition, with pyrite ores from AA markedly less radiogenic than those from the other deposits from Tuscany. Geochemical data of pyrite ores from AA give new insights on the genesis of the baryte-pyrite-iron oxide orebodies, relating their formation to low-temperature hydrothermal systems active during early Paleozoic; in addition, these data play a fundamental role in assessing the environmental impact of these deposits.

Assessing the impact of preload on pyrite-rich sediment and groundwater quality.

Science.gov (United States)

Karikari-Yeboah, Ohene; Addai-Mensah, Jonas

2017-02-01

Pyrite-rich sediments would, invariably, undergo redox reactions which would lead to acidic aqueous environment containing solubilized toxic metal species. When such sediments are subjected to preload, a technique employed by geotechnical engineers to improve the load-bearing capacity of highly compressible formation, transient flow of pore water, accompanied by acidity transfer, would occur as a response. Despite the concomitant environmental and socio-economic significance, to date, there has been limited interdisciplinary research on the underpinning geotechnical engineering and geo-environmental science issues for pyrite-rich sediments under preload. In this study, we investigate the effect of pyrite-rich sediment pore water transfer under preload surcharge on the receiving environment and the impact on the groundwater speciation and quality. Sediment samples were obtained at close depth intervals from boreholes established within pristine areas and those subjected to the preload application. Soil and pore water samples were subjected to solid/solution speciation, moisture contents, soil pH and the Atterberg Limits' analyses using standard analytical techniques and methods. Standpipes were also installed in the boreholes for groundwater sampling and in situ monitoring of water quality parameters. It is shown that the imposition of preload surcharge over pyritic sediment created a reducing environment rich in SO 4 2- , iron oxide minerals and organic matter. This reducing environment fostered organic carbon catabolism to generate excess pyrite and bicarbonate alkalinity, which would invariably impact adversely on soil quality and plant growth. These were accompanied by increase in pH, dissolved Al, Ca, Mg and K species beneath the surcharge.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

Science.gov (United States)

Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

2018-05-01

The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

Science.gov (United States)

Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

2014-06-01

Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and

Influence of surface chemistry on inkjet printed carbon nanotube films

International Nuclear Information System (INIS)

Hopkins, Alan R.; Straw, David C.; Spurrell, Kathryn C.

2011-01-01

Carbon nanotube ink chemistry and the proper formulation are crucial for direct-write printing of nanotubes. Moreover, the correct surface chemistry of the self-assembled monolayers that assist the direct deposition of carbon nanotubes onto the substrate is equally important to preserve orientation of the printed carbon nanotubes. We report that the successful formulation of two single walled carbon nanotube (SWNT) inks yields a consistent, homogenous printing pattern possessing the requisite viscosities needed for flow through the microcapillary nozzles of the inkjet printer with fairly modest drying times. The addition of an aqueous sodium silicate allows for a reliable method for forming a uniform carbon nanotube network deposited directly onto unfunctionalized surfaces such as glass or quartz via inkjet deposition. Furthermore, this sodium silicate ingredient helps preserve applied orientation to the printed SWNT solution. Sheet resistivity of this carbon nanotube ink formula printed on quartz decreases as a function of passes and is independent of the substrate. SWNTs were successfully patterned on Au. This amine-based surface chemistry dramatically helps improve the isolation stabilization of the printed SWNTs as seen in the atomic force microscopy (AFM) image. Lastly, using our optimized SWNT ink formula and waveform parameters in the Fuji materials printer, we are able to directly write/print SWNTs into 2D patterns. Dried ink pattern expose and help orient roped carbon nanotubes that are suspended in ordered arrays across the cracks.

The impact of surface chemistry on the performance of localized solar-driven evaporation system.

Science.gov (United States)

Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

2015-09-04

This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications

Energy Technology Data Exchange (ETDEWEB)

Vaithilingam, Jayasheelan, E-mail: Jayasheelan.Vaithilingam@nottingham.ac.uk [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Prina, Elisabetta [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Goodridge, Ruth D.; Hague, Richard J.M. [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Edmondson, Steve [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Rose, Felicity R.A.J. [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Christie, Steven D.R. [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom)

2016-10-01

Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM–AF surface was observed to be porous with an average surface roughness (Ra) of 17.6 ± 3.7 μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. - Highlights: • Surface chemistry of selective laser melted (SLM) Ti6Al4V parts was compared with conventionally forged Ti6Al4V parts. • The surface elemental compositions of the SLM as-fabricated surfaces were significantly different to the forged surface. • Surface oxide-layer of the SLM as-fabricated was thicker than the polished SLM surfaces and the forged Ti6Al4V surfaces.

Recyclable surfaces for amine conjugation chemistry via redox reaction

Energy Technology Data Exchange (ETDEWEB)

Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

2017-02-15

In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

Science.gov (United States)

Dukes, C.; Loeffler, M.J.; Baragiola, R.; Christoffersen, R.; Keller, J.

2009-01-01

Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

Evaluation of stream chemistry trends in US Geological Survey reference watersheds, 1970-2010.

Science.gov (United States)

Mast, M Alisa

2013-11-01

The Hydrologic Benchmark Network (HBN) is a long-term monitoring program established by the US Geological Survey in the 1960s to track changes in the streamflow and stream chemistry in undeveloped watersheds across the USA. Trends in stream chemistry were tested at 15 HBN stations over two periods (1970-2010 and 1990-2010) using the parametric Load Estimator (LOADEST) model and the nonparametric seasonal Kendall test. Trends in annual streamflow and precipitation chemistry also were tested to help identify likely drivers of changes in stream chemistry. At stations in the northeastern USA, there were significant declines in stream sulfate, which were consistent with declines in sulfate deposition resulting from the reductions in SO₂ emissions mandated under the Clean Air Act Amendments. Sulfate declines in stream water were smaller than declines in deposition suggesting sulfate may be accumulating in watershed soils and thereby delaying the stream response to improvements in deposition. Trends in stream chemistry at stations in other part of the country generally were attributed to climate variability or land disturbance. Despite declines in sulfate deposition, increasing stream sulfate was observed at several stations and appeared to be linked to periods of drought or declining streamflow. Falling water tables might have enhanced oxidation of organic matter in wetlands or pyrite in mineralized bedrock thereby increasing sulfate export in surface water. Increasing sulfate and nitrate at a station in the western USA were attributed to release of soluble salts and nutrients from soils following a large wildfire in the watershed.

Evaluation of stream chemistry trends in US Geological Survey reference watersheds, 1970-2010

Science.gov (United States)

Mast, M. Alisa

2013-01-01

The Hydrologic Benchmark Network (HBN) is a long-term monitoring program established by the US Geological Survey in the 1960s to track changes in the streamflow and stream chemistry in undeveloped watersheds across the USA. Trends in stream chemistry were tested at 15 HBN stations over two periods (1970–2010 and 1990–2010) using the parametric Load Estimator (LOADEST) model and the nonparametric seasonal Kendall test. Trends in annual streamflow and precipitation chemistry also were tested to help identify likely drivers of changes in stream chemistry. At stations in the northeastern USA, there were significant declines in stream sulfate, which were consistent with declines in sulfate deposition resulting from the reductions in SO2 emissions mandated under the Clean Air Act Amendments. Sulfate declines in stream water were smaller than declines in deposition suggesting sulfate may be accumulating in watershed soils and thereby delaying the stream response to improvements in deposition. Trends in stream chemistry at stations in other part of the country generally were attributed to climate variability or land disturbance. Despite declines in sulfate deposition, increasing stream sulfate was observed at several stations and appeared to be linked to periods of drought or declining streamflow. Falling water tables might have enhanced oxidation of organic matter in wetlands or pyrite in mineralized bedrock thereby increasing sulfate export in surface water. Increasing sulfate and nitrate at a station in the western USA were attributed to release of soluble salts and nutrients from soils following a large wildfire in the watershed.

Effects of wood fiber surface chemistry on strength of wood–plastic composites

Energy Technology Data Exchange (ETDEWEB)

Migneault, Sébastien, E-mail: sebastien.migneault@uqat.ca [University of Quebec in Abitibi-Temiscamingue (UQAT), 445 boulevard de l’Université, Rouyn-Noranda, Québec J9X 5E4 (Canada); Koubaa, Ahmed, E-mail: ahmed.koubaa@uqat.ca [UQAT (Canada); Perré, Patrick, E-mail: patrick.perre@ecp.fr [École centrale de Paris, Grande Voie des Vignes, F-92 295 Chatenay-Malabry Cedex (France); Riedl, Bernard, E-mail: Bernard.Riedl@sbf.ulaval.ca [Université Laval, 2425 rue de la Terrasse, Québec City, Québec G1V 0A6 (Canada)

2015-07-15

Highlights: • Infrared spectroscopy and X-ray photoelectron spectroscopy analyses showed variations of surface chemical characteristics according to fiber origin. • Surface chemical characteristics of fibers could partly explain the differences in mechanical properties of the wood–plastic composites. • Fibers with carbohydrate rich surface led to stronger wood–plastic composites because the coupling between the matrix and fibers using coupling agent is achieved with polar sites mostly available on carbohydrates. • Conversely, lignin or extractives rich surface do not have oxidized functions for the esterification reaction with coupling agent and thus led to wood–plastic composites with lower mechanical properties. • Other factors such as mechanical interlocking and fiber morphology interfere with the effects of fiber surface chemistry. - Abstract: Because wood–plastic composites (WPC) strength relies on fiber-matrix interaction at fiber surface, it is likely that fiber surface chemistry plays an important role in WPC strength development. The objective of the present study is to investigate the relationships between fiber surface chemical characteristics and WPC mechanical properties. Different fibers were selected and characterized for surface chemical characteristics using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR). WPC samples were manufactured at 40% fiber content and with six different fibers. High density polyethylene was used as matrix and maleated polyethylene (MAPE) was used as compatibility agent. WPC samples were tested for mechanical properties and fiber-matrix interface was observed with scanning electron microscope. It was found WPC strength decreases as the amount of unoxidized carbon (assigned to lignin and extractives) measured with XPS on fiber surface increases. In the opposite case, WPC strength increases with increasing level of oxidized carbon (assigned to carbohydrates) on fiber surface. The same

Effects of wood fiber surface chemistry on strength of wood–plastic composites

International Nuclear Information System (INIS)

Migneault, Sébastien; Koubaa, Ahmed; Perré, Patrick; Riedl, Bernard

2015-01-01

Highlights: • Infrared spectroscopy and X-ray photoelectron spectroscopy analyses showed variations of surface chemical characteristics according to fiber origin. • Surface chemical characteristics of fibers could partly explain the differences in mechanical properties of the wood–plastic composites. • Fibers with carbohydrate rich surface led to stronger wood–plastic composites because the coupling between the matrix and fibers using coupling agent is achieved with polar sites mostly available on carbohydrates. • Conversely, lignin or extractives rich surface do not have oxidized functions for the esterification reaction with coupling agent and thus led to wood–plastic composites with lower mechanical properties. • Other factors such as mechanical interlocking and fiber morphology interfere with the effects of fiber surface chemistry. - Abstract: Because wood–plastic composites (WPC) strength relies on fiber-matrix interaction at fiber surface, it is likely that fiber surface chemistry plays an important role in WPC strength development. The objective of the present study is to investigate the relationships between fiber surface chemical characteristics and WPC mechanical properties. Different fibers were selected and characterized for surface chemical characteristics using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR). WPC samples were manufactured at 40% fiber content and with six different fibers. High density polyethylene was used as matrix and maleated polyethylene (MAPE) was used as compatibility agent. WPC samples were tested for mechanical properties and fiber-matrix interface was observed with scanning electron microscope. It was found WPC strength decreases as the amount of unoxidized carbon (assigned to lignin and extractives) measured with XPS on fiber surface increases. In the opposite case, WPC strength increases with increasing level of oxidized carbon (assigned to carbohydrates) on fiber surface. The same

Acid mine drainage in the Iberian Pyrite Belt: 1. Hydrochemical characteristics and pollutant load of the Tinto and Odiel rivers.

Science.gov (United States)

Nieto, Jose M; Sarmiento, Aguasanta M; Canovas, Carlos R; Olias, Manuel; Ayora, Carlos

2013-11-01

Acid mine drainage in the Iberian Pyrite Belt is probably the worst case in the world of surface water pollution associated with mining of sulphide mineral deposits. The Iberian Pyrite Belt is located in SW Iberian Peninsula, and it has been mined during the last 4,500 years. The central and eastern part of the Iberian Pyrite Belt is drained by the Tinto and Odiel rivers, which receive most of the acidic leachates from the mining areas. As a result, the main channels of the Tinto and Odiel rivers are very rich in metals and highly acidic until reaching the Atlantic Ocean. A significant amount of the pollutant load transported by these two rivers is delivered during the rainy season, as is usual in rivers of Mediterranean climate regions. Therefore, in order to have an accurate estimation of the pollutant loads transported by the Tinto and Odiel rivers, a systematic sampling on a weekly basis and a high temporal resolution sampling of floods events were both performed. Results obtained show that metal fluxes are strongly dependent on the study period, highlighting the importance of inter-annual studies involving dry and wet years.

A surface-chemistry study of barium ferrite nanoplates with DBSa-modified surfaces

Energy Technology Data Exchange (ETDEWEB)

Lisjak, Darja, E-mail: darja.lisjak@ijs.si [Jožef Stefan Institute, Ljubljana (Slovenia); Ovtar, Simona; Kovač, Janez [Jožef Stefan Institute, Ljubljana (Slovenia); Gregoratti, Luca; Aleman, Belen; Amati, Matteo [Elettra – Sincrotrone Trieste S.C.p.A. di interesse nazionale, Trieste (Italy); Fanetti, Mattia [University of Nova Gorica, Nova Gorica (Slovenia); Istituto Officina dei Materiali CNR, Area Science Park, Trieste (Italy); Makovec, Darko [Jožef Stefan Institute, Ljubljana (Slovenia)

2014-06-01

Barium ferrite (BaFe{sub 12}O{sub 19}) is a ferrimagnetic oxide with a high magnetocrystalline anisotropy that can be exploited in magnetically aligned ceramics or films for self-biased magnetic applications. Magnetic alignment of the films can be achieved by the directed assembly of barium ferrite nanoplates. In this investigation the nanoplates were synthesized hydrothermally and suspended in 1-butanol using dodecylbenzene sulphonic acid (DBSa) as a surfactant. They were then deposited in an electric or magnetic field on flat substrates and exhibited a significant preferential alignment in the plane of the substrate, allowing a differentiation between the analysis of their basal and side planes using scanning photoelectron microscopy with a lateral resolution down to 100 nm. The surface chemistry of the nanoplates was additionally studied with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. For a comparison, bare barium ferrite nanoplates were also analyzed after decomposing the DBSa at 460 °C. The deviation of the surface chemistry from the stoichiometric composition was observed and the adsorption of the DBSa molecules on the nanoplates was confirmed with all three methods. Different types of bonding (physi- or chemisorption) were possible and considered with respect to the assembly of the barium ferrite nanoplates into anisotropic magnetic films.

Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

Science.gov (United States)

Pegalajar-Jurado, Adoracion; Easton, Christopher D; Crawford, Russell J; McArthur, Sally L

2015-03-26

Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

Ion-enhanced gas-surface chemistry: The influence of the mass of the incident ion

International Nuclear Information System (INIS)

Gerlach-Meyer, U.; Coburn, J.W.; Kay, E.

1981-01-01

There are many examples of situations in which a gas-surface reaction rate is increased when the surface is simultaneously subjected to energetic particle bombardment. There are several possible mechanisms which could be involved in this radiation-enhanced gas-surface chemistry. In this study, the reaction rate of silicon, as determined from the etch yield, is measured during irradiation of the Si surface with 1 keV He + , Ne + , and Ar + ions while the surface is simultaneously subjected to fluxes of XeF 2 or Cl 2 molecules. Etch yields as high as 25 Si atoms/ion are observed for XeF 2 and Ar + on Si. A discussion is presented of the extent to which the results clarify the mechanisms responsible for ion-enhanced gas-surface chemistry. (orig.)

Source and Enrichment of Toxic Elements in Coal Seams around Mafic Intrusions: Constraints from Pyrites in the Yuandian Coal Mine in Anhui, Eastern China

Directory of Open Access Journals (Sweden)

Yanfei An

2018-04-01

Full Text Available Pyrite, a mineral that can cause potential environmental issues in coal mining, is commonly found in coal seams around intrusions. In this paper, pyrites from the Yuandian Coal Mine (Huaibei Coalfield, Anhui, Eastern China were studied using SEM, Raman and LA-ICP-MS. The pyrite morphologic and geochemical data suggest that (1 four pyrite generations are present (framboidal sedimentary pyrites (Py I in the original coal, coarse-grained magmatic pyrites (Py II in the intruding diabase, fine-grained metamorphic pyrites (Py III in the intrusive contact aureole, and spheroid/vein hydrothermal pyrites (Py IV in the cokeite; and (2 concentrations of cobalt, nickel, arsenic, selenium, lead and copper in the metamorphic pyrites are much higher than the other pyrite generations. We propose that mafic magmatism is the main contributor of the toxic elements to the intrusion-related cokeite at Yuandian.

Ferroelectric based catalysis: Switchable surface chemistry

Science.gov (United States)

Kakekhani, Arvin; Ismail-Beigi, Sohrab

2015-03-01

We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

Paleoredoc and pyritization of soft-bodied fossils in the Ordovician Frankfort Shale of New York

DEFF Research Database (Denmark)

Farrell, Una C.; Briggs, Derek E. G.; Hammarlund, Emma U.

2013-01-01

Multiple beds in the Frankfort Shale (Upper Ordovician, New York State), including the original "Beecher's Trilobite Bed," yield fossils with pyritized soft-tissues. A bed-by-bed geochemical and sedimentological analysis was carried out to test previous models of soft-tissue pyritization...

Element migration of pyrites during ductile deformation of the Yuleken porphyry Cu deposit (NW-China)

Science.gov (United States)

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Li, Jilei; Cao, Mingjian; Xiang, Peng; Wu, Chu; You, Jun

2017-01-01

The strongly deformed Yuleken porphyry Cu deposit (YPCD) occurs in the Kalaxiangar porphyry Cu belt (KPCB), which occupies the central area of the Central Asian Orogenic Belt (CAOB) between the Sawu’er island arc and the Altay Terrane in northern Xinjiang. The YPCD is one of several typical subduction-related deposits in the KPCB, which has undergone syn-collisional and post-collisional metallogenic overprinting. The YPCD is characterized by three pyrite-forming stages, namely a hydrothermal stage A (Py I), a syn-ductile deformation stage B (Py II) characterized by Cu-Au enrichment, and a fracture-filling stage C (Py III). In this study, we conducted systematic petrographic and geochemical studies of pyrites and coexist biotite, which formed during different stages, in order to constrain the physicochemical conditions of the ore formation. Euhedral, fragmented Py I has low Pb and high Te and Se concentration and Ni contents are low with Co/Ni ratios mostly between 1 and 10 (average 9.00). Py I is further characterized by enrichments of Bi, As, Ni, Cu, Te and Se in the core relative to the rim domains. Anhedral round Py II has moderate Co and Ni contents with high Co/Ni ratios >10 (average 95.2), and average contents of 46.5 ppm Pb and 5.80 ppm Te. Py II is further characterized by decreasing Bi, Cu, Pb, Zn, Ag, Te, Mo, Sb and Au contents from the rim to the core domains. Annealed Py III has the lowest Co content of all pyrite types with Co/Ni ratios mostly <0.1 (average 1.33). Furthermore, Py III has average contents of 3.31 ppm Pb, 1.33 ppm Te and 94.6 ppm Se. In addition, Fe does not correlate with Cu and S in the Py I and Py III, while Py II displays a negative correlation between Fe and Cu as well as a positive correlation between Fe and S. Therefore, pyrites which formed during different tectonic regimes also have different chemical compositions. Biotite geothermometer and oxygen fugacity estimates display increasing temperatures and oxygen

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

Directory of Open Access Journals (Sweden)

Sheikh Uddin

2013-05-01

Full Text Available The strong affinity of carbon nanotubes (CNTs to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB from multi-walled carbon nanotubes (MWNTs. The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH 7. In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs.

Morphology control of anatase TiO2 for well-defined surface chemistry

KAUST Repository

Jeantelot, Gabriel; Ould-Chikh, Samy; Sofack-Kreutzer, Julien; Abou-Hamad, Edy; Anjum, Dalaver H.; Lopatin, Sergei; Harb, Moussab; Cavallo, Luigi; Basset, Jean-Marie

2018-01-01

A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed.

Morphology control of anatase TiO2 for well-defined surface chemistry

KAUST Repository

Jeantelot, Gabriel

2018-05-16

A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed.

Bacterial leaching of pyritic gold ores

Energy Technology Data Exchange (ETDEWEB)

Gagliardi, F.M.; Cashion, J.D.; Brown, L.J. [Monash Univ., Clayton, VIC (Australia). Dept. of Physics; Jay, W.H. [Monash Univ., Clayton, VIC (Australia). Chemical Engineering Department

1996-12-31

The bacterial oxidation process is well known in nature but has only recently come under investigation as a viable and relatively clean method of gold recovery from ores. However there is currently little information about the process at an atomic scale. It is known that the bacterial attack progresses preferentially along grain boundaries which is precisely where the gold has been deposited from aqueous infiltration. Samples have been obtained from the Wiluna mine in Western Australia consisting of the original ore, 2 pre-treatments, and from six successive bacterial reactors. {sup 57}Fe Moessbauer spectra taken at room temperature show only two quadrupole split doublets which can be ascribed to pyrite, FeS{sub 2}, and arsenopyrite, FeAsS. However, the presence of any superparamagnetic oxide or oxyhydroxide species would be expected to give a spectrum very similar to that of pyrite and would be undetectable in small quantities. At a temperature of 5K, a broad magnetically split sextet is observable with a mean hyperfine field of approximately 50T. This field is characteristic of magnetically ordered ferric iron surrounded by an octahedron of oxygens. The intensity and characteristics of this subspectrum alters through the series and interpretations will be given on the oxidation products of the bacterial leaching

Bacterial leaching of pyritic gold ores

International Nuclear Information System (INIS)

Gagliardi, F.M.; Cashion, J.D.; Brown, L.J.; Jay, W.H.

1996-01-01

The bacterial oxidation process is well known in nature but has only recently come under investigation as a viable and relatively clean method of gold recovery from ores. However there is currently little information about the process at an atomic scale. It is known that the bacterial attack progresses preferentially along grain boundaries which is precisely where the gold has been deposited from aqueous infiltration. Samples have been obtained from the Wiluna mine in Western Australia consisting of the original ore, 2 pre-treatments, and from six successive bacterial reactors. 57 Fe Moessbauer spectra taken at room temperature show only two quadrupole split doublets which can be ascribed to pyrite, FeS 2 , and arsenopyrite, FeAsS. However, the presence of any superparamagnetic oxide or oxyhydroxide species would be expected to give a spectrum very similar to that of pyrite and would be undetectable in small quantities. At a temperature of 5K, a broad magnetically split sextet is observable with a mean hyperfine field of approximately 50T. This field is characteristic of magnetically ordered ferric iron surrounded by an octahedron of oxygens. The intensity and characteristics of this subspectrum alters through the series and interpretations will be given on the oxidation products of the bacterial leaching

Chemostratigraphy and trace element pattern of authigenic pyrite in a Frasnian-Fammenian transition section (Büdesheimer bach, Germany)

Science.gov (United States)

Pujol, F.; Berner, Z.; Neumann, T.; Stüben, D.

2003-04-01

Trace element contents in authigenic pyrite were investigated in relationship to the geochemistry of host rocks in a 160 m deep drilling at Büdesheimer Bach (Prümer Mulde, Germany), in order to put constrains on possible changes in depositional conditions and seawater composition related to the Kellwasser events (Frasnian/Fammenian transition). The approach is based on the observation that the trace element pattern of authigenic pyrite is controlled by genetic conditions (Stüben et al., 2002) and that the content of elements with generally high degree of pyritization (DTMP, degree of trace metal pyritization, like As, Mo, Co, Ni, etc.) depends on their availability at the site of pyrite formation (e.g. Huerta-Diaz and Morse, 1992). The distribution of trace elements in the bulk rock essentially reflects mineralogical composition and redox conditions which are mainly controlled by the flux of organic matter entering the sediment. The lower and upper Kellwasser horizons are marked by an increase in carbonate and organic carbon content (up to 2%), coupled with an increase in the degree of pyritization of Fe (DOP: 0.4-0.8), indicating a change from normal marine to suboxic/anoxic conditions. A simultaneous drop in the Ba content of the host lithology, which usually is used as a proxy for paleoproductivity, can be explained by the removal of Ba dissolved in pore water under anoxic conditions (McManus et al., 1998). While low in the host rock, the Ba content of authigenic pyrite is high in these horizons, suggesting that pyrite may preserve the initial composition of pore water even for some elements with generally low DTMP, like Ba. Consequently, Ba content in pyrite may serve as indicator for productivity even when the Ba content of sediment can not be used due to its poor preservation. During these anoxic episodes also a significant increase in the content of As, U, V was registered in pyrite. Opposite to these, others like Ni, Co, Ag show a decrease in their

Chemical and sulphur isotope compositions of pyrite in the ...

Indian Academy of Sciences (India)

sulphide mineralization and their chemical evo- lution in relative .... properties and chemical compositions. Electron ..... from the sulphide lode provide clues to the chang- ing fluid ..... Raymond O L 1996 Pyrite composition and ore geneis in.

Surface topography and chemistry shape cellular behavior on wide band-gap semiconductors.

Science.gov (United States)

Bain, Lauren E; Collazo, Ramon; Hsu, Shu-Han; Latham, Nicole Pfiester; Manfra, Michael J; Ivanisevic, Albena

2014-06-01

The chemical stability and electrical properties of gallium nitride make it a promising material for the development of biocompatible electronics, a range of devices including biosensors as well as interfaces for probing and controlling cellular growth and signaling. To improve the interface formed between the probe material and the cell or biosystem, surface topography and chemistry can be applied to modify the ways in which the device interacts with its environment. PC12 cells are cultured on as-grown planar, unidirectionally polished, etched nanoporous and nanowire GaN surfaces with and without a physisorbed peptide sequence that promotes cell adhesion. While cells demonstrate preferential adhesion to roughened surfaces over as-grown flat surfaces, the topography of that roughness also influences the morphology of cellular adhesion and differentiation in neurotypic cells. Addition of the peptide sequence generally contributes further to cellular adhesion and promotes development of stereotypic long, thin neurite outgrowths over alternate morphologies. The dependence of cell behavior on both the topographic morphology and surface chemistry is thus demonstrated, providing further evidence for the importance of surface modification for modulating bio-inorganic interfaces. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

Science.gov (United States)

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Engineering of Surface Chemistry for Enhanced Sensitivity in Nanoporous Interferometric Sensing Platforms.

Science.gov (United States)

Law, Cheryl Suwen; Sylvia, Georgina M; Nemati, Madieh; Yu, Jingxian; Losic, Dusan; Abell, Andrew D; Santos, Abel

2017-03-15

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au 3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules from approaches i and ii, respectively, were combined into a third sensing strategy whereby the NAA platforms are functionalized on both the top and inner surfaces concurrently. Engineering of the surface according to this approach resulted in an additive enhancement in sensitivity of up to 5-fold compared to previously reported systems. This study advances the rational engineering of surface chemistry for interferometric sensing on nanoporous platforms with potential applications for real-time monitoring of multiple analytes in dynamic environments.

Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

Science.gov (United States)

Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

2016-10-01

Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Trace element mapping of pyrite from Archean gold deposits – A comparison between PIXE and EPMA

Energy Technology Data Exchange (ETDEWEB)

Agangi, A., E-mail: aagangi@uj.ac.za [University of Johannesburg, Department of Geology, Auckland Park 2006 (South Africa); Przybyłowicz, W., E-mail: przybylowicz@tlabs.ac.za [Materials Research Department, iThemba LABS, National Research Foundation, Somerset West 7129 (South Africa); AGH University of Science and Technology, Faculty of Physics & Applied Computer Science, Al. A. Mickiewicza 30, 30-059 Krakow (Poland); Hofmann, A., E-mail: ahofmann@uj.ac.za [University of Johannesburg, Department of Geology, Auckland Park 2006 (South Africa)

2015-04-01

Chemical zoning of pyrites can record the evolution of mineralising fluids at widely varying P–T conditions ranging from diagenesis to medium-grade metamorphism. If preserved, zoning can reveal growth textures, brecciation and veining, resorption and recrystallisation events, thus shedding light on the processes that contributed to ore formation. Chemical zoning of sulfides is invisible in optical microscopy, but can be studied by chemical etching, high-contrast back-scattering electron images, and elemental imaging. In this study we compared micro-PIXE and WDS-EPMA elemental maps on the chemically zoned pyrites in mineralised vein-bearing samples from the Sheba and Fairview gold mines in the Barberton Greenstone Belt, South Africa. Elemental images show complex distribution of trace elements, suggesting multiple events of pyrite crystallisation and gold deposition. EPMA maps show fine-scale variations reflecting growth and recrystallisation textures marked, in particular, by variations of As, Ni, and Co. In PIXE maps, gold occurs both as finely-distributed and discrete inclusions, suggesting incorporation in the pyrite structure as solid solution, and deposition as electrum inclusions, respectively. Micro-PIXE and EPMA provide complementary information, forming together a powerful tool to obtain information on chemical zoning of pyrites in ore deposits.

Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

Science.gov (United States)

Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

2013-05-21

Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

Science.gov (United States)

Barry, Seán T; Teplyakov, Andrew V; Zaera, Francisco

2018-03-20

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be

Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

Science.gov (United States)

Yonata, B.; Nasrudin, H.

2018-01-01

A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

Science.gov (United States)

Zhang, Peng; Yuan, Songhu

2017-12-01

Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe

Sulfur-oxidizing bacteria dominate the microbial diversity shift during the pyrite and low-grade pyrolusite bioleaching process.

Science.gov (United States)

Han, Yifan; Ma, Xiaomei; Zhao, Wei; Chang, Yunkang; Zhang, Xiaoxia; Wang, Xingbiao; Wang, Jingjing; Huang, Zhiyong

2013-10-01

The microbial ecology of the pyrite-pyrolusite bioleaching system and its interaction with ore has not been well-described. A 16S rRNA gene clone library was created to evaluate changes in the microbial community at different stages of the pyrite-pyrolusite bioleaching process in a shaken flask. The results revealed that the bacterial community was disturbed after 5 days of the reaction. Phylogenetic analysis of 16S rRNA sequences demonstrated that the predominant microorganisms were members of a genus of sulfur-oxidizing bacteria, Thiomonas sp., that subsequently remained dominant during the bioleaching process. Compared with iron-oxidizing bacteria, sulfur-oxidizing bacteria were more favorable to the pyrite-pyrolusite bioleaching system. Decreased pH due to microbial acid production was an important condition for bioleaching efficiency. Iron-oxidizing bacteria competed for pyrite reduction power with Mn(IV) in pyrolusite under specific conditions. These results extend our knowledge of microbial dynamics during pyrite-pyrolusite bioleaching, which is a key issue to improve commercial applications. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Investigations of nitrogen oxide plasmas: Fundamental chemistry and surface reactivity and monitoring student perceptions in a general chemistry recitation

Science.gov (United States)

Blechle, Joshua M.

Part I of this dissertation focuses on investigations of nitrogen oxide plasma systems. With increasing concerns over the environmental presence of NxOy species, there is growing interest in utilizing plasma-assisted conversion techniques. Advances, however, have been limited because of the lack of knowledge regarding the fundamental chemistry of these plasma systems. Understanding the kinetics and thermodynamics of processes in these systems is vital to realizing their potential in a range of applications. Unraveling the complex chemical nature of these systems, however, presents numerous challenges. As such, this work serves as a foundational step in the diagnostics and assessment of these NxOy plasmas. The partitioning of energy within the plasma system is essential to unraveling these complications as it provides insight into both gas and surface reactivity. To obtain this information, techniques such as optical emission spectroscopy (OES), broadband absorption spectroscopy (BAS), and laser induced fluorescence (LIF) were utilized to determine species energetics (vibrational, rotational, translational temperatures). These temperature data provide mechanistic insight and establish the relationships between system parameters and energetic outcomes. Additionally, these data are also correlated to surface reactivity data collected with the Imaging of Radicals Interacting with Surfaces (IRIS) technique. IRIS data demonstrate the relationship between internal temperatures of radicals and their observed surface scatter coefficients (S), the latter of which is directly related to surface reactivity (R) [R = 1-S]. Furthermore, time-resolved (TR) spectroscopic techniques, specifically TR-OES, revealed kinetic trends in NO and N2 formation from a range of precursors (NO, N2O, N2/O2). By examining the rate constants associated with the generation and destruction of various plasma species we can investigate possible mechanistic implications. All told, such data provides

Pyritization processes and greigite formation in the advancing sulfidization front in the Upper Pleistocene sediments of the Black Sea

DEFF Research Database (Denmark)

Neretin, LN; Bottcher, ME; Jørgensen, BB

2004-01-01

Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above...... and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeSn (n = 1.10-1.29), including greigite. Elemental sulfur...... and polysulfides, formed from H,S by a reductive dissolution of Fe(Ill)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a "direct" pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate...

40Ar/39Ar dating of pyrite

International Nuclear Information System (INIS)

York, D.; Masliwec, A.; Kuybida, P.; Hanes, J.A.; Hall, C.M.; Kenyon, W.J.; Spooner, E.T.C.; Scott, S.D.

1982-01-01

To overcome difficulties encountered in the customary method of determining the age of mineralization of sulphide ore deposits by analysing silicate material, the sulphide minerals themselves have been examined to see if they contained sufficient potassium and argon for 40 Ar/ 39 Ar age determination. Initial results indicate that this is the case for pyrite from the Geco ore body in northwestern Ontario, Canada. (U.K.)

Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

Directory of Open Access Journals (Sweden)

Milena Becelic-Tomin

2014-01-01

Full Text Available Pyrite ash (PA is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4 degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH=2.5; [PA]0=0.2 g L−1; [H2O2]0=5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.

Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

Science.gov (United States)

Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

2015-01-01

The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

DEFF Research Database (Denmark)

Binning, Philip John; Postma, Diederik Jan; Russel, T.F.

2007-01-01

Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed at...... parameters; for example, the time to approach steady state depends exponentially on the distance between the soil surface and the subsurface reactive zone. Copyright 2007 by the American Geophysical Union....... at depth in the unsaturated zone, a pressure gradient is created between the reactive zone and the ground surface, causing a substantial advective air flow into the subsurface. To determine the balance between advective and diffusive transport, a one-dimensional multicomponent unsaturated zone gas...

Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry

Science.gov (United States)

2016-01-01

Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of ‘polar ice’ mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm ‘carbonyl’ absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes. PMID:28083090

Effect of Surface Chemistry on the Fluorescence of Detonation Nanodiamonds.

Science.gov (United States)

Reineck, Philipp; Lau, Desmond W M; Wilson, Emma R; Fox, Kate; Field, Matthew R; Deeleepojananan, Cholaphan; Mochalin, Vadym N; Gibson, Brant C

2017-11-28

Detonation nanodiamonds (DNDs) have unique physical and chemical properties that make them invaluable in many applications. However, DNDs are generally assumed to show weak fluorescence, if any, unless chemically modified with organic molecules. We demonstrate that detonation nanodiamonds exhibit significant and excitation-wavelength-dependent fluorescence from the visible to the near-infrared spectral region above 800 nm, even without the engraftment of organic molecules to their surfaces. We show that this fluorescence depends on the surface functionality of the DND particles. The investigated functionalized DNDs, produced from the same purified DND as well as the as-received polyfunctional starting material, are hydrogen, hydroxyl, carboxyl, ethylenediamine, and octadecylamine-terminated. All DNDs are investigated in solution and on a silicon wafer substrate and compared to fluorescent high-pressure high-temperature nanodiamonds. The brightest fluorescence is observed from octadecylamine-functionalized particles and is more than 100 times brighter than the least fluorescent particles, carboxylated DNDs. The majority of photons emitted by all particle types likely originates from non-diamond carbon. However, we locally find bright and photostable fluorescence from nitrogen-vacancy centers in diamond in hydrogenated, hydroxylated, and carboxylated detonation nanodiamonds. Our results contribute to understanding the effects of surface chemistry on the fluorescence of DNDs and enable the exploration of the fluorescent properties of DNDs for applications in theranostics as nontoxic fluorescent labels, sensors, nanoscale tracers, and many others where chemically stable and brightly fluorescent nanoparticles with tailorable surface chemistry are needed.

Ethers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry

KAUST Repository

Pecher, Lisa

2017-09-15

Using computational chemistry, we show that the adsorption of ether molecules on Si(001) under ultra-high vacuum conditions can be understood with textbook organic chemistry. The two-step reaction mechanism of (1) dative bond formation between the ether oxygen and a Lewis acidic surface atom and (2) a nucleophilic attack of a nearby Lewis basic surface atom is analysed in detail and found to mirror the acid-catalysed ether cleavage in solution. The O-Si dative bond is found to be the strongest of its kind and reactivity from this state defies the Bell-Evans-Polanyi principle. Electron rearrangement during the C-O bond cleavage is visualized using a newly developed bonding analysis method, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular chemistry SN2 reactions. Our findings thus illustrate how the fields of surface science and molecular chemistry can mutually benefit and unexpected insight can be gained.

Ethers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry

KAUST Repository

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf Ewald

2017-01-01

Using computational chemistry, we show that the adsorption of ether molecules on Si(001) under ultra-high vacuum conditions can be understood with textbook organic chemistry. The two-step reaction mechanism of (1) dative bond formation between the ether oxygen and a Lewis acidic surface atom and (2) a nucleophilic attack of a nearby Lewis basic surface atom is analysed in detail and found to mirror the acid-catalysed ether cleavage in solution. The O-Si dative bond is found to be the strongest of its kind and reactivity from this state defies the Bell-Evans-Polanyi principle. Electron rearrangement during the C-O bond cleavage is visualized using a newly developed bonding analysis method, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular chemistry SN2 reactions. Our findings thus illustrate how the fields of surface science and molecular chemistry can mutually benefit and unexpected insight can be gained.

Experimental studies of lithium-based surface chemistry for fusion plasma-facing materials applications

International Nuclear Information System (INIS)

Allain, J.P.; Rokusek, D.L.; Harilal, S.S.; Nieto-Perez, M.; Skinner, C.H.; Kugel, H.W.; Heim, B.; Kaita, R.; Majeski, R.

2009-01-01

Lithium has enhanced the operational performance of fusion devices such as: TFTR, CDX-U, FTU, T-11 M, and NSTX. Lithium in the solid and liquid state has been studied extensively in laboratory experiments including its erosion and hydrogen-retaining properties. Reductions in physical sputtering up to 40-60% have been measured for deuterated solid and liquid lithium surfaces. Computational modeling indicates that up to a 1:1 deuterium volumetric retention in lithium is possible. This paper presents the results of systematic in situ laboratory experimental studies on the surface chemistry evolution of ATJ graphite under lithium deposition. Results are compared to post-mortem analysis of similar lithium surface coatings on graphite exposed to deuterium discharge plasmas in NSTX. Lithium coatings on plasma-facing components in NSTX have shown substantial reduction of hydrogenic recycling. Questions remain on the role lithium surface chemistry on a graphite substrate has on particle sputtering (physical and chemical) as well as hydrogen isotope recycling. This is particularly due to the lack of in situ measurements of plasma-surface interactions in tokamaks such as NSTX. Results suggest that the lithium bonding state on ATJ graphite is lithium peroxide and with sufficient exposure to ambient air conditions, lithium carbonate is generated. Correlation between both results is used to assess the role of lithium chemistry on the state of lithium bonding and implications on hydrogen pumping and lithium sputtering. In addition, reduction of factors between 10 and 30 reduction in physical sputtering from lithiated graphite compared to pure lithium or carbon is also measured.

Surface chemistry and size influence the release of model therapeutic nanoparticles from poly(ethylene glycol) hydrogels

International Nuclear Information System (INIS)

Hume, Stephanie L.; Jeerage, Kavita M.

2013-01-01

Nanoparticles have emerged as promising therapeutic and diagnostic tools, due to their unique physicochemical properties. The specific core and surface chemistries, as well as nanoparticle size, play critical roles in particle transport and interaction with biological tissue. Localized delivery of therapeutics from hydrogels is well established, but these systems generally release molecules with hydrodynamic radii less than ∼5 nm. Here, model nanoparticles with biologically relevant surface chemistries and diameters between 10 and 35 nm are analyzed for their release from well-characterized hydrogels. Functionalized gold nanoparticles or quantum dots were encapsulated in three-dimensional poly(ethylene glycol) hydrogels with varying mesh size. Nanoparticle size, surface chemistry, and hydrogel mesh size all influenced the release of particles from the hydrogel matrix. Size influenced nanoparticle release as expected, with larger particles releasing at a slower rate. However, citrate-stabilized gold nanoparticles were not released from hydrogels. Negatively charged carboxyl or positively charged amine-functionalized quantum dots were released from hydrogels at slower rates than neutrally charged PEGylated nanoparticles of similar size. Transmission electron microscopy images of gold nanoparticles embedded within hydrogel sections demonstrated uniform particle distribution and negligible aggregation, independent of surface chemistry. The nanoparticle-hydrogel interactions observed in this work will aid in the development of localized nanoparticle delivery systems.

Venting temperature determines surface chemistry of magnetron sputtered TiN films

Energy Technology Data Exchange (ETDEWEB)

Greczynski, G. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden); Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, D-52074 Aachen (Germany); Mráz, S.; Schneider, J. M. [Materials Chemistry, RWTH Aachen University, Kopernikusstr. 10, D-52074 Aachen (Germany); Hultman, L. [Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping (Sweden)

2016-01-25

Surface properties of refractory ceramic transition metal nitride thin films grown by magnetron sputtering are essential for resistance towards oxidation necessary in all modern applications. Here, typically neglected factors, including exposure to residual process gases following the growth and the venting temperature T{sub v}, each affecting the surface chemistry, are addressed. It is demonstrated for the TiN model materials system that T{sub v} has a substantial effect on the composition and thickness-evolution of the reacted surface layer and should therefore be reported. The phenomena are also shown to have impact on the reliable surface characterization by x-ray photoelectron spectroscopy.

Micropatterning of Functional Conductive Polymers with Multiple Surface Chemistries in Register

DEFF Research Database (Denmark)

Lind, Johan Ulrik; Acikgöz, Canet; Daugaard, Anders Egede

2012-01-01

A versatile procedure is presented for fast and efficient micropatterning of multiple types of covalently bound surface chemistry in perfect register on and between conductive polymer microcircuits. The micropatterning principle is applied to several types of native and functionalized PEDOT (poly(3...... functionalized conjugated polymer systems....

Unpacking paleoenvironmental change across OAE2 using paired d34S records of pyrite and organic matter

Science.gov (United States)

Raven, M. R.; Gomes, M.; Fike, D. A.

2017-12-01

Pyrite sulfur isotopes have proven to be a powerful tool for reconstructing major changes in global redox state and the emergence of microbial metabolisms. Still, pyrite can be a challenging archive, as its formation depends on the availability of reactive iron species and can occur over multiple generations of sedimentary processes. Accordingly, pyrite δ34S records commonly have large point-to-point variability reflecting local processes. By pairing pyrite δ34S records with those of coexisting organic matter (OM), including both kerogens and extractable bitumens, we can begin to parse the various potential causes of this variability and gain greater insights into changes in the sedimentary paleoenvironment. Here, we present the first collection of records of OM δ34S for the Cretaceous, focusing on sections spanning Ocean Anoxic Event 2 (OAE2, 94 Mya), a period of globally widespread marine anoxia and carbon cycle disruption. In carbonates and shales from OAE2 in Pont d'Issole, France, pyrite and OM δ34S values vary in parallel throughout most of the section, consistent with their shared sulfide source. There are also distinct exceptions: In one interval, an excursion in pyrite δ34S is entirely absent from the organic sulfur record but associated with unusual organic sulfur redox speciation (by XAS), potentially reflecting later exposure to oxic porewaters. Across the core interval of shale deposition during OAE2, the offset between pyrite and OM δ34S values declines smoothly from +17.4 to -7.9‰, which we interpret in terms of changes in the speciation of detrital iron minerals that may have regional implications. We then compare these results with data for other well-characterized OAE2 sections, including Cismon (Italy), Tarfaya (Morocco), and the Demerara Rise (offshore Brazil), which represent environments with a variety of apparent redox states. These paired pyrite - OM δ34S profiles yield new information about how the local and global forcings

On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

DEFF Research Database (Denmark)

Vadapoo, Sundar Raja

2014-01-01

Molecular synthesis is essential in the bottom-up approach of achieving highly stable nanostructures. On-surface synthesis is highly interesting from the basic science of view to improve the understanding of molecular behavior adsorbed on metal surfaces, and has potential applications such as mol......Molecular synthesis is essential in the bottom-up approach of achieving highly stable nanostructures. On-surface synthesis is highly interesting from the basic science of view to improve the understanding of molecular behavior adsorbed on metal surfaces, and has potential applications...... such as molecular electronics and surface functionalization. In this thesis, a well-defined click chemistry approach is followed, with the study of azide-alkyne cycloaddition on Cu(111) surface in UHV environment. A successful achievement of the click reaction product via on-surface synthesis has been shown, which...

Bioadhesion of mussels and geckos: Molecular mechanics, surface chemistry, and nanoadhesives

Science.gov (United States)

Lee, Haeshin

The adhesive strategies of living creatures are diverse, ranging from temporary to permanent adhesions with various functions such as locomotion, self-defense, communication, colony formation, and so on. The classic example of temporary adhesion is the gecko, which is known for its ability to walk along vertical and even inverted surfaces; this remarkable adhesion arises from the interfacial weak interactions of van der Waals and capillary forces. In contrast, a celerbrated example of permanent adhesion is found in marine mussels which secrete protein adhesives that function in aqueous environments without mechanical failure against turbulent conditions on the seashore. In addition, mussel adhesives stick to virtually all inorganic and organic surfaces. However, most commonly used man-made adhesives lack such unique adhesion properties compared to their natural counterparts. For example, many commercial adhesives quickly lose their adhesive strength when exposed to solvents, particularly water. The first part of this thesis focused on adhesion mechanics of mussels at a single-molecule level, in which the adhesive molecule showed surprisingly strong yet reversible adhesion on inorganic surfaces but exhibited irreversible covalent bond formation on organic surfaces. Strong and reversible adhesion on mucin surfaces was found, indicating potential application for drug delivery via mucus layers. Next, inspired by the mussel's versatile adhesion on a wide variety of material surfaces, a material-independent surface modification chemistry called 'polydopamine coating' is described. This concept was subsequently adapted to develop a surface-independent polymeric primer for layer-by-layer assembly of multifunctional coatings. Finally, a new bio-hybrid adhesive 'geckel' was developed by the functional combination of adhesion strategies of geckos and mussels. The new bio-inspired adhesive and material-independent surface chemistry can revolutionize the research areas such as

Electrochemical Properties for Co-Doped Pyrite with High Conductivity

Directory of Open Access Journals (Sweden)

Yongchao Liu

2015-09-01

Full Text Available In this paper, the hydrothermal method was adopted to synthesize nanostructure Co-doped pyrite (FeS2. The structural properties and morphology of the synthesized materials were characterized using X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively. Co in the crystal lattice of FeS2 could change the growth rate of different crystal planes of the crystal particles, which resulted in various polyhedrons with clear faces and sharp outlines. In addition, the electrochemical performance of the doping pyrite in Li/FeS2 batteries was evaluated using the galvanostatic discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results showed that the discharge capacity of the doped material (801.8 mAh·g−1 with a doping ratio of 7% was significantly higher than that of the original FeS2 (574.6 mAh·g−1 because of the enhanced conductivity. Therefore, the doping method is potentially effective for improving the electrochemical performance of FeS2.

Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

Science.gov (United States)

Miyoshi, K.; Buckley, D. H.

1986-01-01

An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

Genotoxicity of copper oxide nanoparticles with different surface chemistry on rat bone marrow mesenchymal stem cells

DEFF Research Database (Denmark)

Zhang, Wenjing; Jiang, Pengfei; Chen, Wei

2016-01-01

The surface chemistry of nanoparticles (NPs) is one of the critical factors determining their cellular responses. In this study, the cytotoxicity and genotoxicity of copper oxide (CuO) NPs with a similar size but different surface chemistry to rat bone marrow mesenchymal stem cells (MSCs) were......V and showed a similar tendency to form agglomerates with a size of ∼200 nm in cell culture environment. The cytotoxicity of CuO NPs to MSCs at various concentrations and incubation periods were firstly evaluated. The CuO NPs showed dose-dependent and time-dependent toxicity to MSCs, and their surface...

Resilient carbon encapsulation of iron pyrite (FeS2) cathodes in lithium ion batteries

Science.gov (United States)

Yoder, Tara S.; Tussing, Matthew; Cloud, Jacqueline E.; Yang, Yongan

2015-01-01

Converting iron pyrite (FeS2) from a non-cyclable to a cyclable cathode material for lithium ion batteries has been an ongoing challenge in recent years. Herein we report a promising mitigation strategy: wet-chemistry based conformal encapsulation of synthetic FeS2 nanocrystals in a resilient carbon (RC) matrix (FeS2@RC). The FeS2@RC composite was fabricated by dispersing autoclave-synthesized FeS2 nanocrystals in an aqueous glucose solution, polymerizing the glucose in a hydrothermal reactor, and finally heating the polymer/FeS2 composite in a tube furnace to partially carbonize the polymer. The FeS2@RC electrodes showed superior cyclability compared with the FeS2 electrodes, that is, 25% versus 1% of retention at the 20th cycle. Based on electrochemical analysis, XRD study, and SEM characterization, the performance enhancement was attributed to RC's ability to accommodate volume fluctuation, enhance charge transfer, alleviate detrimental side reactions, and suppress loss of the active material. Furthermore, the remaining issues associated with the current system were identified and future research directions were proposed.

Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

International Nuclear Information System (INIS)

Gaigeot, Marie-Pierre; Sprik, Michiel; Sulpizi, Marialore

2012-01-01

The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, ‘ice-like’ and ‘liquid-like’ features in these spectra are interpreted as the result of hydrogen bonds of different strengths between surface silanols/aluminols and water. (paper)

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

Science.gov (United States)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

The hydrochemistry of glacial Ebba River (Petunia Bay, Central Spitsbergen): Groundwater influence on surface water chemistry

Science.gov (United States)

Dragon, Krzysztof; Marciniak, Marek; Szpikowski, Józef; Szpikowska, Grażyna; Wawrzyniak, Tomasz

2015-10-01

The article presents the investigation of surface water chemistry changes of the glacial Ebba River (Central Spitsbergen) during three melting seasons of 2008, 2009 and 2010. The twice daily water chemistry analyses allow recognition of the surface water chemistry differentiation. The surface water chemistry changes are related to the river discharge and changes in the influence of different water balance components during each melting season. One of the most important process that influence river water component concentration increase is groundwater inflow from active layer occurring on the valley area. The significance of this process is the most important at the end of the melting season when temperatures below 0 °C occur on glaciers (resulting in a slowdown of melting of ice and snow and a smaller recharge of the river by the water from the glaciers) while the flow of groundwater is still active, causing a relatively higher contribution of groundwater to the total river discharge. The findings presented in this paper show that groundwater contribution to the total polar river water balance is more important than previously thought and its recognition allow a better understanding of the hydrological processes occurring in a polar environment.

Gelatin/DMSO. A new approach to enhancing the performance of a pyrite electrode in a lithium battery

Energy Technology Data Exchange (ETDEWEB)

Montoro, L.A.; Rosolen, J.M. [Department of Chemistry, FFCLRP-University of Sao Paulo, 14040-901 Ribeirao Preto, Sao Paulo (Brazil)

2003-04-01

We have studied the electrochemical behavior of natural pyrite (FeS{sub 1.9}, n-type semiconductor) treated nonaqueously with dimethylsulfoxide (DMSO) solvent and also with a gelatin/DMSO solution. Composite electrodes (comprised of pyrite, polyvinilidene fluoride, polyethylene oxide and carbon) were characterized in a lithium cell at room temperature by cyclic voltammetry and galvanostatic measurements; the electrolyte used was LiPF{sub 6} in a solution of ethylene carbonate and dimethyl carbonate (1 mol l{sup -1}). The gelatin/DMSO treatment greatly improved the reversible specific capacity of a pyrite electrode. For galvanostatic discharge/charge at a current density of 0.4 mA cm{sup -2} and between voltage limits of 3.2 and 1.1 V, its reversible specific capacity at the 15th cycle equaled 275 mA h g{sup -1}, an impressive value compared to less than 25 mA h g{sup -1} for a pristine pyrite electrode.

Pyrite thermochemistry, ash agglomeration, and char fragmentation during pulverized coal combustion

Energy Technology Data Exchange (ETDEWEB)

Akan-Etuk, A.; Diaz, R.; Niksa, S.

1991-10-01

The objective of the present work is to introduce an experimental program that will eventually lead to time-resolved iron ash composition over the technological operating domain. The preceding literature survey suggests two important stipulations on any such experimental program. The first stipulation is that good control must be established over the operating conditions, to accurately quantify their effects. The other is that data must be obtained rapidly, to thoroughly cover the important operating domain. This work presents a series of studies that has characterized the desulfurization of pyrite during the early stages of combustion. An experimental system was established and used to monitor the effects of oxygen, temperature, and residence time on the evolution of condensed phase products of the combustion of pure pyrite. (VC)

Bioleaching of low grade uranium ore containing pyrite using A. ferrooxidans and A. thiooxidans

International Nuclear Information System (INIS)

Alexey Borisovich Umanskii; Anton Mihaylovich Klyushnikov

2013-01-01

A process of uranium extraction from ore containing 3.1 % pyrite by bacterial leaching was investigated in shaken flasks during 90 days. The highest uranium recovery amounting to 85.1 % was obtained using binary mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans that was exceeding results obtained by traditional acid leaching technique up to 27 %. High uranium recovery was founded to be due to the high degree of pyrite dissolution that can be readily achieved by bacterial leaching (up to 98.0 %). (author)

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

Energy Technology Data Exchange (ETDEWEB)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

2016-11-15

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

International Nuclear Information System (INIS)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

2016-01-01

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

On the formation of protective sulphide coatings on carbon steel surfaces

International Nuclear Information System (INIS)

Das, C.; Venkateswaran, G.

1987-01-01

A chemical method for protecting carbon steel surfaces by forming pyrrhotite/pyrite coatings has been developed. The protective nature of the coatings has been studied by weight loss kinetics, scanning electron microscopy and electrochemical measurements. A comparison is drawn between the protective nature of pyrite coating with that of magnetite coating. (author)

Influence of chemistry on wetting dynamics of nanotextured hydrophobic surfaces.

Science.gov (United States)

Di Mundo, Rosa; Palumbo, Fabio; d'Agostino, Riccardo

2010-04-06

In this work, the role of a chemical parameter, such as the degree of fluorination, on the wetting behavior of nanotextured hydrophobic surfaces is investigated. Texture and chemistry tuning of the surfaces has been accomplished with single batch radiofrequency low-pressure plasma processes. Polystyrene substrates have been textured by CF(4) plasma etching and subsequently covered by thin films with a tunable F-to-C ratio, obtained in discharges fed with C(4)F(8)-C(2)H(4). Measurements of wetting dynamics reveal a regime transition from adhesive-hydrophobic to slippery-superhydrophobic, i.e., from wet to non wet states, as the F-to-C rises at constant topography. Such achievements are strengthened by calculation of the solid fraction of surface water contact area applying Cassie-Baxter advancing and receding equations to water contact angle data of textured and flat reference surfaces.

Terrestrial sedimentary pyrites as a potential source of trace metal release to groundwater – A case study from the Emsland, Germany

International Nuclear Information System (INIS)

Houben, Georg J.; Sitnikova, Maria A.; Post, Vincent E.A.

2017-01-01

Pyrite is a common minor constituent of terrestrial freshwater sediments and a sink for trace elements. Different amounts and morphological types (framboids and euhedral crystals) of sedimentary pyrites were found in the heavy mineral fraction of cores obtained from several drillholes located in the Emsland region, NW Germany. Their trace element contents were investigated to assess their potential for groundwater contamination after oxidation, e.g. induced by dewatering or autotrophic denitrification. Nickel, arsenic and cadmium were found in significant concentrations in pyrite. Geochemical modeling showed that elevated trace metal concentrations in groundwater, potentially exceeding drinking water standards, should preferentially occur in a less than 1 m thick zone situated around the depth of the redoxcline, where nitrate is reduced by pyrite. This was confirmed by depth-specific groundwater sampling in the Emsland and by previously published studies. The absolute concentration of released trace metals depends on their content in the pyrite but also strongly on the nitrate load of groundwater. - Highlights: • Pyrite from heavy mineral fraction of aquifer sediment analyzed for trace metal content. • Pyrites contain significant concentration of trace metals, such as nickel, arsenic, cadmium. • Trace elements are released by autotrophic denitrification. • Reactive transport model predicts small zone of trace element accumulation. • Release of trace elements strongly dependent on nitrate content of groundwater.

Defective pyrite (100) surface: An ab initio study

International Nuclear Information System (INIS)

Stirling, Andras; Bernasconi, Marco; Parrinello, Michele

2007-01-01

The structural and electronic properties of sulfur monomeric defects at the FeS 2 (100) surface have been studied by periodic density-functional calculations. We have shown that for a monomeric sulfur bound to an originally fivefold coordinated surface Fe site, the defect core features a triplet electronic ground state with unpaired spins localized on the exposed Fe-S unit. At this site, the iron and sulfur ions have oxidation states +4 and -2, respectively. This defect can be seen as produced via heterolytic bond breaking of the S-S sulfur dimer followed by a Fe-S redox reaction. The calculated sulfur 2p core-level shifts of the monomeric defects are in good agreement with experimental photoemission spectra, which allow a compelling assignment of the different spectroscopic features. The effect of water on the stability of the defective surface has also been studied, and it has been shown that the triplet state is stable against the wetting of the surface. The most important implications of the presence of the monomeric sulfur defect on the reactivity are also discussed

Relationships between precipitation and surface water chemistry in three Carolina bays

International Nuclear Information System (INIS)

Monegue, R.L.; Jagoe, C.H.

1995-01-01

Carolina Bays are shallow freshwater wetlands, the only naturally occurring lentic systems on the southeastern coastal plain. Bays are breeding sites for many amphibian species, but data on precipitation/surface water relationships and long-term chemical trends are lacking. Such data are essential to interpret major fluctuations in amphibian populations. Surface water and bulk precipitation were sampled bi-weekly for over two years at three bays along a 25 km transect on the Savannah River Site in South Carolina. Precipitation chemistry was similar at all sites; average pH was 4.56, and the major ions were H + (30.8 % of total), and SO 4 (50.3% of total). H + was positively correlated with SO 4 , suggesting the importance of anthropogenic acids to precipitation chemistry. All three bays, Rainbow Bay (RB), Thunder Bay (TB), and Ellenton Bay (EB), contained soft (specific conductivity 5--90 microS/cm), acidic water (pH 4.0--5.9) with DOM from 4--40 mg/L. The major cation for RB, TB, and EB, respectively, was: Mg (30.8 % of total); Na (27% of total); and Ca (34.2% of total). DOM was the major anion for all bays, and SO 4 represented 13 to 28 % of total anions. H + was not correlated to DOM or SO, in RB; H + was positively correlated to DOM and SO 4 in TB, and negatively correlated to DOM and SO 4 in EB. Different biogeochemical processes probably control pH and other chemical variables in each bay. While surface water H + was not directly correlated with precipitation H + , NO 3 , or SO 4 , precipitation and shallow groundwater are dominant water sources for these bays. Atmospheric inputs of anthropogenic acids and other chemicals are important factors influencing bay chemistry

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

Directory of Open Access Journals (Sweden)

Nicola H. Perry

2016-10-01

Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

Application of positron annihilation induced auger electron spectroscopy to the study of surface chemistry

International Nuclear Information System (INIS)

Weiss, A.H.; Yang, G.; Nangia, A.; Kim, J.H.; Fazleev, N.G.

1996-01-01

Positron annihilation induced Auger Electron Spectroscopy (PAES), makes use a beam of low energy positrons to excite Auger transitions by annihilating core electrons. This novel mechanism provides PAES with a number of unique features which distinguishes it from other methods of surface analysis. In PAES the very large collisionally induced secondary electron background which is present under the low energy Auger peaks using conventional techniques can be eliminated by using a positron beam whose energy is below the range of Auger electron energies. In addition, PAES is more surface selective than conventional Auger Spectroscopy because the PAES signal originates almost exclusively from the topmost atomic layer due to the fact that the positrons annihilating with the core electrons are trapped in an image correlation well just outside the surface. In this paper, recent applications of Positron Annihilation Induced Auger Electron Spectroscopy (PAES) to the study of surface structure and surface chemistry will be discussed including studies of the growth, alloying and inter-diffusion of ultrathin layers of metals, metals on semiconductors, and semiconductors on semiconductors. In addition, the possibilities for future application of PAES to the study of catalysis and surface chemistry will be outlined. (author)

High-energy particle emission from galena and pyrite bombarded with Cs and O ions

International Nuclear Information System (INIS)

Karpuzov, D.S.; McIntyre, N.S.

2002-01-01

The ejection of energetic particles during steady-state ion surface bombardment has been investigated by means of a dynamic computer simulation as well as in a secondary ion mass spectrometry (SIMS)/low-energy ion scattering from surfaces (LEIS) experiment. The emphasis of this comparative study is on the mass dependence of high-energy tails in sputtering and backscattering for the bombardment of galena (PbS) and pyrite (FeS 2 ) with keV energy ion beam of cesium and oxygen. In the experiment, kinetic energy distributions of sputtered secondary ions (S + , Fe + , Pb + , S - ), as well as backscattered or re-sputtered primary ions (Cs + , O + , O - ), have been measured on a modified Cameca IMS-3f magnetic sector mass spectrometer for keV cesium (Cs + ) and oxygen (O 2 + , O - ) bombardment of galena and pyrite. Ejection of high-energy particles, with emission energies of up to ∼40% or up to ∼60% of the bombarding energy for sputtering of the lighter component (S ± ) with cesium or oxygen, respectively, and of up to ∼40% (Cs + ) and ∼80% (O ± ) for backscattering, has been observed for PbS. The computer simulations were based on the well-known MARLOWE code. In order to model the change of the stoichiometry of the binary compounds, dynamic modification of the target composition in the near-surface region was introduced. Cs incorporation was included, and a relative enrichment of the metallic component (Pb, Fe) in the top few layers due to preferential sputtering of sulfur was allowed. The computer simulations provide information on the formation of altered layer under sputter equilibrium as well as on the energy and angular emission distributions of sputtered and backscattered particles in steady-state conditions. Multiple scattering of Cs projectiles and dynamic re-sputtering of cesium that was previously incorporated in the altered near-surface region can be distinguished in the simulation, and matched with the experimental observations. In addition

New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

KAUST Repository

Samantaray, Manoja

2015-08-18

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

Science.gov (United States)

Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

2007-01-01

A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

The origin of copiapite from chlorite pyritic schist (Wiesciszowice, Lower Silesia, Poland) in the light of Moessbauer analysis

Energy Technology Data Exchange (ETDEWEB)

Adamczyk, Z., E-mail: zdzislaw.adamczyk@polsl.pl [Silesian University of Technology, Institute of Applied Geology (Poland); Komraus, J. L., E-mail: komraus@us.edu.pl [University of Silesia, Institute of Physics (Poland)

2008-01-15

This work presents the results of the analysis of copiapite, formed from weathering and oxidation of pyrite in pyritic schist from Wiesciszowice, Lower Silesia (Poland). The pure phase of copiapite was found in secondary minerals after pyrite and identified by optical microscopy, XRD and Moessbauer spectroscopy. In the analyzed copiapite major cations appear to be Fe{sup 2+} and Fe{sup 3+}. Some Fe{sup 3+} is substituted by other cations, mainly Al{sup 3+}. Al{sup 3+} probably comes from leaching of chlorite from which hydrated sulphates of iron, mainly szomolnokite, form followed by hydrated sulphates fibroferrite, which is replaced by copiapite.

In situ remediation of hexavalent chromium with pyrite fines : bench scale demonstration

International Nuclear Information System (INIS)

Cathum, S.; Wong, W.P.; Brown, C.E.

2002-01-01

An in situ remediation technique for chromium contaminated soil with pyrite fines was presented. Past industrial activities and lack of disposal facilities have contributed to a serious problem dealing with chromium, which cannot be eliminated from the environment because it is an element. Both bench-scale and laboratory testing was conducted to confirm the efficiency of the proposed process which successfully converted Cr(VI) into Cr(III) in soil and water. Cr(III) is less toxic and immobile in the environment compared to Cr(VI) which moves freely in the soil matrix, posing a risk to the groundwater quality. pH in the range of 2.0 to 7.6 has no effect on the reactivity of pyrite towards Cr(VI). The optimization of the bench-scale treatment resulted in a large volume of chromium waste, mostly from the control experiments and column hydrology testing. These waste streams were treated according to municipal guidelines before disposal to the environment. Samples of chromium waste before and after treatment were analyzed. Cr (VI) was completely mineralized to below guideline levels. It was determined that several conditions, including contact time between pyrite and Cr(VI), are crucial for complete mineralization of Cr(VI). 13 refs., 8 tabs., 9 figs

Influence of surface microstructure and chemistry on osteoinduction and osteoclastogenesis by biphasic calcium phosphate discs

Directory of Open Access Journals (Sweden)

NL Davison

2015-06-01

Full Text Available It has been reported that surface microstructural dimensions can influence the osteoinductivity of calcium phosphates (CaPs, and osteoclasts may play a role in this process. We hypothesised that surface structural dimensions of ≤ 1 μm trigger osteoinduction and osteoclast formation irrespective of macrostructure (e.g., concavities, interconnected macropores, interparticle space or surface chemistry. To test this, planar discs made of biphasic calcium phosphate (BCP: 80 % hydroxyapatite, 20 % tricalcium phosphate were prepared with different surface structural dimensions – either ~ 1 μm (BCP1150 or ~ 2-4 μm (BCP1300 – and no macropores or concavities. A third material was made by sputter coating BCP1150 with titanium (BCP1150Ti, thereby changing its surface chemistry but preserving its surface structure and chemical reactivity. After intramuscular implantation in 5 dogs for 12 weeks, BCP1150 formed ectopic bone in 4 out of 5 samples, BCP1150Ti formed ectopic bone in 3 out of 5 samples, and BCP1300 formed no ectopic bone in any of the 5 samples. In vivo, large multinucleated osteoclast-like cells densely colonised BCP1150, smaller osteoclast-like cells formed on BCP1150Ti, and osteoclast-like cells scarcely formed on BCP1300. In vitro, RAW264.7 cells cultured on the surface of BCP1150 and BCP1150Ti in the presence of osteoclast differentiation factor RANKL (receptor activator for NF-κB ligand proliferated then differentiated into multinucleated osteoclast-like cells with positive tartrate resistant acid phosphatase (TRAP activity. However, cell proliferation, fusion, and TRAP activity were all significantly inhibited on BCP1300. These results indicate that of the material parameters tested – namely, surface microstructure, macrostructure, and surface chemistry – microstructural dimensions are critical in promoting osteoclastogenesis and triggering ectopic bone formation.

Molecular-level chemistry of model single-crystal oxide surfaces with model halogenated compounds

Science.gov (United States)

Adib, Kaveh

Synchrotron-based X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD) and low energy electron diffraction (LEED) have been used to investigate, at a molecular level, the chemistry of different terminations of single crystal iron-oxide surfaces with probe molecules (CCl4 and D2O). Comparisons of the reactivity of these surfaces towards CCl4, indicate that the presence of an uncapped surface Fe cation (strong Lewis acid site) and an adjacent oxygen site capped by that cation can effect the C-Cl bond cleavage in CCl4, resulting in dissociatively adsorbed Cl-adatoms and carbon-containing fragments. If in addition to these sites, an uncapped surface oxygen (Lewis base) site is also available, the carbon-containing moiety can then move that site, coordinate itself with that uncapped oxygen, and stabilize itself. At a later step, the carbon-containing fragment may form a strong covalent bond with the uncapped oxygen and may even abstract that surface oxygen. On the other hand, if an uncapped oxygen is not available to stabilize the carbon-containing fragment, the surface coordination will not occur and upon the subsequent thermal annealing of the surface the Cl-adatoms and the carbon-containing fragments will recombine and desorb as CCl4. Finally, the presence of surface deuteroxyls blocking the strong Lewis acid and base sites of the reactive surface, passivates this surface. Such a deuteroxylated surface will be unreactive towards CCl 4. Such a molecular level understanding of the surface chemistry of metal-oxides will have applications in the areas of selective catalysis, including environmental catalysis, and chemical sensor technology.

Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases.

Science.gov (United States)

De Roo, Jonathan; Van den Broeck, Freya; De Keukeleere, Katrien; Martins, José C; Van Driessche, Isabel; Hens, Zeger

2014-07-09

We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

Science.gov (United States)

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Impact of water chemistry on surface charge and aggregation of polystyrene microspheres suspensions.

Science.gov (United States)

Lu, Songhua; Zhu, Kairuo; Song, Wencheng; Song, Gang; Chen, Diyun; Hayat, Tasawar; Alharbi, Njud S; Chen, Changlun; Sun, Yubing

2018-07-15

The discharge of microplastics into aquatic environment poses the potential threat to the hydrocoles and human health. The fate and transport of microplastics in aqueous solutions are significantly influenced by water chemistry. In this study, the effect of water chemistry (i.e., pH, foreign salts and humic acid) on the surface charge and aggregation of polystyrene microsphere in aqueous solutions was conducted by batch, zeta potentials, hydrodynamic diameters, FT-IR and XPS analysis. Compared to Na + and K + , the lower negative zeta potentials and larger hydrodynamic diameters of polystyrene microspheres after introduction of Mg 2+ were observed within a wide range of pH (2.0-11.0) and ionic strength (IS, 0.01-500mmol/L). No effect of Cl - , HCO 3 - and SO 4 2- on the zeta potentials and hydrodynamic diameters of polystyrene microspheres was observed at low IS concentrations (10mmol/L). The zeta potentials of polystyrene microspheres after HA addition were decreased at pH2.0-11.0, whereas the lower hydrodynamic diameters were observed at pH<4.0. According to FT-IR and XPS analysis, the change in surface properties of polystyrene microspheres after addition of hydrated Mg 2+ and HA was attributed to surface electrostatic and/or steric repulsions. These investigations are crucial for understanding the effect of water chemistry on colloidal stability of microplastics in aquatic environment. Copyright © 2018 Elsevier B.V. All rights reserved.

Influence of Sulfobacillus thermosulfidooxidans on Initial Attachment and Pyrite Leaching by Thermoacidophilic Archaeon Acidianus sp. DSM 29099

Directory of Open Access Journals (Sweden)

Jing Liu

2016-07-01

Full Text Available At the industrial scale, bioleaching of metal sulfides includes two main technologies, tank leaching and heap leaching. Fluctuations in temperature caused by the exothermic reactions in a heap have a pronounced effect on the growth of microbes and composition of mixed microbial populations. Currently, little is known on the influence of pre-colonized mesophiles or moderate thermophiles on the attachment and bioleaching efficiency by thermophiles. The objective of this study was to investigate the interspecies interactions of the moderate thermophile Sulfobacillus thermosulfidooxidans DSM 9293T and the thermophile Acidianus sp. DSM 29099 during initial attachment to and dissolution of pyrite. Our results showed that: (1 Acidianus sp. DSM 29099 interacted with S. thermosulfidooxidansT during initial attachment in mixed cultures. In particular, cell attachment was improved in mixed cultures compared to pure cultures alone; however, no improvement of pyrite leaching in mixed cultures compared with pure cultures was observed; (2 active or inactivated cells of S. thermosulfidooxidansT on pyrite inhibited or showed no influence on the initial attachment of Acidianus sp. DSM 29099, respectively, but both promoted its leaching efficiency; (3 S. thermosulfidooxidansT exudates did not enhance the initial attachment of Acidianus sp. DSM 29099 to pyrite, but greatly facilitated its pyrite dissolution efficiency. Our study provides insights into cell-cell interactions between moderate thermophiles and thermophiles and is helpful for understanding of the microbial interactions in a heap leaching environment.

Bacterial resistance of self-assembled surfaces using PPOm-b-PSBMAn zwitterionic copolymer - concomitant effects of surface topography and surface chemistry on attachment of live bacteria.

Science.gov (United States)

Hsiao, Sheng-Wen; Venault, Antoine; Yang, Hui-Shan; Chang, Yung

2014-06-01

Three well-defined diblock copolymers made of poly(sulfobetaine methacrylate) (poly(SBMA)) and poly(propylene oxide) (PPO) groups were synthesized by atom transfer radical polymerization (ATRP) method. They were physically adsorbed onto three types of surfaces having different topography, including smooth flat surface, convex surface, and indented surface. Chemical state of surfaces was characterized by XPS while the various topographies were examined by SEM and AFM. Hydrophilicity of surfaces was dependent on both the surface chemistry and the surface topography, suggesting that orientation of copolymer brushes can be tuned in the design of surfaces aimed at resisting bacterial attachment. Escherichia coli, Staphylococcus epidermidis, Streptococcus mutans and Escherichia coli with green fluorescent protein (E. coli GFP) were used in bacterial tests to assess the resistance to bacterial attachment of poly(SBMA)-covered surfaces. Results highlighted a drastic improvement of resistance to bacterial adhesion with the increasing of poly(SBMA) to PPO ratio, as well as an important effect of surface topography. The chemical effect was directly related to the length of the hydrophilic moieties. When longer, more water could be entrapped, leading to improved anti-bacterial properties. The physical effect impacted on the orientation of the copolymer brushes, as well as on the surface contact area available. Convex surfaces as well as indented surfaces wafer presented the best resistance to bacterial adhesion. Indeed, bacterial attachment was more importantly reduced on these surfaces compared with smooth surfaces. It was explained by the non-orthogonal orientation of copolymer brushes, resulting in a more efficient surface coverage of zwitterionic molecules. This work suggests that not only the control of surface chemistry is essential in the preparation of surfaces resisting bacterial attachment, but also the control of surface topography and orientation of antifouling

Matrix composition and community structure analysis of a novel bacterial pyrite leaching community.

Science.gov (United States)

Ziegler, Sibylle; Ackermann, Sonia; Majzlan, Juraj; Gescher, Johannes

2009-09-01

Here we describe a novel bacterial community that is embedded in a matrix of carbohydrates and bio/geochemical products of pyrite (FeS(2)) oxidation. This community grows in stalactite-like structures--snottites--on the ceiling of an abandoned pyrite mine at pH values of 2.2-2.6. The aqueous phase in the matrix contains 200 mM of sulfate and total iron concentrations of 60 mM. Micro-X-ray diffraction analysis showed that jarosite [(K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6)] is the major mineral embedded in the snottites. X-ray absorption near-edge structure experiments revealed three different sulfur species. The major signal can be ascribed to sulfate, and the other two features may correspond to thiols and sulfoxides. Arabinose was detected as the major sugar component in the extracellular polymeric substance. Via restriction fragment length polymorphism analysis, a community was found that mainly consists of iron oxidizing Leptospirillum and Ferrovum species but also of bacteria that could be involved in dissimilatory sulfate and dissimilatory iron reduction. Each snottite can be regarded as a complex, self-contained consortium of bacterial species fuelled by the decomposition of pyrite.

An experimental study on the geochemical behavior of highly siderophile elements (HSE) and metalloids (As, Se, Sb, Te, Bi) in a mss-iss-pyrite system at 650 °C: A possible magmatic origin for Co-HSE-bearing pyrite and the role of metalloid-rich phases in the fractionation of HSE

Science.gov (United States)

Cafagna, Fabio; Jugo, Pedro J.

2016-04-01

Pyrite, the most abundant sulfide in the Earth's crust, is an accessory mineral in several magmatic sulfide deposits. Although most pyrite is hydrothermal, previous experimental studies have shown that pyrite can also have a primary magmatic origin, by exsolving from monosulfide solid solution (mss) during cooling of a sulfide melt, if sulfur fugacity is sufficiently high. Pyrite from some localities has significant amounts of Co, and complex zonation in some low-melting-point chalcophile elements (LMCE), such as As, Se, Sb, Te, Bi (henceforth referred to as metalloids) and some platinum-group elements (PGE: Ru, Rh, Pd, Os, Ir, Pt). However, the origin of such pyrite and the causes of zonation are not clear. Because the distribution of some of these elements is heterogeneous and seems to be developed in concentric zones, the zonation has been interpreted to represent growth stages, some of them secondary and caused partly by hydrothermal fluids. Better constraints on the origin of Co-PGE-bearing pyrite could help unravel the geochemical processes affecting the sulfide assemblages in which it is found; thus, an experimental study was undertaken to characterize pyrite formation in magmatic sulfide environments and its relationship with metalloids and highly siderophile elements (HSE: PGE, Re, Au). Natural pyrrhotite, chalcopyrite, pentlandite and elemental S were mixed and doped with approximately 50 ppm of each HSE. A mixture of metalloids was added at 0.2 wt.% or 3 wt.% to aliquots of sulfide mixtures. Starting materials were sealed in evacuated silica tubes and fused at 1200 °C. The temperature was subsequently reduced to 750 °C (at 60 °C/h), then to 650 °C (at 0.5 °C/h) to produce relatively large euhedral pyrite crystals, then quenched. The experiments were analyzed using reflected light, SEM, EPMA and LA-ICP-MS. Experimental products contained euhedral pyrite, mss, intermediate solid solution (iss) and metalloid-rich phases, interpreted as quench product

Surface chemistry manipulation of gold nanorods preserves optical properties for bio-imaging applications

Energy Technology Data Exchange (ETDEWEB)

Polito, Anthony B.; Maurer-Gardner, Elizabeth I.; Hussain, Saber M., E-mail: saber.hussain@us.af.mil [Air Force Research Laboratory, Molecular Bioeffects Branch, Bioeffects Division, Human Effectiveness Directorate (United States)

2015-12-15

Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable optical properties within the near-infrared (NIR) region. However, cetyl trimethylammonium bromide-related cytotoxicity, overall poor cellular uptake following surface chemistry modifications, and loss of NIR optical properties due to material intracellular aggregation in combination remain as obstacles for nanobased biomedical GNR applications. In this article, we report that tannic acid-coated 11-mercaptoundecyl trimethylammonium bromide (MTAB) GNRs (MTAB-TA) show no significant decrease in either in vitro cell viability or stress activation after exposures to A549 human alveolar epithelial cells. In addition, MTAB-TA GNRs demonstrate a substantial level of cellular uptake while displaying a unique intracellular clustering pattern. This clustering pattern significantly reduces intracellular aggregation, preserving the GNRs NIR optical properties, vital for biomedical imaging applications. These results demonstrate how surface chemistry modifications enhance biocompatibility, allow for higher rate of internalization with low intracellular aggregation of MTAB-TA GNRs, and identify them as prime candidates for use in nanobased bio-imaging applications.Graphical Abstract.

Model-based analysis of δ34S signatures to trace sedimentary pyrite oxidation during managed aquifer recharge in a heterogeneous aquifer

Science.gov (United States)

Seibert, Simone; Descourvieres, Carlos; Skrzypek, Grzegorz; Deng, Hailin; Prommer, Henning

2017-05-01

The oxidation of pyrite is often one of the main drivers affecting groundwater quality during managed aquifer recharge in deep aquifers. Data and techniques that allow detailed identification and quantification of pyrite oxidation are therefore crucial for assessing and predicting the adverse water quality changes that may be associated with this process. In this study, we explore the benefits of combining stable sulphur isotope analysis with reactive transport modelling to improve the identification and characterisation of pyrite oxidation during an aquifer storage and recovery experiment in a chemically and physically heterogeneous aquifer. We characterise the stable sulphur isotope signal (δ34S) in both the ambient groundwater and the injectant as well as its spatial distribution within the sedimentary sulphur species. The identified stable sulphur isotope signal for pyrite was found to vary between -32 and +34‰, while the signal of the injectant ranged between +9.06 and +14.45‰ during the injection phase of the experiment. Both isotope and hydrochemical data together suggest a substantial contribution of pyrite oxidation to the observed, temporally variable δ34S signals. The variability of the δ34S signal in pyrite and the injectant were both found to complicate the analysis of the stable isotope data. However, the incorporation of the data into a numerical modelling approach allowed to successfully employ the δ34S signatures as a valuable additional constraint for identifying and quantifying the contribution of pyrite oxidation to the redox transformations that occur in response to the injection of oxygenated water.

Galvanic Interaction between Chalcopyrite and Pyrite with Low Alloy and High Carbon Chromium Steel Ball

Directory of Open Access Journals (Sweden)

Asghar Azizi

2013-01-01

Full Text Available This study was aimed to investigate the galvanic interaction between pyrite and chalcopyrite with two types of grinding media (low alloy and high carbon chromium steel ball in grinding of a porphyry copper sulphide ore. Results indicated that injection of different gases into mill altered the oxidation-reduction environment during grinding. High carbon chromium steel ball under nitrogen gas has the lowest galvanic current, and low alloy steel ball under oxygen gas had the highest galvanic current. Also, results showed that the media is anodic relative to pyrite and chalcopyrite, and therefore pyrite or chalcopyrite with a higher rest potential acted as the cathode, whilst the grinding media with a lower rest potential acted as the anode, when they are electrochemically contacted. It was also found that low alloy steel under oxygen produced the highest amount of EDTA extractable iron in the slurry, whilst high carbon chromium steel under nitrogen atmosphere led to the lowest amount.

Measuring restoration progress using pore- and surface-water chemistry across a chronosequence of formerly afforested blanket bogs.

Science.gov (United States)

Gaffney, Paul P J; Hancock, Mark H; Taggart, Mark A; Andersen, Roxane

2018-08-01

During the restoration of degraded bogs and other peatlands, both habitat and functional recovery can be closely linked with nutrient cycling, which is reflected in pore- and surface-water chemistry. Several peatland restoration studies have shown that the time required for recovery of target conditions is slow (>10 years); for heavily-impacted, drained and afforested peatlands of northern Scotland, recovery time is unknown. We monitored pore- and surface-water chemistry across a chronosequence of formerly drained, afforested bog restoration sites spanning 0-17 years, using a space-for-time substitution, and compared them with open blanket bog control sites. Our aims were to measure rate of recovery towards bog conditions and to identify the best suite of water chemistry variables to indicate recovery. Our results show progress in recovery towards bog conditions over a 0-17 year period post-restoration. Elements scavenged by trees (Mg, Na, S) completely recovered within that period. Many water chemistry variables were affected by the restoration process itself, but recovered within 11 years, except ammonium (NH 4 + ), Zn and dissolved organic carbon (DOC) which remained elevated (when compared to control bogs) 17 years post restoration. Other variables did not completely recover (water table depth (WTD), pH), exhibiting what we term "legacy" effects of drainage and afforestation. Excess N and a lowered WTD are likely to slow the recovery of bog vegetation including key bog plants such as Sphagnum mosses. Over 17 years, we measured near-complete recovery in the chemistry of surface-water and deep pore-water but limited progress in shallow pore-water. Our results suggest that at least >17 years are required for complete recovery of water chemistry to bog conditions. However, we expect that newer restoration methods including conifer harvesting (stem plus brash) and the blocking of plough furrows (to increase the WTD) are likely to accelerate the restoration process

Chemical vapour transport of pyrite (FeS 2) with halogen (Cl, Br, I)

Science.gov (United States)

Fiechter, S.; Mai, J.; Ennaoui, A.; Szacki, W.

1986-12-01

A systematic study of chemical vapour transport (CVT) of pyrite with halogen, hydrogen halides and ammonium halides as transporting agents has shown that the transport with chlorine and bromine in a temperature gradient Δ T = 920-820 K yields the highest transport rates (˜6 mg/h) with crystals up to 5 mm edge length. Computing thermochemical equilibria and flux functions in the system Fe-S-Hal (Hal = Cl, Br, I) it has been confirmed that the transport velocity of pyrite is limited by the concentration of FeHal 2 in the vapour phase, the equilibrium position between FeHal 2(g) and FeHal 3(g) and the flux directions of the iron gas species.

Adsorption and enzymatic cleavage of osteopontin at interfaces with different surface chemistries

DEFF Research Database (Denmark)

Malmström, Jenny; Shipovskov, Stepan; Christensen, Brian

2009-01-01

(methyl-, carboxylic-, and amine-terminated alkanethiol self-assembled monolayers and bare gold) have been studied utilizing a combination of the quartz crystal microbalance with dissipation and surface plasmon resonance. Full length bovine milk osteopontin was used which is well characterized...... at the polar surfaces with the highest level of hydration being observed at the gold surface. The energy dissipation of these thin films (as measured by the DeltaD/DeltaF value) was altered at the different surface chemistries and interestingly a higher dissipation correlated with a higher density. Thrombin...... with respect to post-translational modifications. Osteopontin adsorbed at all the surfaces formed thin (approximately 2-5 nm) hydrated layers with the highest amount of protein and the highest density layers observed at the hydrophobic surface. Less protein and a higher level of hydration was observed...

Quantum confinement and surface chemistry of 0.8–1.6 nm hydrosilylated silicon nanocrystals

International Nuclear Information System (INIS)

Pi Xiao-Dong; Wang Rong; Yang De-Ren

2014-01-01

In the framework of density functional theory (DFT), we have studied the electronic properties of alkene/alkyne-hydrosilylated silicon nanocrystals (Si NCs) in the size range from 0.8 nm to 1.6 nm. Among the alkenes with all kinds of functional groups considered in this work, only those containing —NH 2 and —C 4 H 3 S lead to significant hydrosilylation-induced changes in the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of an Si NC at the ground state. The quantum confinement effect is dominant for all of the alkene-hydrosilylated Si NCs at the ground state. At the excited state, the prevailing effect of surface chemistry only occurs at the smallest (0.8 nm) Si NCs hydrosilylated with alkenes containing —NH 2 and —C 4 H 3 S. Although the alkyne hydrosilylation gives rise to a more significant surface chemistry effect than alkene hydrosilylation, the quantum confinement effect remains dominant for alkyne-hydrosilylated Si NCs at the ground state. However, at the excited state, the effect of surface chemistry induced by the hydrosilylation with conjugated alkynes is strong enough to prevail over that of quantum confinement. (condensed matter: structural, mechanical, and thermal properties)

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry.

Science.gov (United States)

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf

2017-11-20

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two-step reaction mechanism-1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom-shows that it mirrors acid-catalyzed ether cleavage in solution. The O-Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell-Evans-Polanyi principle. Electron rearrangement during C-O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S N 2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Influence of Pyrite on the Solubility of Minjingu and Panda ...

African Journals Online (AJOL)

28.5 million tons of sulphur. This study was ... bining PRs with elemental S, FYM ot 'and pyrite rock rere used.in this compost (Chien et al., ... Some of the possibility of using locally available the chemical properties of the rocks materials in ...

3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

Science.gov (United States)

Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

2015-01-01

Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

Gold and trace element zonation in pyrite using a laser imaging technique: Implications for the timing of gold in orogenic and carlin-style sediment-hosted deposits

Science.gov (United States)

Large, R.R.; Danyushevsky, L.; Hollit, C.; Maslennikov, V.; Meffre, S.; Gilbert, S.; Bull, S.; Scott, R.; Emsbo, P.; Thomas, H.; Singh, B.; Foster, J.

2009-01-01

Laser ablation ICP-MS imaging of gold and other trace elements in pyrite from four different sediment- hosted gold-arsenic deposits has revealed two distinct episodes of gold enrichment in each deposit: an early synsedimentary stage where invisible gold is concentrated in arsenian diagenetic pyrite along with other trace elements, in particular, As, Ni, Pb, Zn, Ag, Mo, Te, V, and Se; and a later hydrothermal stage where gold forms as either free gold grains in cracks in overgrowth metamorphic and/or hydrothermal pyrite or as narrow gold- arsenic rims on the outermost parts of the overgrowth hydrothermal pyrite. Compared to the diagenetic pyrites, the hydrothermal pyrites are commonly depleted in Ni, V, Zn, Pb, and Ag with cyclic zones of Co, Ni, and As concentration. The outermost hydrothermal pyrite rims are either As-Au rich, as in moderate- to high- grade deposits such as Carlin and Bendigo, or Co-Ni rich and As-Au poor as in moderate- to low-grade deposits such as Sukhoi Log and Spanish Mountain. The early enrichment of gold in arsenic-bearing syngenetic to diagenetic pyrite, within black shale facies of sedimentary basins, is proposed as a critical requirement for the later development of Carlin-style and orogenic gold deposits in sedimentary environments. The best grade sediment-hosted deposits appear to have the gold climax event, toward the final stages of deformation-related hydrothermal pyrite growth and fluid flow. ?? 2009 Society of Economic Geologists, Inc.

Review: Impacts of permafrost degradation on inorganic chemistry of surface fresh water

Science.gov (United States)

Colombo, Nicola; Salerno, Franco; Gruber, Stephan; Freppaz, Michele; Williams, Mark; Fratianni, Simona; Giardino, Marco

2018-03-01

Recent studies have shown that climate change is impacting the inorganic chemical characteristics of surface fresh water in permafrost areas and affecting aquatic ecosystems. Concentrations of major ions (e.g., Ca2 +, Mg2 +, SO42 -, NO3-) can increase following permafrost degradation with associated deepening of flow pathways and increased contributions of deep groundwater. In addition, thickening of the active layer and melting of near-surface ground ice can influence inorganic chemical fluxes from permafrost into surface water. Permafrost degradation has also the capability to modify trace element (e.g., Ni, Mn, Al, Hg, Pb) contents in surface water. Although several local and regional modifications of inorganic chemistry of surface fresh water have been attributed to permafrost degradation, a comprehensive review of the observed changes is lacking. The goal of this paper is to distil insight gained across differing permafrost settings through the identification of common patterns in previous studies, at global scale. In this review we focus on three typical permafrost configurations (pervasive permafrost degradation, thermokarst, and thawing rock glaciers) as examples and distinguish impacts on (i) major ions and (ii) trace elements. Consequences of warming climate have caused spatially-distributed progressive increases of major ion and trace element delivery to surface fresh water in both polar and mountain areas following pervasive permafrost degradation. Moreover, localised releases of major ions and trace elements to surface water due to the liberation of soluble materials sequestered in permafrost and ground ice have been found in ice-rich terrains both at high latitude (thermokarst features) and high elevation (rock glaciers). Further release of solutes and related transport to surface fresh water can be expected under warming climatic conditions. However, complex interactions among several factors able to influence the timing and magnitude of the impacts

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

KAUST Repository

Cabán-Acevedo, Miguel

2015-09-14

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS 2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm at overpotentials as low as 48mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n -p-p silicon micropyramids achieved photocurrents up to 35 mA cm at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine

Science.gov (United States)

Cravotta, C.A.

1998-01-01

Data on rock, ground water, vadose water, and vadose gas chemistry were collected for two years after sewage sludge was applied at a reclaimed surface coal mine in Pennsylvania to determine if surface-applied sludge is an effective barrier to oxygen influx, contributes metals and nutrients to ground water, and promotes the acidification of ground water. Acidity, sulfate, and metals concentrations were elevated in the ground water (6- to 21-m depth) from spoil relative to unmined rock because of active oxidation of pyrite and dissolution of aluminosilicate, carbonate, and Mn-Fe-oxide minerals in the spoil. Concentrations of acidity, sulfate, metals (Fe, Mn, Al, Cd, Cu, Cr, Ni, Zn), and nitrate, and abundances of iron-oxidizing bacteria were elevated in the ground water from sludge-treated spoil relative to untreated spoil having a similar mineral composition; however, gaseous and dissolved oxygen concentrations did not differ between the treatments. Abundances of iron-oxidizing bacteria in the ground water samples were positively correlated with concentrations of ammonia, nitrate, acidity, metals, and sulfate. Concentrations of metals in vadose water samples (oxidation of pyrite by nitrate. Thus, sewage sludge added to pyritic spoil can increase the growth of iron-oxidizing bacteria, the oxidation of pyrite, and the acidification of ground water. Nevertheless, the overall effects on ground water chemistry from the sludge were small and probably short-lived relative to the effects from mining only.

Archaeal diversity and the extent of iron and manganese pyritization in sediments from a tropical mangrove creek (Cardoso Island, Brazil)

Science.gov (United States)

Otero, X. L.; Lucheta, A. R.; Ferreira, T. O.; Huerta-Díaz, M. A.; Lambais, M. R.

2014-06-01

Even though several studies on the geochemical processes occurring in mangrove soils and sediments have been performed, information on the diversity of Archaea and their functional roles in these ecosystems, especially in subsurface environments, is scarce. In this study, we have analyzed the depth distribution of Archaea and their possible relationships with the geochemical transformations of Fe and Mn in a sediment core from a tropical mangrove creek, using 16S rRNA gene profiling and sequential extraction of different forms of Fe and Mn. A significant shift in the archaeal community structure was observed in the lower layers (90-100 cm), coinciding with a clear decrease in total organic carbon (TOC) content and an increase in the percentage of sand. The comparison of the archaeal communities showed a dominance of methanogenic Euryarchaeota in the upper layers (0-20 cm), whereas Crenarchaeota was the most abundant taxon in the lower layers. The dominance of methanogenic Euryarchaeota in the upper layer of the sediment suggests the occurrence of methanogenesis in anoxic microenvironments. The concentrations of Fe-oxyhydroxides in the profile were very low, and showed positive correlation with the concentrations of pyrite and degrees of Fe and Mn pyritization. Additionally, a partial decoupling of pyrite formation from organic matter concentration was observed, suggesting excessive Fe pyritization. This overpyritization of Fe can be explained either by the anoxic oxidation of methane by sulfate and/or by detrital pyrite tidal transportation from the surrounding mangrove soils. The higher pyritization levels observed in deeper layers of the creek sediment were also in agreement with its Pleistocenic origin.

Biogeochemistry of pyrite and iron sulfide oxidation in marine sediments

DEFF Research Database (Denmark)

Schippers, A.; Jørgensen, BB

2002-01-01

as substrates and NO3- as electron acceptor, in the presence of (FeS2)-Fe-55, to test for co-oxidation of FeS2, but an anaerobic microbial dissolution of (FeS2)-Fe-55, could not been detected. FeS2 and FeS were not oxidized by amorphous Fe(III) oxide in the presence of Fe-complexing organic compounds......Pyrite (FeS2) and iron monosulfide (FeS) play a central role in the sulfur and iron cycles of marine sediments, They may be buried in the sediment or oxidized by O-2 after transport by bioturbation to the sediment surface. FeS2 and FeS may also be oxidized within the anoxic sediment in which NO3...... marine sediments and incubated at different temperatures for > 1 yr. Bacteria could not be enriched with FeS2 as substrate or with FeS and amorphous Fe(III) oxide. With FeS and NO3-, 14 enrichments were obtained. One of these enrichments was further cultivated anaerobically with Fe2+ and S-0...

Emphasizing the role of surface chemistry on hydrophobicity and cell adhesion behavior of polydimethylsiloxane/TiO2 nanocomposite films.

Science.gov (United States)

Yousefi, Seyedeh Zahra; Tabatabaei-Panah, Pardis-Sadat; Seyfi, Javad

2018-07-01

Improving the bioinertness of materials is of great importance for developing biomedical devices that contact human tissues. The main goal of this study was to establish correlations among surface morphology, roughness and chemistry with hydrophobicity and cell adhesion in polydimethylsiloxane (PDMS) nanocomposites loaded with titanium dioxide (TiO 2 ) nanoparticles. Firstly, wettability results showed that the nanocomposite loaded with 30 wt.% of TiO 2 exhibited a superhydrophobic behavior; however, the morphology and roughness analysis proved that there was no discernible difference between the surface structures of samples loaded with 20 and 30 wt.% of nanoparticles. Both cell culture and MTT assay experiments showed that, despite the similarity between the surface structures, the sample loaded with 30 wt.% nanoparticles exhibits the greatest reduction in the cell viability (80%) as compared with the pure PDMS film. According to the X-ray photoelectron spectroscopy results, the remarkable reduction in cell viability of the superhydrophobic sample could be majorly attributed to the role of surface chemistry. The obtained results emphasize the importance of adjusting the surface properties especially surface chemistry to gain the optimum cell adhesion behavior. Copyright © 2018 Elsevier B.V. All rights reserved.

Surface chemistry of first wall materials - From fundamental data to modeling

International Nuclear Information System (INIS)

Linsmeier, Ch.; Reinelt, M.; Schmid, K.

2011-01-01

The application of different materials at the first wall of fusion devices, like beryllium, carbon, and tungsten in the case of ITER, unavoidably leads to the formation of compounds. These compounds are created dynamically during operation and depend on the local parameters like surface temperature, incoming particle energies and species. In dedicated, well-defined laboratory experiments, using mainly X-ray photoelectron spectroscopy and Rutherford backscattering analysis for qualitative and quantitative chemical surface analysis, the parameter space in relevant element combinations are investigated. These studies lead to a deep understanding of the reaction mechanisms under the applied conditions and to a quantitative description of reaction and diffusion processes. These data can be parameterized and integrated into a modeling approach which combines dynamic surface chemistry with the modeling of the transport in the plasma. Two different approaches for surface reaction modeling are compared and benchmarked with experimental data.

Endothelial cell behaviour on gas-plasma-treated PLA surfaces: the roles of surface chemistry and roughness.

Science.gov (United States)

Shah, Amita; Shah, Sarita; Mani, Gopinath; Wenke, Joseph; Agrawal, Mauli

2011-04-01

Glow-discharge gas-plasma (GP) treatment has been shown to induce surface modifications such that cell adhesion and growth are enhanced. However, it is not known which gas used in GP treatment is optimal for endothelial cell function. Polylactic acid (PLA) films treated oxygen, argon, or nitrogen GP were characterized using contact angles, scanning electron microscopy, atomic force microscopy, optical profilometry, and x-ray photoelectron spectroscopy. All three GP treatments decreased the carbon atomic concentration and surface roughness and increased the oxygen atomic concentration. Human umbilical vein endothelial cells were cultured on the PLA films for up to 7 days. Based on proliferation and live/dead assays, surface chemistry was shown to have the greatest effect on the attachment, proliferation, and viability of these cells, while roughness did not have a significant influence. Of the different gases, endothelial cell viability, attachment and proliferation were most significantly increased on PLA surfaces treated with oxygen and argon gas plasma. Copyright © 2010 John Wiley & Sons, Ltd.

Microbial leaching of iron from pyrite by moderate thermophile chemolithotropic bacteria

International Nuclear Information System (INIS)

Ilyas, S.; Niazi, S.B.

2007-01-01

The present work was aimed at studying the bioleachability of iron from pyrite by the selected moderately thermophilic strains of acidophilic chemolithotrophic and acidophilic heterotrophic bacteria. These included Sulfobacillus thermosulfidooxidans (chemolithotroph) and an un-identified strain of acidophilic heterotroph (code 6A1TSB) isolated from local environments. As compared to inoculated flasks, dissolution of metal (due to acid leaching) was significantly low in the un-inoculated control flasks in all the experiments in ore. A decrease in the bioleaching activity was observed at the later stages of bioleaching of metal from ore. Among the strategies adopted to enhance the metal leaching rates, a mixed consortium of the metal adapted cultures of the above-mentioned bacteria was found to exhibit the maximum metal leaching efficiency. In all the flasks where high metal leaching rates were observed, concomitantly biomass production rates were also high indicating high growth rates. It showed that the metal bioleaching capability of the bacteria was associated with their growth. Pyrite contained 42% iron. (author)

Isolation and characterization of bacteria on the drainage water from Ratones mine and its behaviour on pyrite

International Nuclear Information System (INIS)

Merino, J. L.; Saez, R. M.

1974-01-01

This paper describes some of the studies made about iron and sulfur oxidizing bacteria on the drainage water from Ratones mine. Different liquid and solid media were utilized as well as some energy sources, ferrous sulphate, thiosulfate and sulfur. Some experiment were al so realized on museum grade pyrite aimed at determining the possibilities of applying the mentioned bacteria on the leaching of pyrite and subsequently on the leaching of uranium ores. (Author) 27 refs

The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

Science.gov (United States)

Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

1994-01-01

Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

Interaction between carbon fibers and polymer sizing: Influence of fiber surface chemistry and sizing reactivity

Science.gov (United States)

Moosburger-Will, Judith; Bauer, Matthias; Laukmanis, Eva; Horny, Robert; Wetjen, Denise; Manske, Tamara; Schmidt-Stein, Felix; Töpker, Jochen; Horn, Siegfried

2018-05-01

Different aspects of the interaction of carbon fibers and epoxy-based polymer sizings are investigated, e.g. the wetting behavior, the strength of adhesion between fiber and sizing, and the thermal stability of the sizing layer. The influence of carbon fiber surface chemistry and sizing reactivity is investigated using fibers of different degree of anodic oxidation and sizings with different number of reactive epoxy groups per molecule. Wetting of the carbon fibers by the sizing dispersion is found to be specified by both, the degree of fiber activation and the sizing reactivity. In contrast, adhesion strength between fibers and sizing is dominated by the surface chemistry of the carbon fibers. Here, the number of surface oxygen groups seems to be the limiting factor. We also find that the sizing and the additional functionalities induced by anodic oxidation are removed by thermal treatment at 600 °C, leaving the carbon fiber in its original state after carbonization.

The influence of the surface chemistry of silver nanoparticles on cell death

International Nuclear Information System (INIS)

Sur, Ilknur; Altunbek, Mine; Kahraman, Mehmet; Culha, Mustafa

2012-01-01

The influence of the surface chemistry of silver nanoparticles (AgNPs) on p53 mediated cell death was evaluated using human dermal fibroblast (HDF) and lung cancer (A549) cells. The citrate reduced AgNPs (C-AgNPs) were modified with either lactose (L-AgNPs) or a 12-base long oligonucleotide (O-AgNPs). Both unmodified and modified AgNPs showed increased concentration and time dependent cytotoxicity and genotoxicity causing an increased p53 up-regulation within 6 h and led to apoptotic or necrotic cell deaths. The C-AgNPs induced more cytotoxicity and cellular DNA damage than the surface modified AgNPs. Modifying the C-AgNPs with lactose or the oligonucleotide reduced both necrotic and apoptotic cell deaths in the HDF cells. The C-AgNPs caused an insignificant necrosis in A549 cells whereas the modified AgNPs caused necrosis and apoptosis in both cell types. Compared to the O-AgNPs, the L-AgNPs triggered more cellular DNA damage, which led to up-regulation of p53 gene inducing apoptosis in A549 cells compared to HDF cells. This suggests that the different surface chemistries of the AgNPs cause different cellular responses that may be important not only for their use in medicine but also for reducing their toxicity. (paper)

Understanding surface structure and chemistry of single crystal lanthanum aluminate

KAUST Repository

Pramana, Stevin S.

2017-03-02

The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10−10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10−6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

Characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems.

Science.gov (United States)

Bryant, M; Ward, M; Farrar, R; Freeman, R; Brummitt, K; Nolan, J; Neville, A

2014-04-01

This study presents the characterisation of the surface topography, tomography and chemistry of fretting corrosion product found on retrieved polished femoral stems. Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FI-IR) were utilised in order to assess the surface morphology of retrieved Metal-on-Metal Total Hip Replacements and surface chemistry of the films found on the surface. Gross slip, plastic deformation and directionality of the surface were extensively seen on the proximal surfaces of the retrievals. A more corrosive phenomenon was observed in the distal regions of the stem, demonstrating a seemingly intergranular attack. Tribochemical reactions were seen to occur within the stem-cement interfaces with tribofilms being observed on the femoral stem and counterpart PMMA bone cement. XPS, TEM-EDX and FT-IR analyses demonstrated that the films present in the stem surfaces were a complex mixture of chromium oxide and amorphous organic material. A comparison between current experimental and clinical literature has been conducted and findings from this study demonstrate that the formation and chemistry of films are drastically influenced by the type of wear or degradation mechanism. Films formed in the stem-cement interface are thought to further influence the biological environment outside the stem-cement interface due to the formation of Cr and O rich films within the interface whilst Co is free to migrate away. © 2013 Elsevier Ltd. All rights reserved.

WATER CHEMISTRY ASSESSMENT METHODS

Science.gov (United States)

This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

The hidden radiation chemistry in plasma modification and XPS analysis of polymer surfaces

International Nuclear Information System (INIS)

George, G.A.; Le, T.T.; Elms, F.M.; Wood, B.J.

1996-01-01

Full text: The surface modification of polymers using plasma treatments is being widely researched to achieve changes in the surface energetics and consequent wetting and reactivity for a range of applications. These include i) adhesion for polymer bonding and composite material fabrication and ii) biocompatibility of polymers when used as orthopedic implants, catheters and prosthetics. A low pressure rf plasma produces a variety of species from the introduced gas which may react with the surface of a hydrocarbon polymer, such as polyethylene. In the case of 0 2 and H 2 0, these species include oxygen atoms, singlet molecular oxygen and hydroxyl radicals, all of which may oxidise and, depending on their energy, ablate the polymer surface. In order to better understand the reactive species formed both in and downstream from a plasma and the relative contributions of oxidation and ablation, self-assembled monolayers of n-alkane thiols on gold are being used as well characterised substrates for quantitative X-ray photoelectron spectroscopy (XPS). The identification and quantification of oxidised carbon species on plasma treated polymers from broad, asymmetric XPS signals is difficult, so derivatisation is often used to enhance sensitivity and specificity. For example, trifluoroacetic anhydride (TFAA) selectively labels hydroxyl functionality. The surface analysis of a modified polymer surface may be confounded by high energy radiation chemistry which may occur during XPS analysis. Examples include scission of carbon-halogen bonds (as in TFM adducts), decarboxylation and main-chain polyene formation. The extent of free-radical chemistry occurring in polyethylene while undergoing XPS analysis may be seen by both ESR and FT-IR analysis

Surface and interfacial chemistry of high-k dielectric and interconnect materials on silicon

Science.gov (United States)

Kirsch, Paul Daniel

Surfaces and interfaces play a critical role in the manufacture and function of silicon based integrated circuits. It is therefore reasonable to study the chemistries at these surfaces and interfaces to improve existing processes and to develop new ones. Model barium strontium titanate high-k dielectric systems have been deposited on ultrathin silicon oxynitride in ultrahigh vacuum. The resulting nanostructures are characterized with secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). An interfacial reaction between Ba and Sr atoms and SiOxNy was found to create silicates, BaSixOy or SrSi xOy. Inclusion of N in the interfacial oxide decreased silicate formation in both Ba and Sr systems. Furthermore, inclusion of N in the interfacial oxide decreased the penetration of Ba and Sr containing species, such as silicides and silicates. Sputter deposited HfO2 was studied on nitrided and unnitrided Si(100) surfaces. XPS and SIMS were used to verify the presence of interfacial HfSixOy and estimate its relative amount on both nitrided and unnitrided samples. More HfSixOy formed without the SiNx interfacial layer. These interfacial chemistry results are then used to explain the electrical measurements obtained from metal oxide semiconductor (MOS) capacitors. MOS capacitors with interfacial SiNx exhibit reduced leakage current and increased capacitance. Lastly, surface science techniques were used to develop a processing technique for reducing thin films of copper (II) and copper (I) oxide to copper. Deuterium atoms (D*) and methyl radicals (CH3*) were shown to reduce Cu 2+ and/or Cu1+ to Cu0 within 30 min at a surface temperature of 400 K under a flux of 1 x 1015 atoms/cm2s. Temperature programmed desorption experiments suggest that oxygen leaves the surface as D2O and CO2 for the D* and CH3* treated surfaces, respectively.

Acid mine drainage - the chemistry

CSIR Research Space (South Africa)

Garland, Rebecca M

2011-01-01

Full Text Available into smaller fragments. These smaller fragments have a larger surface area so more of the pyrite is exposed at any one time to air and water. This is especially seen in the mine dumps such as gold tailing dumps, where rainwater can seep through the dump... then has to be constantly pumped out of the mine in order to prevent the reactions shown in the equations from occurring. In equation (2), the iron (II) cation goes on to further react with oxygen and some of the H+ from equation (1...

THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

Science.gov (United States)

In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

DEFF Research Database (Denmark)

Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun

2018-01-01

functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

Non-thermally activated chemistry

International Nuclear Information System (INIS)

Stiller, W.

1987-01-01

The subject is covered under the following headings: state-of-the art of non-thermally activated chemical processes; basic phenomena in non-thermal chemistry including mechanochemistry, photochemistry, laser chemistry, electrochemistry, photo-electro chemistry, high-field chemistry, magneto chemistry, plasma chemistry, radiation chemistry, hot-atom chemistry, and positronium and muonium chemistry; elementary processes in non-thermal chemistry including nuclear chemistry, interactions of electromagnetic radiations, electrons and heavy particles with matter, ionic elementary processes, elementary processes with excited species, radicalic elementary processes, and energy-induced elementary processes on surfaces and interfaces; and comparative considerations. An appendix with historical data and a subject index is given. 44 figs., 41 tabs., and 544 refs

Acidic deposition: State of science and technology. Report 14. Methods for projecting future changes in surface water acid-base chemistry. Final report

International Nuclear Information System (INIS)

Thornton, K.W.; Marmorek, D.; Ryan, P.F.; Heltcher, K.; Robinson, D.

1990-09-01

The objectives of the report are to: critically evaluate methods for projecting future effects of acidic deposition on surface water acid-base chemistry; review and evaluate techniques and procedures for analyzing projection uncertainty; review procedures for estimating regional lake and stream population attributes; review the U.S. Environmental Protection Agency (EPA) Direct/Delayed Response Project (DDRP) methodology for projecting the effects of acidic deposition on future changes in surface water acid-base chemistry; and present the models, uncertainty estimators, population estimators, and proposed approach selected to project the effects of acidic deposition on future changes in surface water acid-base chemistry in the NAPAP 1990 Integrated Assessment and discuss the selection rationale

Effects of various tailings covers on radon gas emanation from pyritic uranium tailings

International Nuclear Information System (INIS)

Dave, N.K.; Lim, T.P.

1987-01-01

Radon emanation studies were carried out at an inactive pyritic uranium tailings site in Elliot Lake, Ontario, Canada, to evaluate the effects of various existing dry and wet covers on radon flux rates. Measurements were taken using activated charcoal cartridges for various surface covers consisting of bare, vegetated, acidophilic moss with high degree of water saturation, compacted crushed rock and gravel, and winter snow. The results showed that at a given site, there was no significant difference in radon emanation rates between various tailings covers and bare tailings. In particular, no increase In radon emanation rates from vegetated areas compared to bare tailings was observed. Radon emanation rates varied spatially depending on tailings grain size, porosity, moisture content and on pressure and water table variations. The emanation rates were higher for tailings with low water contents compared to those for wet and moss covered tailings

Pyrite thermochemistry, ash agglomeration, and char fragmentation during pulverized coal combustion. Final technical report

Energy Technology Data Exchange (ETDEWEB)

Akan-Etuk, A.; Diaz, R.; Niksa, S.

1991-10-01

The objective of the present work is to introduce an experimental program that will eventually lead to time-resolved iron ash composition over the technological operating domain. The preceding literature survey suggests two important stipulations on any such experimental program. The first stipulation is that good control must be established over the operating conditions, to accurately quantify their effects. The other is that data must be obtained rapidly, to thoroughly cover the important operating domain. This work presents a series of studies that has characterized the desulfurization of pyrite during the early stages of combustion. An experimental system was established and used to monitor the effects of oxygen, temperature, and residence time on the evolution of condensed phase products of the combustion of pure pyrite. (VC)

Electron tunneling in chemistry

International Nuclear Information System (INIS)

Zamaraev, K.I.; Khajrutdinov, R.F.; Zhdanov, V.P.; Molin, Yu.N.

1985-01-01

Results of experimental and theoretical investigations are outlined systematically on electron tunnelling in chemical reactions. Mechanism of electron transport to great distances is shown to be characteristic to chemical compounds of a wide range. The function of tunnel reactions is discussed for various fields of chemistry, including radiation chemistry, electrochemistry, chemistry of solids, chemistry of surface and catalysis

Estimating the Analytical and Surface Enhancement Factors in Surface-Enhanced Raman Scattering (SERS): A Novel Physical Chemistry and Nanotechnology Laboratory Experiment

Science.gov (United States)

Pavel, Ioana E.; Alnajjar, Khadijeh S.; Monahan, Jennifer L.; Stahler, Adam; Hunter, Nora E.; Weaver, Kent M.; Baker, Joshua D.; Meyerhoefer, Allie J.; Dolson, David A.

2012-01-01

A novel laboratory experiment was successfully implemented for undergraduate and graduate students in physical chemistry and nanotechnology. The main goal of the experiment was to rigorously determine the surface-enhanced Raman scattering (SERS)-based sensing capabilities of colloidal silver nanoparticles (AgNPs). These were quantified by…

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

Science.gov (United States)

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study on the surface sulfidization behavior of smithsonite at high temperature

Science.gov (United States)

Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

2018-04-01

Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

Controlled surface chemistry of diamond/β-SiC composite films for preferential protein adsorption.

Science.gov (United States)

Wang, Tao; Handschuh-Wang, Stephan; Yang, Yang; Zhuang, Hao; Schlemper, Christoph; Wesner, Daniel; Schönherr, Holger; Zhang, Wenjun; Jiang, Xin

2014-02-04

Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/β-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/β-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/β-SiC ratio of the composite films shows a continuous change from pure diamond to β-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/β-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on β-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/β-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on β-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/β-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/β-SiC gradient film can be a promising material for biomedical applications which

Rapid changes in surface water carbonate chemistry during Antarctic sea ice melt

Science.gov (United States)

Jones, Elizabeth M.; Bakker, Dorothee C. E.; Venables, Hugh J.; Whitehouse, Michael J.; Korb, Rebecca E.; Watson, Andrew J.

2010-11-01

ABSTRACT The effect of sea ice melt on the carbonate chemistry of surface waters in the Weddell-Scotia Confluence, Southern Ocean, was investigated during January 2008. Contrasting concentrations of dissolved inorganic carbon (DIC), total alkalinity (TA) and the fugacity of carbon dioxide (fCO2) were observed in and around the receding sea ice edge. The precipitation of carbonate minerals such as ikaite (CaCO3.6H2O) in sea ice brine has the net effect of decreasing DIC and TA and increasing the fCO2 in the brine. Deficits in DIC up to 12 +/- 3 μmol kg-1 in the marginal ice zone (MIZ) were consistent with the release of DIC-poor brines to surface waters during sea ice melt. Biological utilization of carbon was the dominant processes and accounted for 41 +/- 1 μmol kg-1 of the summer DIC deficit. The data suggest that the combined effects of biological carbon uptake and the precipitation of carbonates created substantial undersaturation in fCO2 of 95 μatm in the MIZ during summer sea ice melt. Further work is required to improve the understanding of ikaite chemistry in Antarctic sea ice and its importance for the sea ice carbon pump.

Defect formation energies and homogeneity ranges of rock salt-, pyrite-, chalcopyrite- and molybdenite-type compound semiconductors

Energy Technology Data Exchange (ETDEWEB)

Fiechter, S. [Hahn-Meitner-Institut, Glienicker Strasse 100, Berlin D-14109 (Germany)

2004-07-01

Employing the generalisation of Van Vechten's cavity model, formation energies of neutral point defects in pyrites (FeS{sub 2}, RuS{sub 2}), chalcopyrites (II-IV-V{sub 2} and I-III-VI{sub 2}) as well as molybdenites (MoS{sub 2}, WS{sub 2}) have been estimated. As input parameters the fundamental band gaps, work functions, electron affinities, surface energies, coordination numbers, covalent or ionic radii and unit cell parameters were used. The values calculated for tetrahedrally and octahedrally coordinated compounds agreed well with measured values. The data obtained can be used to calculate point defect concentrations and homogeneity ranges as a function of partial pressure and temperature. Introducing charged vacancies, the conductivity type can be predicted.

Uranium pollution in an estuary affected by pyrite acid mine drainage and releases of naturally occurring radioactive materials

International Nuclear Information System (INIS)

Villa, M.; Manjon, G.; Hurtado, S.; Garcia-Tenorio, R.

2011-01-01

Highlights: → Huelva estuary is affected by former phosphogypsum releases and pyrite acid mine drainage. → Time evolution of uranium concentration is analyzed after halting of NORM releases. → Two new contamination sources are preventing the complete uranium cleaning: (1) The leaching of phosphogypsum stacks located close to Tinto River. (2) Pyrite acid mine drainage. → High uranium concentrations are dissolved in water and precipitate subsequently. - Abstract: After the termination of phosphogypsum discharges to the Huelva estuary (SW Spain), a unique opportunity was presented to study the response of a contaminated environmental compartment after the cessation of its main source of pollution. The evolution over time of uranium concentrations in the estuary is presented to supply new insights into the decontamination of a scenario affected by Naturally Occurring Radioactive Material (NORM) discharges. The cleaning of uranium isotopes from the area has not taken place as rapidly as expected due to leaching from phosphogypsum stacks. An in-depth study using various techniques of analysis, including 234 U/ 238 U and 230 Th/ 232 Th ratios and the decreasing rates of the uranium concentration, enabled a second source of uranium contamination to be discovered. Increased uranium levels due to acid mine drainage from pyrite mines located in the Iberian Pyrite Belt (SW Spain) prevent complete uranium decontamination and, therefore, result in levels nearly twice those of natural background levels.

Clathrin to Lipid Raft-Endocytosis via Controlled Surface Chemistry and Efficient Perinuclear Targeting of Nanoparticle.

Science.gov (United States)

Chakraborty, Atanu; Jana, Nikhil R

2015-09-17

Nanoparticle interacts with live cells depending on their surface chemistry, enters into cell via endocytosis, and is commonly trafficked to an endosome/lysozome that restricts subcellular targeting options. Here we show that nanoparticle surface chemistry can be tuned to alter their cell uptake mechanism and subcellular trafficking. Quantum dot based nanoprobes of 20-30 nm hydrodynamic diameters have been synthesized with tunable surface charge (between +15 mV to -25 mV) and lipophilicity to influence their cellular uptake processes and subcellular trafficking. It is observed that cationic nanoprobe electrostatically interacts with cell membrane and enters into cell via clathrin-mediated endocytosis. At lower surface charge (between +10 mV to -10 mV), the electrostatic interaction with cell membrane becomes weaker, and additional lipid raft endocytosis is initiated. If a lipophilic functional group is introduced on a weakly anionic nanoparticle surface, the uptake mechanism shifts to predominant lipid raft-mediated endocytosis. In particular, the zwitterionic-lipophilic nanoprobe has the unique advantage as it weakly interacts with anionic cell membrane, migrates toward lipid rafts for interaction through lipophilic functional group, and induces lipid raft-mediated endocytosis. While predominate or partial clathrin-mediated entry traffics most of the nanoprobes to lysozome, predominate lipid raft-mediated entry traffics them to perinuclear region, particularly to the Golgi apparatus. This finding would guide in designing appropriate nanoprobe for subcellular targeting and delivery.

Effect of electrochemical treatments on the surface chemistry of activated carbon

OpenAIRE

Berenguer Betrián, Raúl; Marco Lozar, Juan Pablo; Quijada Tomás, César; Cazorla Amorós, Diego; Morallón Núñez, Emilia

2008-01-01

The effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous structure of a granular activated carbon (GAC) has been analyzed by means of temperature-programmed desorption and N2 (at 77 K) and CO2 (at 273 K) adsorption isotherms. The anodic and cathodic treatments, the applied current (between 0.2 and 2.0 A) and the type of electrolyte (NaOH, H2SO4 and NaCl)have been studied as electrochemical variables. Bo...

On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

DEFF Research Database (Denmark)

Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

2011-01-01

This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying di...

Assessment of the surface chemistry of carbon blacks by TGA-MS, XPS and inverse gas chromatography using statistical chemometric analysis

International Nuclear Information System (INIS)

Strzemiecka, Beata; Voelkel, Adam; Donate-Robles, Jessica; Martín-Martínez, José Miguel

2014-01-01

Highlights: • Carbon blacks with lower specific surface area had basic character (electron donor) due to C=O and C-O groups. • Carbon blacks with higher specific surface area had acidic character (acceptor electron) due to OH groups. • Total surface energy and its dispersive component of carbon blacks increased by increasing their specific surface area. (table) - Abstract: Four carbon blacks with different specific surface areas and surface chemistries (C32, C71, C159 and C178) were analyzed by transmission electron microscopy (TEM) and nitrogen adsorption isotherms at 77 K. Their surface chemistries were analyzed by X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis coupled with mass spectrometry (TGA-MS) and inverse gas chromatography (IGC). The carbon blacks contained 2.7–5.8 wt% volatiles corresponding to -OH, C-O, C=O and COO groups. The surface chemistry parameters obtained with the different experimental techniques were inter-related by using chemometric statistical analysis tools. The application of this methodology showed that the carbon blacks with lower specific surface area (C32 and C71) had basic character (electron donor) mainly due to C=O and C-O groups, whereas the carbon black with the highest specific surface area (C178) showed acidic character (acceptor electron) due to its high content of OH groups. Moreover, the total surface energy and the dispersive component of the surface energy of the carbon blacks increased with the increase of their specific surface area. In general the specific interactions of the carbon blacks also increased with the increase of their specific surface area although C71 is exceptional due to higher oxygen content corresponding to C-O groups

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

Directory of Open Access Journals (Sweden)

Imen Ghouma

2018-04-01

Full Text Available The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy (FTIR techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2.

Control and Characterization of Titanium Dioxide Morphology: Applications in Surface Organometallic Chemistry

KAUST Repository

Jeantelot, Gabriel

2014-05-01

Surface Organometallic Chemistry leads to the combination of the high activity and specificity of homogeneous catalysts with the recoverability and practicality of heterogeneous catalysts. Most metal complexes used in this chemistry are grafted on metal oxide supports such as amorphous silica (SiO2) and γ-alumina (Al2O3). In this thesis, we sought to enable the use of titania (TiO2) as a new support for single-site well-defined grafting of metal complexes. This was achieved by synthesizing a special type of anatase-TiO2, bearing a high density of identical hydroxyl groups, through hydrothermal synthesis then post-treatment under high vacuum followed by oxygen flow, and characterized by several analytical techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and nuclear magnetic resonance. Finally, as a proof of concept, the grafting of vanadium oxychloride (VOCl3) was successfully attempted.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization.

Science.gov (United States)

Struzzi, Claudia; Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

2017-01-01

The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF 4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization

Directory of Open Access Journals (Sweden)

Claudia Struzzi

2017-08-01

Full Text Available The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT is correlated to the CF4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

Science.gov (United States)

Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna; Nowakowska, Maria; Szczubiałka, Krzysztof

2014-12-01

Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2

Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

Directory of Open Access Journals (Sweden)

Anna eMikulska

2015-01-01

Full Text Available Polymeric surfaces suitable for cell culture (DR/Pec were constructed from diazoresin (DR and pectin (Pec in a form of ultrathin films using the layer-by-layer (LbL technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2 to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2

The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

KAUST Repository

Hong, Jongsup

2015-08-01

© 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes

KAUST Repository

Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Cui, Yi

2009-01-01

Silicon nanowires (SiNWs) have the potential to perform as anodes for lithium-ion batteries with a much higher energy density than graphite. However, there has been little work in understanding the surface chemistry of the solid electrolyte

Atomic scale study of the chemistry of oxygen, hydrogen and water at SiC surfaces

International Nuclear Information System (INIS)

Amy, Fabrice

2007-01-01

Understanding the achievable degree of homogeneity and the effect of surface structure on semiconductor surface chemistry is both academically challenging and of great practical interest to enable fabrication of future generations of devices. In that respect, silicon terminated SiC surfaces such as the cubic 3C-SiC(1 0 0) 3 x 2 and the hexagonal 6H-SiC(0 0 0 1) 3 x 3 are of special interest since they give a unique opportunity to investigate the role of surface morphology on oxygen or hydrogen incorporation into the surface. In contrast to silicon, the subsurface structure plays a major role in the reactivity, leading to unexpected consequences such as the initial oxidation starting several atomic planes below the top surface or the surface metallization by atomic hydrogen. (review article)

Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well

Directory of Open Access Journals (Sweden)

Fabienne Poncin-Epaillard

2012-04-01

Full Text Available The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic—phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°, negatively charged and smooth inner surface.

Soil pollution by a pyrite mine spill in Spain: evolution in time

International Nuclear Information System (INIS)

Aguilar, J.; Dorronsoro, C.; Fernandez, E.; Fernandez, J.; Garcia, I.; Martin, F.; Simon, M.

2004-01-01

Soil pollution was studied after the spill of the Aznalcollar pyrite mine between 1998 and 2001, analyzing As, Zn, Cd, Cu and Pb both in total concentrations as well as in soluble and bioavailable forms. The main remediation measures were: clean-up of the tailings and polluted soils, plus application of amendment materials (liming). The results indicate that, after three years, 50-70% of the acidic soils and 25-30% of the basic soils are still highly polluted in total arsenic. The limit of 0.04 mg kg -1 for water-soluble arsenic is exceeded in 15-20% of all soils. The EDTA-extractable arsenic (bioavailable) exceeds the limit of 2 mg kg -1 only in the acidic sectors. After clean-up, the homogenization of the upper 20-25 cm of the soils appears to be the most recommended measure in the reduction of pollution. - Capsule: Remediation measures carried out after the Aznalcollar pyrite mine spill were effective in the reduction of the pollution, although three years after the accident many areas are still polluted by As

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

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Norhan Nady

2016-04-01

Full Text Available A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone (PES membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid—is presented.

PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

Science.gov (United States)

Nady, Norhan

2016-04-18

A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

Surface chemistry and microstructure of metallic biomaterials for hip and knee endoprostheses

Science.gov (United States)

Jenko, Monika; Gorenšek, Matevž; Godec, Matjaž; Hodnik, Maxinne; Batič, Barbara Šetina; Donik, Črtomir; Grant, John T.; Dolinar, Drago

2018-01-01

The surface chemistry and microstructures of titanium alloys (both new and used) and CoCrMo alloys used for hip and knee endoprostheses were determined using SEM (morphology), EBSD (phase analysis), AES and XPS (surface chemistry). Two new and two used endoprostheses were studied. The SEM SE and BE images showed their microstructures, while the EBSD provided the phases of the materials. During the production of the hip and knee endoprostheses, these materials are subject to severe thermomechanical treatments and physicochemical processes that are decisive for CoCrMo alloys. The AES and XPS results showed that thin oxide films on (a) Ti6Al4V are primarily a mixture of TiO2 with a small amount of Al2O3, while the V is depleted, (b) Ti6Al7Nb is primarily a mixture of TiO2 with a small amount of Al2O3 and Nb2O5, and (c) the CoCrMo alloy is primarily a mixture of Cr2O3 with small amounts of Co and Mo oxides. The thin oxide film on the CoCrMo alloy should prevent intergranular corrosion and improve the biocompatibility. The thin oxide films on the Ti alloys prevent further corrosion, improve the biocompatibility, and affect the osseointegration.

Surface chemistry and growth mechanisms studies of homo epitaxial (1 0 0) GaAs by laser molecular beam epitaxy

International Nuclear Information System (INIS)

Yan Dawei; Wu Weidong; Zhang Hong; Wang Xuemin; Zhang Hongliang; Zhang Weibin; Xiong Zhengwei; Wang Yuying; Shen Changle; Peng Liping; Han Shangjun; Zhou Minjie

2011-01-01

In this paper, GaAs thin film has been deposited on thermally desorbed (1 0 0) GaAs substrate using laser molecular beam epitaxy. Scanning electron microscopy, in situ reflection high energy electron diffraction and in situ X-ray photoelectron spectroscopy are applied for evaluation of the surface morphology and chemistry during growth process. The results show that a high density of pits is formed on the surface of GaAs substrate after thermal treatment and the epitaxial thin film heals itself by a step flow growth, resulting in a smoother surface morphology. Moreover, it is found that the incorporation of As species into GaAs epilayer is more efficient in laser molecular beam epitaxy than conventional molecular beam epitaxy. We suggest the growth process is impacted by surface chemistry and morphology of GaAs substrate after thermal treatment and the growth mechanisms are discussed in details.

A Reactive Transport Model for Marcellus Shale Weathering

Science.gov (United States)

Li, L.; Heidari, P.; Jin, L.; Williams, J.; Brantley, S.

2017-12-01

Shale formations account for 25% of the land surface globally. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil chemistry and water data. The simulation was carried out for 10,000 years, assuming bedrock weathering and soil genesis began right after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1,000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small with the presence of soil CO2. The field observations were only simulated successfully when the specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals, reflecting the lack of accessibility of fluids to mineral surfaces and potential surface coating. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude that availability of reactive surface area and transport of H2O and gases are the most important

Production of pyrite nanoparticles using high energy planetary ball milling for sonocatalytic degradation of sulfasalazine.

Science.gov (United States)

Khataee, Alireza; Fathinia, Siavash; Fathinia, Mehrangiz

2017-01-01

Sonocatalytic performance of pyrite nanoparticles was evaluated by the degradation of sulfasalazine (SSZ). Pyrite nanoparticles were produced via a high energy mechanical ball milling (MBM) in different processing time from 2h to 6h, in the constant milling speed of 320rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer-Emmett-Teller (BET) confirmed the production of pyrite nanoparticles during 6h of ball milling with the average size distribution of 20-80nm. The effects of various operational parameters including pH value, catalyst amount (mg/L), SSZ concentration (mg/L), ultrasonic frequency (kHz) and reaction time on the SSZ removal efficiency were examined. The obtained results showed that the maximum removal efficiency of 97.00% was obtained at pH value of 4, catalyst dosage of 0.5g/L, SSZ concentration of 10mg/L and reaction time of 30min. Experimental results demonstrated that the kinetic of the degradation process can be demonstrated using Langmuir-Hinshelwood (L-H) kinetic model. The effect of different inorganic ions such as Cl - , CO 3 2- and SO 4 2- was investigated on the L-H reaction rate (k r ) and adsorption (K s ) constants. Results showed that the presence of the mentioned ions significantly influenced the L-H constants. The impact of ethanol as a OH radical scavenger and some enhancers including H 2 O 2 and K 2 S 2 O 8 was investigated on the SSZ removal efficiency. Accordingly, the presence of ethanol suppressed SSZ degradation due to the quenching of OH radicals and the addition of K 2 S 2 O 8 and H 2 O 2 increased the SSZ removal efficiency, due to the formation of SO 4 - and additional OH radicals, respectively. Under the identical conditions of operating parameters, pyrite nanoparticles maintained their catalytic activity during four consecutive runs. Copyright © 2016 Elsevier B.V. All rights reserved.

Questa baseline and pre-mining ground-water quality investigation. 5. Well installation, water-level data, and surface- and ground-water geochemistry in the Straight Creek drainage basin, Red River Valley, New Mexico, 2001-03

Science.gov (United States)

Naus, Cheryl A.; McCleskey, R. Blaine; Nordstrom, D. Kirk; Donohoe, Lisa C.; Hunt, Andrew G.; Paillet, Frederick L.; Morin, Roger H.; Verplanck, Philip L.

2005-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, northern New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site, proximal analog. The Straight Creek drainage basin, chosen for this purpose, consists of the same quartz-sericite-pyrite altered andesitic and rhyolitic volcanic rock of Tertiary age as the mine site. The weathered and rugged volcanic bedrock surface is overlain by heterogeneous debris-flow deposits that interfinger with alluvial deposits near the confluence of Straight Creek and the Red River. Pyritized rock in the upper part of the drainage basin is the source of acid rock drainage (pH 2.8-3.3) that infiltrates debris-flow deposits containing acidic ground water (pH 3.0-4.0) and bedrock containing water of circumneutral pH values (5.6-7.7). Eleven observation wells were installed in the Straight Creek drainage basin. The wells were completed in debris-flow deposits, bedrock, and interfingering debris-flow and Red River alluvial deposits. Chemical analyses of ground water from these wells, combined with chemical analyses of surface water, water-level data, and lithologic and geophysical logs, provided information used to develop an understanding of the processes contributing to the chemistry of ground water in the Straight Creek drainage basin. Surface- and ground-water samples were routinely collected for determination of total major cations and selected trace metals; dissolved major cations, selected trace metals, and rare-earth elements; anions and alkalinity; and dissolved-iron species. Rare-earth elements were determined on selected samples only. Samples were collected for determination of dissolved organic carbon, mercury, sulfur isotopic composition (34S and 18O of sulfate), and water isotopic composition (2H and 18O) during

Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine

Science.gov (United States)

Cravotta, C.A.

1998-01-01

Data on rock, ground water, vadose water, and vadose gas chemistry were collected for two years after sewage sludge was applied at a reclaimed surface coal mine in Pennsylvania to determine if surface-applied sludge is an effective barrier to oxygen influx, contributes metals and nutrients to ground water, and promotes the acidification of ground water. Acidity, sulfate, and metals concentrations were elevated in the ground water (6- to 21-m depth) from spoil relative to unmined rock because of active oxidation of pyrite and dissolution of aluminosilicate, carbonate, and Mn-Fe-oxide minerals in the spoil. Concentrations of acidity, sulfate, metals (Fe, Mn, Al, Cd, Cu, Cr, Ni, Zn), and nitrate, and abundances of iron-oxidizing bacteria were elevated in the ground water from sludge-treated spoil relative to untreated spoil having a similar mineral composition; however, gaseous and dissolved oxygen concentrations did not differ between the treatments. Abundances of iron-oxidizing bacteria in the ground water samples were positively correlated with concentrations of ammonia, nitrate, acidity, metals, and sulfate. Concentrations of metals in vadose water samples (water samples from sludge-treated spoil, frequently exceeding 10 mg/L. Downgradient decreases in nitrate to less than 3 mg/L and increases in sulfate concentrations in underlying ground water could result from oxidation of pyrite by nitrate. Thus, sewage sludge added to pyritic spoil can increase the growth of iron-oxidizing bacteria, the oxidation of pyrite, and the acidification of ground water. Nevertheless, the overall effects on ground water chemistry from the sludge were small and probably short-lived relative to the effects from mining only.

A combined kinetic and diffusion model for pyrite oxidation in tailings - a change in controls with time

International Nuclear Information System (INIS)

Elberling, B.; Nicholson, R.V.; Scharer, J.M.

1994-01-01

Acidic drainage from the oxidation of mine tailing wastes is an important environmental problem. The purpose of this paper is to develop a model (1) to simulate the rate of oxidation of pyrite over time, (2) to verify the importance of chemical kinetic control and diffusion control on the oxidation rate with time and, (3) to evaluate the sensitivity of the model to critical parameters of the tailings, such as grain size, pyrite content and the effective diffusion coefficient. The source code comprises four main modules including parameter allocation (kinetics, transport), sulphide oxidation (shrinking particle), oxygen transport and pyrite mass balance. The results show that high oxidation rates are observed in the initial time after tailings deposition. During this initial period of high rates, an apparent shift occurs from kinetic to diffusional control over a period of time that depends on the composition and properties of the tailings. Based on the simulation results, it is evident that the overall rate of oxidation after a few years will be controlled dominantly by the diffusion of oxygen rather than by biological or non-biological kinetics in the tailings

SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

KAUST Repository

Baumgardner, William J.; Choi, Joshua J.; Lim, Yee-Fun; Hanrath, Tobias

2010-01-01

The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

KAUST Repository

Baumgardner, William J.

2010-07-21

The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

Science.gov (United States)

Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

1992-01-01

A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois. Chemical data were evaluated to determine the principal naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on- site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rain water or snowmelt changed to an ionic canposition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The

Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

Energy Technology Data Exchange (ETDEWEB)

Somorjai, Gabor A.; Li, Yimin

2009-11-21

Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.

Monitoring the Extent of Contamination from Acid Mine Drainage in the Iberian Pyrite Belt (SW Spain Using Hyperspectral Imagery

Directory of Open Access Journals (Sweden)

Asuncion Riaza

2011-10-01

Full Text Available Monitoring mine waste from sulfide deposits by hyperspectral remote sensing can be used to predict surface water quality by quantitatively estimating acid drainage and metal contamination on a yearly basis. In addition, analysis of the mineralogy of surface crusts rich in soluble salts can provide a record of annual humidity and temperature. In fact, temporal monitoring of salt efflorescence from mine wastes at a mine site in the Iberian Pyrite Belt (Huelva, Spain has been achieved using hyperspectral airborne Hymap data. Furthermore, climate variability estimates are possible based on oxidation stages derived from well-known sequences of minerals, by tracing sulfide oxidation intensity using archive spectral libraries. Thus, airborne and spaceborne hyperspectral remote sensing data can be used to provide a short-term record of climate change, and represent a useful set of tools for assessing environmental geoindicators in semi-arid areas. Spectral and geomorphological indicators can be monitored on a regular basis through image processing, supported by field and laboratory spectral data. In fact, hyperspectral image analysis is one of the methods selected by the Joint Research Centre of the European Community (Ispra, Italy to study abandoned mine sites, in order to assess the enforcement of the European Mine Waste Directive (2006/21/EC of the European Parliament and of the Council 15 March 2006 on the management of waste from extractive industries (Official Journal of the European Union, 11 April 2006. The pyrite belt in Andalucia has been selected as one of the core mission test sites for the PECOMINES II program (Cracow, November 2005, using imaging spectroscopy; and this technique is expected to be implemented as a monitoring tool by the Environmental Net of Andalucía (REDIAM, Junta de Andalucía, Spain.

Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

Science.gov (United States)

Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

2012-11-01

Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

Nitrate pollution and surface water chemistry in Shimabara, Nagasaki Prefecture, Japan

Science.gov (United States)

Nakagawa, K.; Amano, H.

2017-12-01

Shimabara city has been experiencing serious nitrate pollution in groundwater. To evaluate nitrate pollution and water chemistry in surface water, water samples were collected at 42 sampling points in 15 rivers in Shimabara including a part of Unzen city from January to February 2017. Firstly, spatial distribution of water chemistry was assessed by describing stiff and piper-trilinear diagrams using major ions concentrations. Most of the samples showed Ca-HCO3 or Ca-(NO3+SO4) water types. It corresponds to groundwater chemistry. Some samples were classified into characteristic water types such as Na-Cl, (Na+K)-HCO3, and Ca-Cl. These results indicate sea water mixing and anthropogenic pollution. At the upstream of Nishi-river, although water chemistry showed Ca-HCO3, ions concentrations were higher than that of the other rivers. It indicates that this site was affected by the peripheral anthropogenic activities. Secondly, nitrate-pollution assessment was performed by using NO3-, NO2-, coprostanol (5β(H)-Cholestan-3β-ol), and cholestanol (5α(H)-Cholestan-3β-ol). NO2-N was detected at the 2 sampling points and exceeded drinking standard 0.9 mg L-1 for bottle-fed infants (WHO, 2011). NO3-N + NO2-N concentrations exceeded Japanese drinking standard 10 mg L-1 at 18 sampling points. The highest concentration was 27.5 mg L-1. Higher NO3-N levels were observed in the rivers in the northern parts of the study area. Coprostanol has been used as a fecal contamination indicator, since it can be found in only feces of higher animals. Coprostanol concentrations at 8 sampling points exceeded 700 ng L-1 (Australian drinking water standard). Coprostanol has a potential to distinguish the nitrate pollution sources between chemical fertilizer or livestock wastes, since water samples with similar NO3-N + NO2-N concentration showed distinct coprostanol concentration. The sterols ratio (5β/ (5β+5α)) exceeded 0.5 at 18 sampling points. This reveals that fecal pollution has occurred.

Trace element geochemistry and surface water chemistry of the Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Science.gov (United States)

Shaver, S.A.; Hower, J.C.; Eble, C.F.; McLamb, E.D.; Kuers, K.

2006-01-01

Mean contents of trace elements and ash in channel, bench-column, and dump samples of the abandoned Bon Air coal (Lower Pennsylvanian) in Franklin County, Tennessee are similar to Appalachian COALQUAL mean values, but are slightly lower for As, Fe, Hg, Mn, Na, Th, and U, and slightly higher for ash, Be, Cd, Co, Cr, REEs, Sr, and V, at the 95% confidence level. Compared to channel samples, dump sample means are slightly lower in chalcophile elements (As, Cu, Fe, Ni, Pb, S, Sb, and V) and slightly higher in clay or heavy-mineral elements (Al, K, Mn, REEs, Th, Ti, U, and Y), but at the 95% confidence level, only As and Fe are different. Consistent abundances of clay or heavy-mineral elements in low-Br, high-S, high-ash benches that are relatively enriched in quartz and mire-to-levee species like Paralycopodites suggest trace elements are largely fluvial in origin. Factor analysis loadings and correlation coefficients between elements suggest that clays host most Al, Cr, K, Ti, and Th, significant Mn and V, and some Sc, U, Ba, and Ni. Heavy accessory minerals likely house most REEs and Y, lesser Sc, U, and Th, and minor Cr, Ni, and Ti. Pyrite appears to host As, some V and Ni, and perhaps some Cu, but Cu probably exists largely as chalcopyrite. Data suggest that organic debris houses most Be and some Ni and U, and that Pb and Sb occur as Pb-Sb sulfosalt(s) within organic matrix. Most Hg, and some Mn and Y, appear to be hosted by calcite, suggesting potential Hg remobilization from original pyrite, and Hg sorption by calcite, which may be important processes in abandoned coals. Most Co, Zn, Mo, and Cd, significant V and Ni, and some Mn probably occur in non-pyritic sulfides; Ba, Sr, and P are largely in crandallite-group phosphates. Selenium does not show organic or "clausthalite" affinities, but Se occurrence is otherwise unclear. Barium, Mn, Ni, Sc, U, and V, with strongly divided statistical affinities, likely occur subequally in multiple modes. For study area

Photografting of perfluoroalkanes onto polyethylene surfaces via azide/nitrene chemistry

Energy Technology Data Exchange (ETDEWEB)

Siegmann, Konstantin, E-mail: konstantin.siegmann@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Inauen, Jan, E-mail: jan.inauen@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Villamaina, Diego, E-mail: diego.villamaina@gmail.com [Visiting scientist at IMPE, Permanent address: Rapidplatz 3, CH-8953 Dietikon (Switzerland); Winkler, Martin, E-mail: martin.winkler@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland)

2017-02-28

The purpose of this study is to render polyethylene surfaces strongly and permanently hydrophobic. Polyethylene is a common plastic and, because of its inertness, difficult to graft. We chose polyethylene as example because of its ubiquity and model character. As graft chains linear perfluoroalkyl residues (−C{sub 4}F{sub 9}, −C{sub 6}F{sub 13}, −C{sub 8}F{sub 17} and −C{sub 10}F{sub 21}) were chosen, and photografting was selected as grafting method. Photolytically generated nitrenes can insert into carbon–hydrogen bonds and are therefore suited for binding to polyethylene. Hydrophobic photo reactive surface modifiers based on azide/nitrene chemistry are designed, synthesized in high yield and characterized. Four new molecules are described. Water contact angles exceeding 110° were achieved on grafted polyethylene. One problem is to demonstrate that the photografted surface modifiers are bound covalently to the polyethylene. Abrasion tests show that all new molecules, when photografted to polyethylene, have a higher abrasion resistance than a polyethylene surface coated with a long-chain perfluoroalkane. Relative abrasion resitances of 1.4, 2.0, 2.1 and 2.5 compared to the fluoroalkane coating were obtained for the four compounds. An abrasion model using ice is developed. Although all four compounds have the same λ{sub max} of 266 nm in acetonitrile solution, their molar extincition coefficients increase from 1.6·10{sup 4} to 2.2·10{sup 4} with increasing length of the fluorotelomer chain. Exitonic coupling of the chromophores of the surface modifiers is observed for specific molecules in the neat state. A linear correlation of water contact angle with fluorine surface content, as measured by photoelectron spectroscopy, in grafted polyethylene surfaces is established.

Tuning Surface Chemistry of Polyetheretherketone by Gold Coating and Plasma Treatment

Science.gov (United States)

Novotná, Zdeňka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdeňka; Hubáček, Tomáš; Borovec, Jakub; Švorčík, Václav

2017-06-01

Polyetheretherketone (PEEK) has good chemical and biomechanical properties that are excellent for biomedical applications. However, PEEK exhibits hydrophobic and other surface characteristics which cause limited cell adhesion. We have investigated the potential of Ar plasma treatment for the formation of a nanostructured PEEK surface in order to enhance cell adhesion. The specific aim of this study was to reveal the effect of the interface of plasma-treated and gold-coated PEEK matrices on adhesion and spreading of mouse embryonic fibroblasts. The surface characteristics (polarity, surface chemistry, and structure) before and after treatment were evaluated by various experimental techniques (gravimetry, goniometry, X-ray photoelectron spectroscopy (XPS), and electrokinetic analysis). Further, atomic force microscopy (AFM) was employed to examine PEEK surface morphology and roughness. The biological response of cells towards nanostructured PEEK was evaluated in terms of cell adhesion, spreading, and proliferation. Detailed cell morphology was evaluated by scanning electron microscopy (SEM). Compared to plasma treatment, gold coating improved PEEK wettability. The XPS method showed a decrease in the carbon concentration with increasing time of plasma treatment. Cell adhesion determined on the interface between plasma-treated and gold-coated PEEK matrices was directly proportional to the thickness of a gold layer on a sample. Our results suggest that plasma treatment in a combination with gold coating could be used in biomedical applications requiring enhanced cell adhesion.

Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

KAUST Repository

Al-Shareef, Reem A.

2017-01-01

Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx

Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

Energy Technology Data Exchange (ETDEWEB)

Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

1990-03-01

Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

A combinatorial variation in surface chemistry and pore size of three-dimensional porous poly(ε-caprolactone) scaffolds modulates the behaviors of mesenchymal stem cells

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yingdi; Tan, Ke; Zhou, Yan; Ye, Zhaoyang, E-mail: zhaoyangye@ecust.edu.cn; Tan, Wen-Song

2016-02-01

Biomaterial properties play significant roles in controlling cellular behaviors. The objective of the present study was to investigate how pore size and surface chemistry of three-dimensional (3D) porous scaffolds regulate the fate of mesenchymal stem cells (MSCs) in vitro in combination. First, on poly(ε-caprolactone) (PCL) films, the hydrolytic treatment was found to stimulate the adhesion, spreading and proliferation of human MSCs (hMSCs) in comparison with pristine films, while the aminolysis showed mixed effects. Then, 3D porous PCL scaffolds with varying pore sizes (100–200 μm, 200–300 μm and 300–450 μm) were fabricated and subjected to either hydrolysis or aminolysis. It was found that a pore size of 200–300 μm with hydrolysis in 3D scaffolds was the most favorable condition for growth of hMSCs. Importantly, while a pore size of 200–300 μm with hydrolysis for 1 h supported the best osteogenic differentiation of hMSCs, the chondrogenic differentiation was greatest in scaffolds with a pore size of 300–450 μm and treated with aminolysis for 1 h. Taken together, these results suggest that surface chemistry and pore size of 3D porous scaffolds may potentially have a synergistic impact on the behaviors of MSCs. - Highlights: • Surface chemistry of poly(ε-caprolactone) films actively modulates MSC behaviors. • Varying surface chemistry and pore size in combination is enabled in 3D scaffolds. • Surface chemistry and pore size potentially dictate MSC fates in synergy.

A combinatorial variation in surface chemistry and pore size of three-dimensional porous poly(ε-caprolactone) scaffolds modulates the behaviors of mesenchymal stem cells

International Nuclear Information System (INIS)

Zhao, Yingdi; Tan, Ke; Zhou, Yan; Ye, Zhaoyang; Tan, Wen-Song

2016-01-01

Biomaterial properties play significant roles in controlling cellular behaviors. The objective of the present study was to investigate how pore size and surface chemistry of three-dimensional (3D) porous scaffolds regulate the fate of mesenchymal stem cells (MSCs) in vitro in combination. First, on poly(ε-caprolactone) (PCL) films, the hydrolytic treatment was found to stimulate the adhesion, spreading and proliferation of human MSCs (hMSCs) in comparison with pristine films, while the aminolysis showed mixed effects. Then, 3D porous PCL scaffolds with varying pore sizes (100–200 μm, 200–300 μm and 300–450 μm) were fabricated and subjected to either hydrolysis or aminolysis. It was found that a pore size of 200–300 μm with hydrolysis in 3D scaffolds was the most favorable condition for growth of hMSCs. Importantly, while a pore size of 200–300 μm with hydrolysis for 1 h supported the best osteogenic differentiation of hMSCs, the chondrogenic differentiation was greatest in scaffolds with a pore size of 300–450 μm and treated with aminolysis for 1 h. Taken together, these results suggest that surface chemistry and pore size of 3D porous scaffolds may potentially have a synergistic impact on the behaviors of MSCs. - Highlights: • Surface chemistry of poly(ε-caprolactone) films actively modulates MSC behaviors. • Varying surface chemistry and pore size in combination is enabled in 3D scaffolds. • Surface chemistry and pore size potentially dictate MSC fates in synergy.

Color and surface chemistry changes of extracted wood flour after heating at 120 °C

Science.gov (United States)

Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark

2013-01-01

To investigate the effect of heat on color and surface chemistry of wood flour (WF), unextracted, extracted and delignified samples of commercial WF were heated at 120 °C for 24 h and analyzed by colorimetry, diffuse reflectance visible (DRV), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Fourier transform Raman (FT-Raman) spectroscopies....

Enhanced photoresponse of FeS2 films: the role of Marcasite-Pyrite phase junctions

NARCIS (Netherlands)

Wu, L.; Dzade, N.Y.; Gao, L.; Scanlon, D.O.; Öztürk, Z.; Hollingsworth, N.; Weckhuysen, B.M.; Hensen, E.J.M.; De Leeuw, N.H.; Hofmann, J.P.

2016-01-01

The beneficial role of marcasite in iron-sulfide-based photo-electrochemical applications is reported for the first time. A spectacular improvement of the photoresponse observed experimentally for mixed pyrite/marcasite-FeS2 films can be ascribed to the presence of p/m phase junctions at the

Enhanced Photoresponse of FeS2 Films : The Role of Marcasite–Pyrite Phase Junctions

NARCIS (Netherlands)

Wu, Longfei; Dzade, N.Y.; Gao, L.; Scanlon, D. O.; Özturk, Zafer; Hollingsworth, N.; Weckhuysen, B.M.; Hensen, E. J. M.; de Leeuw, Nora H.; Hofmann, J. P.

2016-01-01

The beneficial role of marcasite in iron sulfide-based photo-electrochemical applications is reported for the first time. A spectacular improvement of the photoresponse observed experimentally for mixed pyrite/marcasite-FeS2 films can be ascribed to the presence of p/m phase junctions at the

Soil infiltration bioreactor incorporated with pyrite-based (mixotrophic) denitrification for domestic wastewater treatment.

Science.gov (United States)

Kong, Zhe; Li, Lu; Feng, Chuanping; Chen, Nan; Dong, Shanshan; Hu, Weiwu

2015-01-01

In this study, an integrated two-stage soil infiltration bioreactor incorporated with pyrite-based (mixotrophic) denitrification (SIBPD) was designed for domestic wastewater treatment. Benefited from excellent adsorption ability and water-permeability, soil infiltration could avoid clogging, shorten operating time and lower maintenance cost. Respiration and nitrification were mostly engaged in aerobic stage (AES), while nitrate was majorly removed by pyrite-based mixotrophic denitrification mainly occurred in anaerobic stage (ANS). Fed with synthetic and real wastewater for 120days at 1.5h HRT, SIBPD demonstrated good removal performance showing 87.14% for COD, 92.84% for NH4(+)-N and 82.58% for TP along with 80.72% of nitrate removed by ANS. TN removal efficiency was 83.74% when conducting real wastewater. Compared with sulfur-based process, the effluent pH of SIBPD was maintained at 6.99-7.34 and the highest SO4(2-) concentration was only 64.63mgL(-1). This study revealed a promising and feasible application prospect for on-site domestic wastewater treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Annual report 1985 Chemistry Department

International Nuclear Information System (INIS)

1987-01-01

This annual report describes the activities carried out in 1985 by the Chemistry Department in the following fields: Chemistry, Inorganic Chemistry, Physicochemistry (Interphases, Surfaces), General Chemical Analysis, Active Materials Analysis, X Ray Fluorescence Analysis, Mass Spectroscopy (Isotopic Analysis, Instrumentation) and Optical Spectroscopy. A list of publications is enclosed. (M.E.L.) [es

A reactive transport model for Marcellus shale weathering

Science.gov (United States)

Heidari, Peyman; Li, Li; Jin, Lixin; Williams, Jennifer Z.; Brantley, Susan L.

2017-11-01

Shale formations account for 25% of the land surface globally and contribute a large proportion of the natural gas used in the United States. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water in the surface or deep subsurface, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil and water chemistry data. The simulation was carried out for 10,000 years since deglaciation, assuming bedrock weathering and soil genesis began after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small if CO2 was not present in the soil gas. The field observations were only simulated successfully when the modeled specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals. Small surface areas could be consistent with the lack of accessibility of some fluids to mineral surfaces due to surface coatings. In addition, some mineral surface is likely interacting only with equilibrated pore

Preparation of Metallic Iron Powder from Pyrite Cinder by Carbothermic Reduction and Magnetic Separation

Directory of Open Access Journals (Sweden)

Hongming Long

2016-04-01

Full Text Available The reduction and magnetic separation procedure of pyrite cinder in the presence of a borax additive was performed for the preparation of reduced powder. The effects of borax dosage, reduction temperature, reduction time and grinding fineness were investigated. The results show that when pyrite cinder briquettes with 5% borax were pre-oxidized at 1050 °C for 10 min, and reduced at 1050 °C for 80 min, with the grinding fineness (<0.44 mm passing 81%, the iron recovery was 91.71% and the iron grade of the magnetic concentrate was 92.98%. In addition, the microstructures of the products were analyzed by optical microscope, scanning electron microscope (SEM, and mineralography, and the products were also studied by the X-ray powder diffraction technique (XRD to investigate the mechanism; the results show that the borax additive was approved as a good additive to improve the separation of iron and gangue.

Celebrating Two Centuries of Research in Selenium Chemistry: State of the Art and New Prospective

Directory of Open Access Journals (Sweden)

Claudio Santi

2017-12-01

Full Text Available In 2017, the 200th anniversary of the discovery of selenium was celebrated. In 1817, the Swedish chemists, Berzelius and Gahn, on roasting 200 kg of sulfur from a pyrite from the Falun mine, obtained about 3 g of a precipitate that they first wrongly identified as tellurium. Berzelius doubted this result and repeated the analysis some months later realizing that a new element was in his hands and he named this element Selenium (Greek: Selene, moon in consideration of its resemblance to Tellurium (Latin: Tellus, earth. Several events were organized in the year for this special celebration and this Special Issue would like to be an additional contribution to the success of a research that, especially during the last decades, rapidly grew in different fields: synthesis, medicinal chemistry, biology, material, and environment. These studies are strongly characterized by multi- and interdisciplinary connections, and, for this reason, we collected here contributions coming from different areas and disciplines, not exclusively synthetic organic chemistry.

Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

Science.gov (United States)

Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

2014-12-10

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

Preparation of Carbon Nanotube/TiO2 Mesoporous Hybrid Photoanode with Iron Pyrite (FeS2) Thin Films Counter Electrodes for Dye-Sensitized Solar Cell

OpenAIRE

Bayram Kilic; Sunay Turkdogan; Aykut Astam; Oguz Can Ozer; Mansur Asgin; Hulya Cebeci; Deniz Urk; Selin Pravadili Mucur

2016-01-01

Multi-walled carbon nanotube (MWCNT)/TiO2 mesoporous networks can be employed as a new alternative photoanode in dye-sensitized solar cells (DSSCs). By using the MWCNT/TiO2 mesoporous as photoanodes in DSSC, we demonstrate that the MWCNT/TiO2 mesoporous photoanode is promising alternative to standard FTO/TiO2 mesoporous based DSSC due to larger specific surface area and high electrochemical activity. We also show that iron pyrite (FeS2) thin films can be used as an efficient counter electrode...

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

Science.gov (United States)

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

Invisible and microscopic gold in pyrite: Methods and new data for massive sulfide ores of the Urals

Science.gov (United States)

Vikentyev, I. V.

2015-07-01

Au speciation in sulfides (including "invisible" Au), which mostly controls the loss of Au during ore dressing, is discussed. Modern methods of analysis of Au speciation, with discussion of limitations by locality and sensitivity, are reviewed. The results of sulfide investigation by the methods of scanning and transmission electron microscopy, mass spectrometric analysis with laser ablation (LA-ICP-MS), the thermochemical method (study of ionic Au speciation), and automated "quantitative mineralogy," are demonstrated for weakly metamorphosed VHMS deposits of the Urals (Galkinsk and Uchaly). Significant content of Au is scattered in sulfides, such as pyrite, chalcopyrite, and sphalerite, with quantitative predomination of pyrite. The portion of such "invisible" gold ranges from flakes) with a monocrystal diffraction pattern of some particles and a ring diffraction pattern of other particles was registered in the ores of these deposits by the methods of transmission electron microscopy. The low degree (or absence) of metamorphic recrystallization results in (1) predomination of thin intergrowths of sulfides, which is the main reason for the bad concentration of ores (especially for the Galkinsk deposit) and (2) the high portion of "invisible" gold in the massive sulfide ores, which explains the low yield of Au in copper and zinc concentrates, since it is lost in tailings with predominating pyrite.

The synergy of ultrasonic treatment and organic modifiers for tuning the surface chemistry and conductivity of multiwalled carbon nanotubes

Czech Academy of Sciences Publication Activity Database

Omastová, M.; Mičušík, M.; Fedorko, P.; Pionteck, J.; Kovářová, Jana; Chehimi, M. M.

2014-01-01

Roč. 46, 10-11 (2014), s. 940-944 ISSN 0142-2421. [European Conference on Applications of Surface and Interface Analysis /15./ - ECASIA 2013. Cagliari, 13.10.2013-18.10.2013] Institutional support: RVO:61389013 Keywords : carbon nanotubes * surface modification * surfactant Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.245, year: 2014

Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

Energy Technology Data Exchange (ETDEWEB)

Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

2015-09-14

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co₃O₄ or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

Vapor phase epitaxial growth of FeS sub 2 pyrite and evaluation of the carrier collection in liquid-junction solar cell

Energy Technology Data Exchange (ETDEWEB)

Ennaoui, A.; Schlichthoerl, G.; Fiechter, S.; Tributsch, H. (Hahn-Meitner-Inst., Abt. Solare Energetik und Materialforschung, Berlin (Germany))

1992-01-01

Photoactive epitaxial layers of FeS{sub 2} were grown using bromine as a transport agent and a simple closed ampoule technique. The substrates used were (100)-oriented slices of natural pyrite 1 mm thick. A vapor-liquid-solid (VLS) growth mechanism was elucidated by means of optical microscopy. Macrosteps, terrace surfaces and protuberances are often accompanied with the presence of liquid FeBr{sub 3} droplets. In the absence of a liquid phase growth hillocks are found. Localized photovoltaic response for the evaluation of carrier collection using a scanning laser spot system has been used to effectively locate and characterize non-uniformities present in the epitaxial thin films. (orig.).

Mimicking the surface and prebiotic chemistry of early Earth using flow chemistry.

Science.gov (United States)

Ritson, Dougal J; Battilocchio, Claudio; Ley, Steven V; Sutherland, John D

2018-05-08

When considering life's aetiology, the first questions that must be addressed are "how?" and "where?" were ostensibly complex molecules, considered necessary for life's beginning, constructed from simpler, more abundant feedstock molecules on primitive Earth. Previously, we have used multiple clues from the prebiotic synthetic requirements of (proto)biomolecules to pinpoint a set of closely related geochemical scenarios that are suggestive of flow and semi-batch chemistries. We now wish to report a multistep, uninterrupted synthesis of a key heterocycle (2-aminooxazole) en route to activated nucleotides starting from highly plausible, prebiotic feedstock molecules under conditions which mimic this scenario. Further consideration of the scenario has uncovered additional pertinent and novel aspects of prebiotic chemistry, which greatly enhance the efficiency and plausibility of the synthesis.

Hydrology and geochemistry of a surface coal mine in northwestern Colorado

Science.gov (United States)

Williams, R.S.; Clark, G.M.

1994-01-01

The hydrology and geochemistry of a reclaimed coal mine in northwestern Colorado were monitored during water years 1988 and 1989. Some data also were collected in water years 1987 and 1990. This report describes (1) the sources of hydrologic recharge to and discharge from reclaimed spoil, (2) the relative contributions of recharge to the reclaimed spoil aquifer from identified source waters and the rate of water movement from those sources to the reclaimed spoil, and (3) the geochemical reactions that control water quality in reclaimed spoil. The study area was at a dip-slope coal mine encompassing about 7 square miles with land slopes of varying aspect. The area was instrumented and monitored at five sites; two sites had unmined and reclaimed- spoil areas adjacent to each other and three sites were unmined. The mined areas had been reclaimed. Instrumentation at the study sites included 1 climate station, 3 rain gages, 19 soil-water access tubes, 2 lysimeters, 18 wells completed in bedrock, 7 wells completed in reclaimed spoil, and 2 surface- water gaging stations. The results of the study indicate that the reclaimed spoil is recharged from surface recharge and underburden aquifers. Discharge, as measured by lysimeters, was about 3 inches per year and occurred during and after snowmelt. Hydraulic-head measurements indicated a potential for ground-water movement from deeper to shallower aquifers. Water levels rose in the reclaimed-spoil aquifer and spring discharge at the toe of the spoil slopes increased rapidly in response to snowmelt. Water chemistry, stable isotopes, geochemical models, and mass-balance calculations indicate that surface recharge and the underburden aquifers each contribute about 50 percent of the water to the reclaimed-spoil aquifers. Geochemical information indicates that pyrite oxidation and dissolution of carbonate and efflorescent sulfate minerals control the water chemistry of the reclaimed-spoil aquifer.

S/Se ratio of pyrite from eastern Australian VHMS deposits: implication of magmatic input into volcanogenic hydrothermal systems

Energy Technology Data Exchange (ETDEWEB)

Huston, D L [Geological Survey of Canada, Ottawa, ON (Canada); Sie, S H; Suter, G F [Commonwealth Scientific and Industrial Research Organisation (CSIRO), North Ryde, NSW (Australia). Div. of Exploration Geoscience; Cooke, D R [Tasmania Univ., Sandy Bay, TAS (Australia)

1994-12-31

The proton microprobe was used to determine the concentrations of over twenty trace elements in pyrite grains from four volcanic-hosted massive sulphide (VHMS) deposits in eastern Australia. Of the elements determined, Se has the most potential in resolving important problems in the genesis of this class of ore deposits. This paper summarises analytical conditions, describes the distribution of Se in pyrite in VHMS deposits as determined in this and other studies, discusses the speciation of Se in hydrothermal fluids, and presents a genetic model on the relative contribution of magmatic versus sea water Se (and S) in VHMS systems. 2 refs., 1 fig.

S/Se ratio of pyrite from eastern Australian VHMS deposits: implication of magmatic input into volcanogenic hydrothermal systems

Energy Technology Data Exchange (ETDEWEB)

Huston, D.L. [Geological Survey of Canada, Ottawa, ON (Canada); Sie, S.H.; Suter, G.F. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), North Ryde, NSW (Australia). Div. of Exploration Geoscience; Cooke, D.R. [Tasmania Univ., Sandy Bay, TAS (Australia)

1993-12-31

The proton microprobe was used to determine the concentrations of over twenty trace elements in pyrite grains from four volcanic-hosted massive sulphide (VHMS) deposits in eastern Australia. Of the elements determined, Se has the most potential in resolving important problems in the genesis of this class of ore deposits. This paper summarises analytical conditions, describes the distribution of Se in pyrite in VHMS deposits as determined in this and other studies, discusses the speciation of Se in hydrothermal fluids, and presents a genetic model on the relative contribution of magmatic versus sea water Se (and S) in VHMS systems. 2 refs., 1 fig.

Substantial difference in target surface chemistry between reactive dc and high power impulse magnetron sputtering

Science.gov (United States)

Greczynski, G.; Mráz, S.; Schneider, J. M.; Hultman, L.

2018-02-01

The nitride layer formed in the target race track during the deposition of stoichiometric TiN thin films is a factor 2.5 thicker for high power impulse magnetron sputtering (HIPIMS), compared to conventional dc processing (DCMS). The phenomenon is explained using x-ray photoelectron spectroscopy analysis of the as-operated Ti target surface chemistry supported by sputter depth profiles, dynamic Monte Carlo simulations employing the TRIDYN code, and plasma chemical investigations by ion mass spectrometry. The target chemistry and the thickness of the nitride layer are found to be determined by the implantation of nitrogen ions, predominantly N+ and N2+ for HIPIMS and DCMS, respectively. Knowledge of this method-inherent difference enables robust processing of high quality functional coatings.

Atmospheric Constraints on the Surface UV Environment of Mars at 3.9 Ga Relevant to Prebiotic Chemistry

Science.gov (United States)

Ranjan, Sukrit; Wordsworth, Robin; Sasselov, Dimitar D.

2017-08-01

Recent findings suggest that Mars may have been a clement environment for the emergence of life and may even have compared favorably to Earth in this regard. These findings have revived interest in the hypothesis that prebiotically important molecules or even nascent life may have formed on Mars and been transferred to Earth. UV light plays a key role in prebiotic chemistry. Characterizing the early martian surface UV environment is key to understanding how Mars compares to Earth as a venue for prebiotic chemistry. Here, we present two-stream, multilayer calculations of the UV surface radiance on Mars at 3.9 Ga to constrain the surface UV environment as a function of atmospheric state. We explore a wide range of atmospheric pressures, temperatures, and compositions that correspond to the diversity of martian atmospheric states consistent with available constraints. We include the effects of clouds and dust. We calculate dose rates to quantify the effect of different atmospheric states on UV-sensitive prebiotic chemistry. We find that, for normative clear-sky CO2-H2O atmospheres, the UV environment on young Mars is comparable to young Earth. This similarity is robust to moderate cloud cover; thick clouds (τcloud ≥ 100) are required to significantly affect the martian UV environment, because cloud absorption is degenerate with atmospheric CO2. On the other hand, absorption from SO2, H2S, and dust is nondegenerate with CO2, meaning that, if these constituents build up to significant levels, surface UV fluence can be suppressed. These absorbers have spectrally variable absorption, meaning that their presence affects prebiotic pathways in different ways. In particular, high SO2 environments may admit UV fluence that favors pathways conducive to abiogenesis over pathways unfavorable to it. However, better measurements of the spectral quantum yields of these pathways are required to evaluate this hypothesis definitively.

Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.

Science.gov (United States)

Tang, Chuyang Y; Shiang Fu, Q; Gao, Dawen; Criddle, Craig S; Leckie, James O

2010-04-01

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns, yet very limited information has been available on PFOS adsorption onto mineral surfaces. PFOS adsorption onto goethite and silica was investigated by batch adsorption experiments under various solution compositions. Adsorption onto silica was only marginally affected by pH, ionic strength, and calcium concentration, likely due to the dominance of non-electrostatic interactions. In contrast, PFOS uptake by goethite increased significantly at high [H+] and [Ca2+], which was likely due to enhanced electrostatic attraction between the negatively charged PFOS molecules and positively charged goethite surface. The effect of pH was less significant at high ionic strength, likely due to electrical double layer compression. PFOS uptake was reduced at higher ionic strength for a strongly positively charged goethite surface (pH 3), while it increased for a weakly charged surface (pH 7 and 9), which could be attributed to the competition between PFOS-surface electrostatic attraction and PFOS-PFOS electrostatic repulsion. A conceptual model that captures PFOS-surface and PFOS-PFOS electrostatic interactions as well as non-electrostatic interaction was also formulated to understand the effect of solution chemistry on PFOS adsorption onto goethite and silica surfaces. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

2015-08-15

Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

Surface Chemistry Involved in Epitaxy of Graphene on 3C-SiC(111/Si(111

Directory of Open Access Journals (Sweden)

Abe Shunsuke

2010-01-01

Full Text Available Abstract Surface chemistry involved in the epitaxy of graphene by sublimating Si atoms from the surface of epitaxial 3C-SiC(111 thin films on Si(111 has been studied. The change in the surface composition during graphene epitaxy is monitored by in situ temperature-programmed desorption spectroscopy using deuterium as a probe (D2-TPD and complementarily by ex situ Raman and C1s core-level spectroscopies. The surface of the 3C-SiC(111/Si(111 is Si-terminated before the graphitization, and it becomes C-terminated via the formation of C-rich (6√3 × 6√3R30° reconstruction as the graphitization proceeds, in a similar manner as the epitaxy of graphene on Si-terminated 6H-SiC(0001 proceeds.

The Effect of Water Vapor on the Thermal Decomposition of Pyrite in N2 Atmosphere

Directory of Open Access Journals (Sweden)

Nesrin BOYABAT

2009-03-01

Full Text Available In this study, the effect of water vapor on the thermal decomposition of pyrite mineral in nitrogen atmosphere has been investigated in a horizontal tube furnace. Temperature, time and water vapor concentration were used as experimental parameters. According to the data obtained at nitrogen/ water vapor environment, it was observed that the water vapor on the decomposition of pyrite increased the decomposition rate. The decomposition reaction is well represented by the "shrinking core" model and can be divided into two regions with different rate controlling step. The rate controlling steps were determined from the heat transfer through the gas film for the low conversions, while it was determined from the mass transfer through product ash layer for the high conversions. The activation energies of this gas and ash film mechanisms were found to be 77 and 81 kJ/mol-1, respectively.

Thermodynamic Cconstraints on Coupled Carbonate-Pyrite Weathering Dynamics and Carbon Fluxes

Science.gov (United States)

Winnick, M.; Maher, K.

2017-12-01

Chemical weathering within the critical zone regulates global biogeochemical cycles, atmospheric composition, and the supply of key nutrients to terrestrial and aquatic ecosystems. Recent studies suggest that thermodynamic limits on solute production act as a first-order control on global chemical weathering rates; however, few studies have addressed the factors that set these thermodynamic limits in natural systems. In this presentation, we investigate the effects of soil CO2 concentrations and pyrite oxidation rates on carbonate dissolution and associated carbon fluxes in the East River watershed in Colorado, using concentration-discharge relationships and thermodynamic constraints. Within the shallow subsurface, soil respiration rates and moisture content determine the extent of carbonic acid-promoted carbonate dissolution through their modulation of soil pCO2 and the balance of open- v. closed-system weathering processes. At greater depths, pyrite oxidation generates sulfuric acid, which alters the approach to equilibrium of infiltrating waters. Through comparisons of concentration-discharge data and reactive transport model simulations, we explore the conditions that determine whether sulfuric acid reacts to dissolve additional carbonate mineral or instead reacts with alkalinity already in solution - the balance of which determines watershed carbon flux budgets. Our study highlights the importance of interactions between the chemical structure of the critical zone and the hydrologic regulation of flowpaths in determining concentration-discharge relationships and overall carbon fluxes.

Surface chemistry and fundamental limitations on the plasma cleaning of metals

Energy Technology Data Exchange (ETDEWEB)

Dong, Bin, E-mail: bindong@my.unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States); Driver, M. Sky, E-mail: Marcus.Driver@unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States); Emesh, Ismail, E-mail: Ismail_Emesh@amat.com [Applied Materials Inc., 3050 Bowers Ave, Santa Clara, CA, 95054 (United States); Shaviv, Roey, E-mail: Roey_Shaviv@amat.com [Applied Materials Inc., 3050 Bowers Ave, Santa Clara, CA, 95054 (United States); Kelber, Jeffry A., E-mail: Jeffry.Kelber@unt.edu [Department of Chemistry, University of North Texas, 1155 Union Circle 305070, Denton, TX, 76203 (United States)

2016-10-30

Highlights: • O{sub 2}-free plasma treatment of air-exposed Co or Cu surfaces yields remnant C layers inert to further plasma cleaning. • The formation of the remnant C layer is graphitic (Cu) or carbidic (Co). • The formation of a remnant C layer is linked to plasma cleaning of a metal surface. - Abstract: In-situ X-ray photoelectron spectroscopy (XPS) studies reveal that plasma cleaning of air-exposed Co or Cu transition metal surfaces results in the formation of a remnant C film 1–3 monolayers thick, which is not reduced upon extensive further plasma exposure. This effect is observed for H{sub 2} or NH{sub 3} plasma cleaning of Co, and He or NH{sub 3} plasma cleaning of Cu, and is observed with both inductively coupled (ICP) and capacitively-coupled plasma (CCP). Changes in C 1 s XPS spectra indicate that this remnant film formation is accompanied by the formation of carbidic C on Co and of graphitic C on Cu. This is in contrast to published work showing no such remnant carbidic/carbon layer after similar treatments of Si oxynitride surfaces. The observation of the remnant carbidic C film on Co and graphitic film on Cu, but not on silicon oxynitride (SiO{sub x}N{sub y}), regardless of plasma chemistry or type, indicates that this effect is due to plasma induced secondary electron emission from the metal surface, resulting in transformation of sp{sup 3} adventitious C to either a metal carbide or graphite. These results suggest fundamental limitations to plasma-based surface cleaning procedures on metal surfaces.

Chemistry of Frozen NaCl and MgSO4 Brines - Implications for Surface Expression of Europa's Ocean Composition

Science.gov (United States)

Johnson, P. V.; Hodyss, R. P.; Choukroun, M.; Vu, T. H.

2015-12-01

The composition of Europa's subsurface ocean is a critical determinant of its habitability, but current analysis of the ocean composition is limited to its expression on the Europan surface. While there is observational evidence indicating that ocean materials make their way to the surface, our understanding of the chemical processes that can alter this material under Europan surface conditions is limited. We present experimental data on the chemistry of mixed solutions of NaCl and MgSO4 as they are frozen to 100 K, replicating the conditions that may occur when subsurface ocean fluids are emplaced onto Europa's surface. Confocal micro-Raman spectroscopy is used to study the formation of salts during the freezing process, and the interaction of ions in the frozen brines. Our data indicate that mixed aqueous solutions of NaCl and MgSO4 form Na2SO4 and MgCl2 preferentially when frozen, rather than making NaCl and MgSO4 precipitates. The detection of epsomite (MgSO4Ÿ•7H2O) on Europa's surface may therefore imply an ocean composition relatively low in sodium, unless radiolytic chemistry converts MgCl2 to MgSO4 as suggested by Hand and Brown 2013 (ApJ 145 110). These results have important implications for the interpretation of remote sensing data of Europa's surface.

Trends in Surface Water Chemistry in Acidified Areas in Europe and North America from 1990 to 2008

Science.gov (United States)

Acidification of lakes and rivers is still an environmental concern despite reduced emissions of acidifying compounds. We analyzed trends in surface water chemistry of 173 acid-sensitive sites from 12 regions in Europe and North America. In 11 of 12 regions, non-marine sulphate (...

Phytoremediation trials on metal- and arsenic-contaminated pyrite wastes (Torviscosa, Italy)

Energy Technology Data Exchange (ETDEWEB)

Vamerali, Teofilo [Department of Environmental Sciences, University of Parma, Viale G.P. Usberti 11/A, 43100 Parma (Italy)], E-mail: teofilo.vamerali@unipd.it; Bandiera, Marianna; Coletto, Lucia; Zanetti, Federica [Department of Environmental Agronomy and Crop Sciences, University of Padova, Viale dell' Universita 16, 35020 Legnaro - Padova (Italy); Dickinson, Nicholas M. [Faculty of Science, Liverpool John Moores University, Byrom Street, Liverpool, L3 3AF (United Kingdom); Mosca, Giuliano [Department of Environmental Agronomy and Crop Sciences, University of Padova, Viale dell' Universita 16, 35020 Legnaro - Padova (Italy)

2009-03-15

At a site in Udine, Italy, a 0.7 m layer of As, Co, Cu, Pb and Zn contaminated wastes derived from mineral roasting for sulphur extraction had been covered with an unpolluted 0.15 m layer of gravelly soil. This study investigates whether woody biomass phytoremediation is a realistic management option. Comparing ploughing and subsoiling (0.35 m depth), the growth of Populus and Salix and trace element uptake were investigated in both pot and field trials. Species differences were marginal and species selection was not critical. Impaired above-ground productivity and low translocation of trace elements showed that bioavailable contaminant stripping was not feasible. The most significant finding was of coarse and fine roots proliferation in surface layers that provided a significant sink for trace elements. We conclude that phytostabilisation and effective immobilisation of metals and As could be achieved at the site by soil amelioration combined with woody species establishment. Confidence to achieve a long-term and sustainable remediation requires a more complete quantification of root dynamics and a better understanding of rhizosphere processes. - In As- and metal-contaminated pyrite wastes, contaminant stripping is not feasible, and root foraging and quantification of root dynamics holds the key to stabilisation in woody species.

Phytoremediation trials on metal- and arsenic-contaminated pyrite wastes (Torviscosa, Italy)

International Nuclear Information System (INIS)

Vamerali, Teofilo; Bandiera, Marianna; Coletto, Lucia; Zanetti, Federica; Dickinson, Nicholas M.; Mosca, Giuliano

2009-01-01

At a site in Udine, Italy, a 0.7 m layer of As, Co, Cu, Pb and Zn contaminated wastes derived from mineral roasting for sulphur extraction had been covered with an unpolluted 0.15 m layer of gravelly soil. This study investigates whether woody biomass phytoremediation is a realistic management option. Comparing ploughing and subsoiling (0.35 m depth), the growth of Populus and Salix and trace element uptake were investigated in both pot and field trials. Species differences were marginal and species selection was not critical. Impaired above-ground productivity and low translocation of trace elements showed that bioavailable contaminant stripping was not feasible. The most significant finding was of coarse and fine roots proliferation in surface layers that provided a significant sink for trace elements. We conclude that phytostabilisation and effective immobilisation of metals and As could be achieved at the site by soil amelioration combined with woody species establishment. Confidence to achieve a long-term and sustainable remediation requires a more complete quantification of root dynamics and a better understanding of rhizosphere processes. - In As- and metal-contaminated pyrite wastes, contaminant stripping is not feasible, and root foraging and quantification of root dynamics holds the key to stabilisation in woody species

Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine

International Nuclear Information System (INIS)

Cravotta, C.A. III

1998-01-01

Data on rock, ground water, vadose water, and vadose gas chemistry were collected for two years after sewage sludge was applied at a reclaimed surface coal mine in Pennsylvania to determine if surface-applied sludge is an effective barrier to oxygen influx, contributes metals and nutrients to ground water, and promotes the acidification of ground water. Acidity, sulfate, and metals concentrations were elevated in the ground water from spoil relative to unmined rock because of active oxidation of pyrite and dissolution of aluminosilicate, carbonate, and Mn-Fe-oxide minerals in the spoil. Concentrations of acidity, sulfate, metals (Fe, Mn, Al, Cd, Cu, Cr, Ni, Zn), and nitrate, and abundances of iron-oxidizing bacteria were elevated in the ground water from sludge-treated spoil relative to untreated spoil having a similar mineral composition; however, gaseous and dissolved oxygen concentrations did not differ between the treatments. Abundances of iron-oxidizing bacteria in the ground water samples were positively correlated with concentrations of ammonia, nitrate, acidity, metals, and sulfate. Concentrations of metals in vadose water samples (< 5-m depth) from sludge-treated spoil (pH 5.9) were not elevated relative to untreated spoil (pH 4.4). In contrast, concentrations of nitrate were elevated in vadose water samples from sludge-treated spoil, frequently exceeding 10 mg/L. Downgradient decreases in nitrate to less than 3 mg/L and increases in sulfate concentrations in underlying ground water could result from oxidation of pyrite by nitrate. Thus, sewage sludge added to pyritic spoil can increase the growth of iron-oxidizing bacteria, the oxidation of pyrite, and the acidification of ground water. Nevertheless, the overall effects on ground water chemistry from the sludge were small and probably short-lived relative to the effects from mining only

Synchrotron-based XPS studies of AlGaN and GaN surface chemistry and its relationship to ion sensor behaviour

Energy Technology Data Exchange (ETDEWEB)

Khir, Farah Liyana Muhammad, E-mail: 21001899@student.uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Myers, Matthew, E-mail: Matt.Myers@csiro.au [School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); CSIRO Earth Science and Resource Engineering, Kensington, Western Australia 6151 (Australia); Podolska, Anna [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Department of Exploration Geophysics, Curtin University of Technology, 26 Dick Perry Avenue, ARRC, Kensington, Western Australia 6151 (Australia); Sanders, Tarun Maruthi [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Baker, Murray V., E-mail: murray.baker@uwa.edu.au [School of Chemistry and Biochemistry, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Nener, Brett D., E-mail: brett.nener@uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia); Parish, Giacinta, E-mail: giacinta.parish@uwa.edu.au [School of Electrical, Electronic and Computer Engineering, The University of Western Australia, 35 Stirling Hwy., Crawley, Western Australia 6009 (Australia)

2014-09-30

Highlights: • Soft X-ray was used to study the surface chemistry of GaN and AlGaN. • The surface chemistry and sensor behaviour were investigated. • The oxide of aluminum is significantly more reactive than gallium. • The Cl{sup −} ions are greater in GaN samples compared to AlGaN samples. - Abstract: Soft X-ray photoelectron spectroscopy was used to investigate the fundamental surface chemistry of both AlGaN and GaN surfaces in the context of understanding the behaviour of AlGaN/GaN heterostructures as chemical field-effect transistor (CHEMFET) ion sensors. AlGaN and GaN samples were subjected to different methods of oxide growth (native oxide and thermally grown oxide) and chemical treatment conditions. Our investigations indicate that the etching of the oxide layer is more pronounced with AlGaN compared to GaN. Also, we observed that chloride ions have a greater tendency to attach to the GaN surface relative to the AlGaN surface. Furthermore, chloride ions are comparatively more prevalent on surfaces treated with 5% HCl acid solution. The concentration of chloride ions is even higher on the HCl treated native oxide surface resulting in a very clear deconvolution of the Cl 2p{sub 1/2} and Cl 2p{sub 3/2} peaks. For GaN and AlGaN surfaces, a linear response (e.g. source-drain current) is typically seen with variation in pH of buffered solutions with constant reference electrode voltage at the surface gate; however, an inverted bath-tub type response (e.g. a maximum at neutral pH and lower values at pH values away from neutral) and a general tendency to negative charge selectivity has been also widely reported. We have shown that our XPS investigations are consistent with the different sensor response reported in the literature for these CHEMFET devices and may help to explain the differing response of these materials.

Physics and Chemistry on Well-Defined Semiconductor and Oxide Surfaces

Science.gov (United States)

Chen, Peijun

High resolution electron energy loss spectroscopy (HREELS) and other surface spectroscopic techniques have been employed to investigate the following two classes of surface/interface phenomena on well-defined semiconductor and oxide surfaces: (i) the fundamental physical and chemical processes involved in gas-solid interaction on silicon single crystal surfaces, and (ii) the physical and chemical properties of metal-oxide interfaces. The particular systems reported in this dissertation are: NH_3, PH_3 and B_ {10}H_{14} on Si(111)-(7 x 7); NH_3 on Si(100) -(2 x 1); atomic H on Si(111)-(7 x 7) and boron-modified Si(111); Al on Al_2O_3 and Sn on SiO_2.. On silicon surfaces, the surface dangling bonds function as the primary adsorption sites where surface chemical processes take place. The unambiguous identification of surface species by vibrational spectroscopy allows the elementary steps involved in these surface chemical processes to be followed on a molecular level. For adsorbate molecules such as NH_3 and PH_3, the nature of the initial low temperature (100 -300 K) adsorption is found to be dissociative, while that for B_{10}H_ {14} is non-dissociative. This has been deduced based upon the presence (or absence) of specific characteristic vibrational mode(s) on surface. By following the evolution of surface species as a function of temperature, the elementary steps leading to silicon nitride thin film growth and doping of silicon are elucidated. In the case of NH_3 on Si(111)-(7 x 7) and Si(100)-(2 x 1), a detailed understanding on the role of substrate surface structure in controlling the surface reactivity has been gained on the basis of a Si adatom backbond-strain relief mechanism on the Si(111) -(7 x 7). The electronic modification to Si(111) surface by subsurface boron doping has been shown to quench its surface chemistry, even for the most aggressive atomic H. This discovery is potentially meaningful to the technology of gas-phase silicon etching. The