Research on solvent-refined coal. Quarterly technical progress report, July 1-September 30, 1981
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1982-07-01
This report describes progress on the Research on Solvent Refined Coal project by The Pittsburg and Midway Coal Mining Company's Merriam Laboratory during the third quarter of 1981. A four-part experiment was conducted with subbituminous Edna coal, pyrite and/or bituminous Ireland coal at 457/sup 0/C and 1800 psig or 450/sup 0/C and 2250 psig. The purpose was to determine the conditions appropriate for processing a 50/50 by weight blend of these coals. A total of four runs (11 experiments) discussed this quarter were directed toward the study of disposable catalysts. Subbituminous coals from the Edna and Belle Ayr Mines weremore » processed in the SRC II mode. Additives investigated were pyrite, ferric oxide, molybdenum doped ferric oxide and iron dispersed on silica-alumina. The level and type of sulfur added in conjunction with ferric oxide catalysts was also explored as well as addition of sulfur by itself. Two solvent hydrogenation runs and five SRC I runs were directed toward a preliminary investigation of short residence time processing of western (Belle Ayr) coals.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kolker,A.; Huggins, F.
2007-01-01
Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period ofmore » 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32-1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26-0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1997-05-01
This report describes the technical progress made on the Advanced Coal Conversion Process (ACCP) Demonstration Project from July 1, 1995 through September 30, 1995. The ACCP Demonstration Project is a US Department of Energy (DOE) Clean Coal Technology Project. This project demonstrates an advanced, thermal, coal upgrading process, coupled with physical cleaning techniques, that is designed to upgrade high-moisture, low-rank coals to a high-quality, low-sulfur fuel, registered as the SynCoal process. The coal is processed through three stages (two heating stages followed by an inert cooling stage) of vibrating fluidized bed reactors that remove chemically bound water, carboxyl groups, andmore » volatile sulfur compounds. After thermal upgrading, the cola is put through a deep-bed stratifier cleaning process to separate the pyrite-rich ash from the coal.« less
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
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pesic, B.; Oliver, D.J.
1990-12-31
The present investigation is a part of our studies on the electro chemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously (1,2) we have examined the effect of T. ferrooxidans and their metabolic products on the redox reactions of Fe{sup 2+}/Fe{sup 3+} couple at the pyrite surface. Results obtained suggest that beyond 1. 5 days during their growth in a batch fermenter, the bacteria and their metabolic products completely cover the pyrite surface and shut down all electron transfer across the electrode-solution interface. In addition, it has been observed that the bacteria serve as the nucleation site for jarosite formation,more » which is found detrimental to bioleaching. In the present work we have focussed on the effect of the presence of vitamins on the redox chemistry of iron. Our examination of the effect of the presence of thiamine hydrochloride in the redox behavior of Fe{sup 2+}/Fe{sup 3+} at the pyrite surface has revealed that thiamine hydrochloride does not undergo chemical interaction with ferrous or ferric iron. However, it may adsorb onto the pyrite surface causing polarization of the pyrite electrode.« less
NASA Astrophysics Data System (ADS)
Graham, Andrew M.; Bouwer, Edward J.
2012-04-01
In-situ reduction of toxic Cr(VI) to nontoxic Cr(III) represents an important natural attenuation process for Cr(VI)-impacted environments. This study investigates the stoichiometry and kinetics of Cr(VI) reduction by pyrite, a reduced iron-sulfur mineral ubiquitous in recent estuarine and marine sediments. Pyrite suspensions at surface loadings of 0.28-2.10 m2/L (typical of estuarine or marine sediments) were capable of completely reducing 7-120 μM Cr(VI) on the timescale of minutes to days, with the time to reaction completion decreasing with increasing pyrite loading, decreasing initial Cr(VI) concentration, and decreasing suspension pH. Analysis of metal species (Cr and Fe) and sulfur species in solution and at the mineral surface indicated that Cr(VI) oxidatively dissolved the pyrite surface, releasing ferrous iron and sulfate into solution as the reaction progressed. Surface disulfide groups were postulated as the Cr(VI)-reactive surface entity. Net production or consumption of aqueous Fe(II) was shown to depend upon the relative rates of proton-promoted Fe(II) release, Fe(II) release due to oxidative dissolution of pyrite in the presence of Cr(VI), and Fe(II) consumption due to homogeneous reaction with Cr(VI). Kinetics of Cr(VI) reduction by pyrite displayed a biphasic pattern, and the time to reaction completion increased dramatically with increasing initial Cr(VI) concentration. Rapid Cr(VI) removal occurred early in the reaction progress, attributable to Cr(VI) loss under an adsorption-limited regime. Slow, approximately zero-order, Cr(VI) removal occurred over the bulk of the time courses, and corresponded to Cr(VI) removal under surface site saturation conditions. Stoichiometric Cr(VI) reduction was able to proceed under surface site limited conditions owing to regeneration of reactive surface sites following desorption/dissolution of oxidized surface products, as demonstrated in repeat Cr(VI)-spiking experiments. The role of surface passivation was evaluated by comparing rates of Cr(VI) reduction in the presence and absence of the Cr(III)-complexing agent citrate. While citrate addition significantly enhanced Cr(III) solubility, rates of Cr(VI) reduction were only marginally accelerated, suggesting that Cr(OH)3(s) coatings did not completely block access of Cr(VI) to reactive surface sites on pyrite. Given the rapid rates of Cr(VI) reduction with pyrite under pH and surface coverage conditions typical of natural environments, we propose that Cr(VI) reduction by pyrite be considered in fate and transport models for Cr in contaminated sediments.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Doyle, F.M.
1993-12-31
The objective of this research is to develop a mechanistic understanding of the oxidation of coal and coal pyrite, and to correlate the intrinsic physical and chemical properties of these minerals, along with changes resulting from oxidation, with those surface properties that influence the behavior in physical cleaning processes. The results will provide fundamental insight into oxidation, in term of the bulk and surface chemistry, the microstructure, and the semiconductor properties of the pyrite. During the thirteenth quarter, wet oxidation tests were done on coal samples from the Pennsylvania State Coal Bank. As-received and oxidized coal samples were studied bymore » Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy to detect functional groups that might be responsible for changing the hydrophobicity of coal samples. Coal samples from the Pennsylvania State Coal Bank were oxidized for 5 hours at room temperature using 10% H{sub 2}O{sub 2} at pH 1.0, 1.0 M HNO{sub 3} or 0.05 M Fe{sub 2}(SO{sub 4}){sub 3} at pH 1.0. Details of the experimental procedure used in the wet oxidation tests were provided in our September 30, 1993 report, along with results of ion-exchange analysis and film flotation tests on as-received and oxidized coal samples. Table II shows the weight percentage of carboxylic and phenolic group oxygen generated by oxidation with different treatments, as determined by ion-exchange. DRIFT spectroscopic analysis was done on as-received and oxidized samples to identify different functionalities directly, to supplement the information on carboxylic and phenolic groups obtained indirectly by ion-exchange methods. The procedure for DRIFT analysis was reported in our June 30, 1993 report.« less
Pyrite Iron Sulfide Solar Cells Made from Solution Final Technical Report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Law, Matt
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 FeS 2) 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)more » 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/MoS 2 bilayers as good ohmic bottom contacts to pyrite films; (3) fabrication of pyrite diodes with a glass/Mo/MoS 2/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-purity pyrite single crystals, proved the existence of a conductive, hole-rich inversion layer at the surface of n-type pyrite crystals and established that the inversion layer is the likely reason for pyrite’s low VOC; (7) developed several surface passivation treatments to reduce the surface hole density, but not enough to expect a significant increase in VOC; (8) by controlling the single crystal growth conditions, reduced the concentration of near-surface deep donors by a factor of ~1000, which should be sufficient to avoid thermionic field emission (i.e., tunneling) across the pyrite surface and thereby increase pyrite VOC. Recent project results will be described in forthcoming peer-reviewed publications.« less
NASA Astrophysics Data System (ADS)
Caban Acevedo, Miguel
The success of solar energy technologies depends not only on highly efficient solar-to-electrical energy conversion, charge storage or chemical fuel production, but also on dramatically reduced cost, to meet the future terawatt energy challenges we face. The enormous scale involved in the development of impactful solar energy technologies demand abundant and inexpensive materials, as well as energy-efficient and cost-effective processes. As a result, the investigation of semiconductor, catalyst and electrode materials made of earth-abundant and sustainable elements may prove to be of significant importance for the long-term adaptation of solar energy technologies on a larger scale. Among earth-abundant semiconductors, iron pyrite (cubic FeS2) has been considered the most promising solar energy absorber with the potential to achieve terawatt energy-scale deployment. Despite extensive synthetic progress and device efforts, the solar conversion efficiency of iron pyrite has remained below 3% since the 1990s, primarily due to a low open circuit voltage (V oc). The low photovoltage (Voc) of iron pyrite has puzzled scientists for decades and limited the development of cost-effective solar energy technologies based on this otherwise promising semiconductor. Here I report a comprehensive investigation of the syntheses and properties of iron pyrite materials, which reveals that the Voc of iron pyrite is limited by the ionization of a high density of intrinsic bulk defect states despite high density surface states and strong surface Fermi level pinning. Contrary to popular belief, bulk defects most-likely caused by intrinsic sulfur vacancies in iron pyrite must be controlled in order to enable this earth-abundant semiconductor for cost-effective and sustainable solar energy conversion. Lastly, the investigation of iron pyrite presented here lead to the discovery of ternary pyrite-type cobalt phosphosulfide (CoPS) as a highly-efficient earth-abundant catalyst material for electrochemical and solar energy driven hydrogen production.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Strongin, Daniel
2014-12-31
Over the course of the scientific program, two areas of research were pursued: reactions of iron oxides with supercritical CO 2 and sulfide and surface reactivity of pyrite. The latter area of interest was to understand the chemistry that results when supercritical CO 2 (scCO 2 ) with H 2 S and/or SO 2 in deep saline formations (DFS) contacts iron bearing minerals. Understanding the complexities the sulfur co-injectants introduce is a critical step in developing CO 2 sequestration as a climate-mitigating strategy. The research strategy was to understand macroscopic observations of this chemistry with anmore » atomic/molecular level view using surface analytical techniques. Research showed that the exposure of iron (oxyhdr)oxides (which included ferrihydrite, goethite, and hematite) to scCO 2 in the presence of sulfide led to reactions that formed siderite (FeCO 3). The results have important implications for the sequestration of CO 2 via carbonation reactions in the Earth’s subsurface. An earlier area of focus in the project was to understand pyrite oxidation in microscopic detail. This understanding was used to understand macroscopic observations of pyrite reactivity. Results obtained from this research led to a better understanding how pyrite reacts in a range of chemical environments. Geochemical and modern surface science techniques were used to understand the chemistry of pyrite in important environmental conditions. The program relied on a strong integration the results of these techniques to provide a fundamental understanding to the macroscopic chemistry exhibited by pyrite in the environment. Major achievements during these studies included developing an understanding of the surface sites on pyrite that controlled its reactivity under oxidizing conditions. In particular sulfur anion vacancies and/or ferric sites were sites of reactivity. Studies also showed that the adsorption of phospholipid on the surface to selectively suppress the reactivity of these sites could of potential importance for suppressing acid mine drainage in the environment (a problem common to coal-mining sites). Biotic studies showed that microbial activity that promotes the oxidation of pyrite to produce AMD could also be suppressed by the adsorption of phospholipid.« less
Pyrite-Type Nanomaterials for Advanced Electrocatalysis.
Gao, Min-Rui; Zheng, Ya-Rong; Jiang, Jun; Yu, Shu-Hong
2017-09-19
Since being proposed by John Bockris in 1970, hydrogen economy has emerged as a very promising alternative to the current hydrocarbon economy. Access to reliable and affordable hydrogen economy, however, requires cost-effective and highly efficient electrocatalytic materials that replace noble metals (e.g., Pt, Ir, Ru) to negotiate electrode processes such as oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). Although substantial advances in the development of inexpensive catalysts, successful deployment of these materials in fuel cells and electrolyzers will depend on their improved activity and robustness. Recent research has demonstrated that the nanostructuring of Earth-abundant minerals provides access to newly advanced energy materials, particularly for nanostructured pyrites, which are attracting great interest. Crystalline pyrites commonly contain the characteristic dianion units and have cations occurring in octahedral coordination-whose generalized formula is MX 2 , where M can be transition metal of groups 8-12 and X is a chalcogen. The diversity of pyrites that are accessible and their versatile and tunable properties make them attractive for a wide range of applications from photovoltaics to energy storage and electrocatalysis. Pyrite-type structures can be further extended to their ternary analogues, for example, CoAsS (cobaltite), NiAsS (gersdorffite), NiSbS (ullmannite), CoPS, and many others. Moreover, improved properties of pyrites can be realized through grafting them with promoter objects (e.g., metal oxides, metal chalcogenides, noble metals, and carbons), which bring favorable interfaces and structural and electronic modulations, thus leading to performance gains. In recent years, research on the synthesis of pyrite nanomaterials and on related structure understanding has dramatically advanced their applications, which offers new perspectives in the search for efficient and robust electrocatalysts, yet a focused review that concentrates the critical developments is still missing. In this Account, we describe our recent progress on the discoveries and applications of nanostructured pyrite-type materials in the area of electrocatalysis. We first briefly highlight some interesting properties of pyrite-type materials and why they are attractive for modern electrocatalysis. Some recent advances on their synthesis that allows access to highly nanostructured pyrite-type materials are reviewed, along with the grafting of resultant pyrites with foreign materials (e.g., metal oxides, metal chalcogenides, noble metals, and carbons) to enable improved catalytic performances. We finally spotlight the exciting examples where pyrite nanostructures were used as efficient electrocatalysts to drive the OER, HER, and methanol-tolerant ORR. It is reasonable to assume that, with significant efforts and focus, the next few years will bring new advances on the pyrites and other minerals for electrocatalysis.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Honaker, R.Q.; Reed, S.; Mohanty, M.K.
1997-05-01
A circuit comprised of advanced fine coal cleaning technologies was evaluated in an operating preparation plant to determine circuit performance and to compare the performance with current technologies used to treat -16 mesh fine coal. The circuit integrated a Floatex hydrosizer, a Falcon enhanced gravity concentrator and a Jameson flotation cell. A Packed-Column was used to provide additional reductions in the pyritic sulfur and ash contents by treatment of the Floatex-Falcon-Jameson circuit product. For a low sulfur Illinois No. 5 coal, the pyritic sulfur content was reduced from 0.67% to 0.34% at a combustible recovery of 93.2%. The ash contentmore » was decreased from 27.6% to 5.84%, which equates to an organic efficiency of 95% according to gravity-based washability data. The separation performance achieved on a high sulfur Illinois No. 5 coal resulted in the rejection of 72.7% of the pyritic sulfur and 82.3% of the ash-forming material at a recovery of 8 1 %. Subsequent pulverization of the cleaned product and retreatment in a Falcon concentrator and Packed-Column resulted in overall circuit ash and pyritic sulfur rejections of 89% and 93%, respectively, which yielded a pyritic sulfur content reduction from 2.43% to 0.30%. This separation reduced the sulfur dioxide emission rating of an Illinois No. 5 coal from 6.21 to 1.75 lbs SO{sub 2}/MBTU, which is Phase I compliance coal. A comparison of the results obtained from the Floatex-Falcon-Jameson circuit with those of the existing circuit revealed that the novel fine coal circuit provides 10% to 20% improvement in mass yield to the concentrate while rejecting greater amounts of ash and pyritic sulfur.« less
Commeau, R.F.; Paull, C.K.; Commeau, J.A.; Poppe, L.J.
1987-01-01
Pyrite is rapidly accumulating at the contact between the Cretaceous limestones of the Florida Platform and the hemipelagic sediments of the abyssal Gulf of Mexico. Sediments sampled with the submersible "Alvin" in 3266 m of water are associated with a dense community of organisms that depend on chemosynthetic primary production as a food source. Analysis of the chemistry, mineralogy, and textural composition of these sediments indicate that iron sulfide mineralization is occurring at the seafloor within an anoxic micro-habitat sustained by the advection of hydrogen sulfide-charged saline brines from the adjacent platform. The chemosynthetic bacteria that directly overlie the sediments oxidize hydrogen sulfide for energy and provide elemental sulfur that reacts with iron monosulfide to form some of the pyrite. The sediments are mixtures of pyrite (??? 30 wt.%), BaSr sulfates (??? 4 wt.%), clays, and locally derived biogenic carbonates and are progressively being cemented by iron sulfides. Oxidation of hydrogen sulfide produces locally acidic conditions that corrode the adjacent limestones. Potential sources of S, H2S, Fe, Ba, and Sr are discussed. ?? 1987.
Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.
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
NASA Astrophysics Data System (ADS)
Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.
2018-02-01
Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.
Fallick, Anthony E; Boyce, Adrian J; McConville, Paul
2012-01-01
Our study focuses on pyrite nodules developed in the Brent Group sandstones, which host the Brent Oilfield, one of the North Sea's greatest oil and gas producers. Timing of nodule formation is equivocal, but due to the forceful, penetrative textures that abound, it is considered late. This pyrite offers a research opportunity because it records the development of the supply of H(2)S in a hydrocarbon reservoir and its sulphur isotopic composition. Laser-based analysis of δ(34)S reveals an extraordinary diversity in values and patterns. The values range from-27 to+72‰, covering half the terrestrial range, with large variations at the submillimetre scale. Isotopically heavy (δ(34)S ∼+30‰ or higher) sulphide is endemic, but low δ(34)S pyrite is also present and appears to represent a temporally though not spatially (on the ∼cm scale) distinct pyritisation event. The distribution of δ(34)S values within individual concretions can be normal (Gaussian), but in some cases may reflect progressive isotope fractionation process(es), conceivably of Rayleigh type. The source of the sulphur and the identity of the isotope fractionation process(es) remain enigmatic.
Research on solvent-refined coal. Quarterly technical progress report, April 1, 1981-June 30, 1981
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1981-10-01
This report describes progress on the Research on Solvent Refined Coal project by The Pittsburg and Midway Coal Mining Co.'s Merriam Laboratory during the second quarter of 1981. Alexander Mine coal was evaluated as a feedstock for major liquefaction facilities and had a yield structure similar to other reactive Pittsburgh seam coals at standard SRC II conditions. Two lots of coal from the Ireland Mine (Pittsburgh seam) were found to be of nearly the same composition and produced essentially the same yields. Two experiments in which coal-derived nonvolatile organic matter was processed without fresh coal feed indicate constant rates ofmore » conversion of SRC to oil and gas. Insoluble organic matter (IOM) remained unconverted. The naphtha and middle distillate products from the deep conversion contained less sulfur but more nitrogen than those from conventional SRC II processing. Encouraging results were obtained when a very small amount of iron oxide dispersed on alumina was added to Kaiparowits coal which cannot be processed at normal SRC II conditions without added catalyst. Subbituminous coals from the McKinley and Edna Mines were processed successfully with added pyrite but would not run when the added catalyst was removed.« less
NASA Astrophysics Data System (ADS)
Syverson, D. D.; Ono, S.; Seyfried, W. E., Jr.
2017-12-01
The rate of exchange and multiple S isotope fractionation between pyrite and dissolved H2S and SO4 was determined at 300°C and 500 bars at physiochemical conditions indicative of natural MOR hydrothermal systems by using the flexible gold cell reactor system [1]. A 34S enriched solution was designed to track reaction progress and to not significantly perturb mass dependent relationships between 33S and 36S, allowing for observations of natural mass dependent fractionation between pyrite and dissolved species during dissolution and recrystallization. The experimental data are compared with previously determined experimental constraints of S isotope exchange between fluid species [2] and with Fe and S isotope experiments conducted at higher temperature and where pyrite was precipitated rapidly from solution at 300 and 350°C and 500 bars [3, 4]. Briefly, the 34S isotope data indicate that the rate of exchange between pyrite and dissolved aqueous species is sluggish, where insignificant exchange occurred after the course of 4000 hours at 300°C, approximately 4%. Furthermore, the 33,36S mineral-fluid data indicate that upon pyrite dissolution, the light isotopes are preferentially removed into solution and incorporated as H2S and SO4-. These data are consistent with natural observations of pyrite-dissolved S disequilibrium and provide important insight towards mineral reactivity and retentiveness of recording mineral formation conditions. [1] Seyfried Jr., W.E., Janecky, D.R. & Berndt, M.E. 1987 Rocking autoclaves for hydrothermal experiments: II. The flexible reaction-cell system. Hydrothermal Experimental Techniques 216-239. [2] Ohmoto, H. & Lasaga, A.C. 1982 Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems. Geochimica et Cosmochimica Acta 46, 1727-1745. [3] Syverson, D.D., Borrok, D.M. & Seyfried Jr., W.E. 2013 Experimental determination of equilibrium Fe isotopic fractionation between pyrite and dissolved Fe under hydrothermal conditions. Geochimica et Cosmochimica Acta 122, 170-183. [4] Syverson, D.D., Ono, S., Shanks, W.C. & Seyfried Jr., W.E. 2015 Multiple sulfur isotope fractionation and mass transfer processes during pyrite precipitation and recrystallization: An experimental study at 300 and 350°C. Geochimica et Cosmochimica Acta 165, 418-434.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harb, J.N.
This report describes work performed in the fifteenth quarter of a fundamental study to examine the effect of staged combustion on ash formation and deposition. Efforts this quarter included addition of a new cyclone for improved particle sampling and modification of the existing sampling probe. Particulate samples were collected under a variety of experimental conditions for both coals under investigation. Deposits formed from the Black Thunder coal were also collected. Particle size and composition from the Pittsburgh No. 8 ash samples support previously reported results. In addition, the authors ability to distinguish char/ash associations has been refined and applied tomore » a variety of ash samples from this coal. The results show a clear difference between the behavior of included and excluded pyrite, and provide insight into the extent of pyrite oxidation. Ash samples from the Black Thunder coal have also been collected and analyzed. Results indicate a significant difference in the particle size of {open_quotes}unclassifiable{close_quotes} particles for ash formed during staged combustion. A difference in composition also appears to be present and is currently under investigation. Finally, deposits were collected under staged conditions for the Black Thunder coal. Specifically, two deposits were formed under similar conditions and allowed to mature under either reducing or oxidizing conditions in natural gas. Differences between the samples due to curing were noted. In addition, both deposits showed skeletal ash structures which resulted from in-situ burnout of the char after deposition.« less
MINERALOGY, PETROGRAPHY, AND RADIOACTIVITY OF REPRESENTATIVE SAMPLES OF CHATTANOOGA SHALE
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bates, T.F.; Strahl, E.O.
1957-01-01
Qualitative and quantitative mineralogical studies of the Chattanooga Shale are in progress. Problems of separation and analysis of mineral and organic components are difficult because the rock is fine-grained. However, the applicaiion of light and electron microscopy, x-ray diffraction, nuclear-track study, and other methods has provided data of interest. Megascopically, the shalc is a massive chocolate-brown sediment which displays faint indications of lamination. Some pyrite lenses, nodules, and crystals and a few mica flakes are large enough to be seen with a hand lens. In thin section the rock is seen to consist of grains of quartz and feldspar inmore » a matrix of yellow to red--brown organic material, which incorporates shreds of mica and probably clay particles and is dotted by small clusters of pyrite. Larger organic fragments with associated pyrite are common and take various forms. Individual mineral particles range from pyrite cubes less than 0.15 micron on a side to quartz and feldspar grains as large as 0.10 mm. X-ray studies show the clay minerals to be illite, kaolinite, and chlorite in decreasing order of abundance. Tourmaline, zircon, and apatite are the characteristic heavy minerals of the sediment. Quantitative studies, accomplished by a combination of chemical and mineralogical methods, have shown the composition of a batch sample of this rock to be approxiinately: 22% quartz, 9% feldspar, 31% illite and kaolinite, 22% organic matter, 11% pyrite and marcasite, 2% chlorite, 2% iron oxides, and l% tourmaline, zircon, and apatite. Alphatrack studies of cniulsion-covered thin sections indicate that no uranium mineral is present. Approximately 70% of the uranium atoms is randomly distributed throughout the finegrained matrix of the rock, whereas another 25% is concentrated in organic-pyrite-clay complexes such as pyrite nodules and discrete organic bodies. In unweathered samples there is no relationship between uranium distribution and textural fcatures such as bedding. The data indicate that the uranium was precipitated from sea water under reducing conditions and has not been redistributed following compaction of the sediment. (auth)« less
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
NASA Astrophysics Data System (ADS)
Khan, S. U. M.; Baltrus, J. P.; Lai, R. W.; Richardson, A. G.
1991-06-01
Coal pyrite and mineral pyrite surfaces were examined by X-ray photoelectron spectroscopy (XPS) before and after treatment in acidic and basic solutions of sodium ethyl xanthate (NaEtX). XPS showed that the degree of oxidation of coal and mineral pyrite surfaces increased when these pyrites were conditioned in basic solutions. However, conditioning in acidic solutions led to partial removal of surface oxidation from the pyrites. Addition of NaEtX to the acidic and basic solutions enhanced the removal of oxidation from pyrite surfaces. Pretreatment with sulfur dioxide further enhanced the removal of surface oxidation in the presence of NaEtX. Surface oxidation was typically less on mineral pyrite than coal pyrite surfaces following identical treatments. The flotation recoveries of the pyrites in the presence of NaEtX are greatest for the pyrites with the least amount of surface oxidation.
The effects of trace element content on pyrite oxidation rates
NASA Astrophysics Data System (ADS)
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 variability of trace element content from the pyrite samples. These data were then used to select areas of interest for NanoSIMS analyses, which in turn was used to select areas for TEM and APT. These analyses show that the trace element content of pyrite can be highly variable, which may significantly affect the rate of pyrite oxidation.
Diehl, S.F.; Goldhaber, M.B.; Koenig, A.E.; Lowers, H.A.; Ruppert, L.F.
2012-01-01
Pennsylvanian coals in the Appalachian Basin host pyrite that is locally enriched in potentially toxic trace elements such as As, Se, Hg, Pb, and Ni. A comparison of pyrite-rich coals from northwestern Alabama, eastern Kentucky, and West Virginia reveals differences in concentrations and mode of occurrence of trace elements in pyrite. Pyrite occurs as framboids, dendrites, or in massive crystalline form in cell lumens or crosscutting veins. Metal concentrations in pyrite vary over all scales, from microscopic to mine to regional, because trace elements are inhomogeneously distributed in the different morphological forms of pyrite, and in the multiple generations of sulfide mineral precipitates. Early diagenetic framboidal pyrite is usually depleted in As, Se, and Hg, and enriched in Pb and Ni, compared to other pyrite forms. In dendritic pyrite, maps of As distribution show a chemical gradient from As-rich centers to As-poor distal branches, whereas Se concentrations are highest at the distal edges of the branches. Massive crystalline pyrite that fills veins is composed of several generations of sulfide minerals. Pyrite in late-stage veins commonly exhibits As-rich growth zones, indicating a probable epigenetic hydrothermal origin. Selenium is concentrated at the distal edges of veins. A positive correlation of As and Se in pyrite veins from Kentucky coals, and of As and Hg in pyrite-filled veins from Alabama coals, suggests coprecipitation of these elements from the same fluid. In the Kentucky coal samples (n = 18), As and Se contents in pyrite-filled veins average 4200 ppm and 200 ppm, respectively. In Alabama coal samples, As in pyrite-filled veins averages 2700 ppm (n = 34), whereas As in pyrite-filled cellular structures averages 6470 ppm (n = 35). In these same Alabama samples, Se averages 80 ppm in pyrite-filled veins, but was below the detection limit in cell structures. In samples of West Virginia massive pyrite, As averages 1700 ppm, and Se averages 270 ppm (n = 24). The highest concentration of Hg (≤ 102 ppm) is in Alabama pyrite veins. Improved detailed descriptions of sulfide morphology, sulfide mineral paragenesis, and trace-element concentration and distribution allow more informed predictions of: (1) the relative rate of release of trace elements during weathering of pyrite in coals, and (2) the relative effectiveness of various coal-cleaning procedures of removing pyrite. For example, trace element-rich pyrite has been shown to be more soluble than stoichiometric pyrite, and fragile fine-grained pyrite forms such as dendrites and framboids are more susceptible to dissolution and disaggregation but less amenable to removal during coal cleaning.
A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance
NASA Astrophysics Data System (ADS)
Deditius, Artur P.; Utsunomiya, Satoshi; Renock, Devon; Ewing, Rodney C.; Ramana, Chintalapalle V.; Becker, Udo; Kesler, Stephen E.
2008-06-01
This report describes a new form of arsenian pyrite, called As3+-pyrite, in which As substitutes for Fe [(Fe,As)S2], in contrast to the more common form of arsenian pyrite, As1--pyrite, in which As1- substitutes for S [Fe(As,S)2]. As3+-pyrite has been observed as colloformic overgrowths on As-free pyrite in a hydrothermal gold deposit at Yanacocha, Peru. XPS analyses of the As3+-pyrite confirm that As is present largely as As3+. EMPA analyses show that As3+-pyrite incorporates up to 3.05 at % of As and 0.53 at. %, 0.1 at. %, 0.27 at. %, 0.22 at. %, 0.08 at. % and 0.04 at. % of Pb, Au, Cu, Zn, Ni, and Co, respectively. Incorporation of As3+ in the pyrite could be written like: As+yAu+1-y(□)⇔2Fe; where Au+ and vacancy (□) help to maintain the excess charge. HRTEM observations reveal a sharp boundary between As-free pyrite and the first overgrowth of As3+-pyrite (20-40 nm thick) and co-linear lattice fringes indicating epitaxial growth of As3+-pyrite on As-free pyrite. Overgrowths of As3+-pyrite onto As-free pyrite can be divided into three groups on the basis of crystal size, 8-20 nm, 100-300 nm and 400-900 nm, and the smaller the crystal size the higher the concentration of toxic arsenic and trace metals. The Yanacocha deposit, in which As3+-pyrite was found, formed under relatively oxidizing conditions in which the dominant form of dissolved As in the stability field of pyrite is As3+; in contrast, reducing conditions are typical of most environments that host As1--pyrite. As3+-pyrite will likely be found in other oxidizing hydrothermal and diagenetic environments, including high-sulfidation epithermal deposits and shallow groundwater systems, where probably kinetically controlled formation of nanoscale crystals such as observed here would be a major control on incorporation and release of As3+ and toxic heavy metals in oxidizing natural systems.
Probing the prodigious strain fringes from Lourdes
NASA Astrophysics Data System (ADS)
Aerden, Domingo G. A. M.; Sayab, Mohammad
2017-12-01
We investigate the kinematics of classic sigmoidal strain fringes from Lourdes (France) and review previous genetic models, strain methods and strain rates for these microstructures. Displacement controlled quartz and calcite fibers within the fringes yield an average strain of 195% with the technique of Ramsay and Huber (1983). This agrees well with strains measured from boudinaged pyrite layers and calcite veins in the same rocks, but conflicts with ca. ∼675% strain in previous analogue models for the studied strain fringes produced by progressive simple shear. We show that the detailed geometry and orientation of fiber patterns are insufficiently explained by simple shear but imply two successive, differently oriented strain fields. Although all strain fringes have the same overall asymmetry, considerable morphological variation resulted from different amounts of rotation of pyrite grains and fringes. Minor rotation led to sharply kinked fibers that record a ca. 70° rotation of the kinematic frame. Larger (up to 145°) rotations, accommodated by antithetic sliding on pyrite-fringe contacts, produced more strongly and smoothly curved fibers. Combined with published Rb-Sr ages for the studied microstructures, our new strain data indicate an average strain rate of 1.41 10-15 s-1 during ca. 37 Myr. continuous growth.
Control of pyrite addition in coal liquefaction process
Schmid, Bruce K.; Junkin, James E.
1982-12-21
Pyrite addition to a coal liquefaction process (22, 26) is controlled (118) in inverse proportion to the calcium content of the feed coal to maximize the C.sub.5 --900.degree. F. (482.degree. C.) liquid yield per unit weight of pyrite added (110). The pyrite addition is controlled in this manner so as to minimize the amount of pyrite used and thus reduce pyrite contribution to the slurry pumping load and disposal problems connected with pyrite produced slag.
Effect of lattice defects on the electronic structures and floatability of pyrites
NASA Astrophysics Data System (ADS)
Xian, Yong-jun; Wen, Shu-ming; Chen, Xiu-ming; Deng, Jiu-shuai; Liu, Jian
2012-12-01
The electronic structures of three types of lattice defects in pyrites (i.e., As-substituted, Co-substituted, and intercrystalline Au pyrites) were calculated using the density functional theory (DFT). In addition, their band structures, density of states, and difference charge density were studied. The effect of the three types of lattice defects on the pyrite floatability was explored. The calculated results showed that the band-gaps of pyrites with Co-substitution and intercrystalline Au decreased significantly, which favors the oxidation of xanthate to dixanthogen and the adsorption of dixanthogen during pyrite flotation. The stability of the pyrites increased in the following order: As-substituted < perfect < Co-substituted < intercrystalline Au. Therefore, As-substituted pyrite is easier to be depressed by intensive oxidization compared to perfect pyrite in a strongly alkaline medium. However, Co-substituted and intercrystalline Au pyrites are more difficult to be depressed compared to perfect pyrite. The analysis of the Mulliken bond population and the electron density difference indicates that the covalence characteristic of the S-Fe bond is larger compared to the S-S bond in perfect pyrite. In addition, the presence of the three types of lattice defects in the pyrite bulk results in an increase in the covalence level of the S-Fe bond and a decrease in the covalence level of the S-S bond, which affect the natural floatability of the pyrites.
Size and maceral association of pyrite in Illinois coals and their float-sink fractions
Harvey, R.D.; DeMaris, P.J.
1987-01-01
The amount of pyrite (FeS2) removed by physical cleaning varies with differences in the amount of pyrite enclosed within minerals and of free pyrite in feed coals. A microscopic procedure for characterizing the size and maceral association of pyrite grains was developed and evaluate by testing three coals and their washed products. The results yield an index to the cleanability of pyrite. The index is dependent upon particle size and has intermediate values for feed coals, lower values for cleaned fractions, and higher values for refuse fractions; furthermore, it correlates with pyritic sulfur content. In the coals examined, the summed percentage of grain diameters of pyrite enclosed in vitrinite, liptinite, and bi- and trimacerite provides a quantitative measure of the proportion of early diagenetic deposition of pyrite. ?? 1987.
Ruppert, L.F.; Minkin, J.A.; McGee, J.J.; Cecil, C.B.
1992-01-01
Scanning electron microscopy and electron microprobe analysis were used to identify a rare type of As-bearing pyrite in selected specific gravity separates from the Pennsylvanian age Upper Freeport coal bed, west-central Pennsylvania. Arsenic was detected mainly in cell-wall replacement pyrite where concentrations ranged from nondetectable to 1.9 wt %. Although the majority of arsenic-bearing pyrite in the Upper Freeport coal bed is concentrated in massive and late diagenetic pyrite morphologies, the rarer As-bearing cell-replacement pyrite was observed in both light and heavy gravity separates from the three coal facies examined. Arsenic was occasionally detected in cell-filling replacement pyrite, but this As appears to be an artifact produced by signals from underlying and/or adjacent As-bearing cell-wall replacement pyrite. It is postulated that some plants of the Upper Freeport paleoswamp may have biomethylated As, which later could have been converted to dimethylarsine or other volatile organoarsenic compounds by either biologically or chemically driven processes. Once liberated, the arsenic may have been incorporated into pyrite during pyritization of the cell walls. The As incorporation occurred early, before significant compaction of the peat, because the pyritized cell walls are not compacted.
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
Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio
2016-01-01
We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution. PMID:26947441
Premature detonation of an NH₄NO₃ emulsion in reactive ground.
Priyananda, Pramith; Djerdjev, Alex M; Gore, Jeff; Neto, Chiara; Beattie, James K; Hawkett, Brian S
2015-01-01
When NH4NO3 emulsions are used in blast holes containing pyrite, they can exothermally react with pyrite, causing the emulsion to intensively heat and detonate prematurely. Such premature detonations can inflict fatal and very costly damages. The mechanism of heating of the emulsions is not well understood though such an understanding is essential for designing safe blasting. In this study the heating of an emulsion in model blast holes was simulated by solving the heat equation. The physical factors contributing to the heating phenomenon were studied using microscopic and calorimetric methods. Microscopic studies revealed the continuous formation of a large number of gas bubbles as the reaction progressed at the emulsion-pyrite interface, which made the reacting emulsion porous. Calculations show that the increase in porosity causes the thermal conductivity of a reacting region of an emulsion column in a blast hole to decrease exponentially. This large reduction in the thermal conductivity retards heat dissipation from the reacting region causing its temperature to rise. The rise in temperature accelerates the exothermic reaction producing more heat. Simulations predict a migration of the hottest spot of the emulsion column, which could dangerously heat the primers and boosters located in the blast hole. Copyright © 2014 Elsevier B.V. All rights reserved.
Synthesis and characterization of pyrite (FeS{sub 2}) using microwave irradiation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kim, Eun Jung, E-mail: ekim229@uwo.ca; Batchelor, Bill
2009-07-01
A procedure using microwave irradiation was studied to develop a fast and reliable method for synthesizing pyrite. Pyrite was successfully synthesized within a few minutes via reaction of ferric iron and hydrogen sulfide under the influence of irradiation by a conventional microwave oven. The SEM-EDX study revealed that the nucleation and growth of pyrite occurred on the surface of elemental sulfur, where polysulfides are available. Compared to conventional heating, using microwave energy results in rapid (<1 min) formation of smaller particulates of pyrite. Higher levels of microwave power can form pyrite even faster, but faster reaction can lead to themore » formation of pyrite with defects.« less
NASA Astrophysics Data System (ADS)
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.
Rye, R.O.; Roberts, R.J.; Snyder, W.S.; Lahusen, G.L.; Motica, J.E.
1984-01-01
The Big Mike deposit is a massive sulphide lens entirely within a carbonaceous argillite of the Palaeozoic Havallah pelagic sequence. The massive ore contains two generations of pyrite, a fine- and a coarse-grained variety; framboidal pyrite occurs in the surrounding carbonaceous argillite. Coarse grained pyrite is largely recrystallized fine-grained pyrite and is proportionately more abundant toward the margins of the lens. Chalcopyrite and sphalerite replace fine-grained pyrite and vein-fragmented coarse-grained pyrite. Quartz fills openings in the sulphide fabric. S-isotope data are related to sulphide mineralogy and textures. Isotopically light S in the early fine-grained pyrite was probably derived from framboidal biogenic pyrite. The S-isotope values of the later coarse-grained pyrite and chalcopyrite probably reflect a combination of reduced sea-water sulphate and igneous S. Combined S- and O-isotope and textural data accord with precipitation of fine-grained pyrite from a hydrothermal plume like those at the East Pacific Rise spreading centre at lat. 21oN. The primary material was recystallized and mineralized by later fluids of distinctly different S-isotope composition. -G.J.N.
Speciation of arsenic in pyrite by micro-X-ray absorption fine- structure spectroscopy (XAFS)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Paktunc, D.
2008-09-30
Pyrite (FeS2) often contains variable levels of arsenic, regardless of the environment of formation. Arsenian pyrite has been reported in coals, sediments and ore deposits. Arsenian pyrite having As concentrations of up to 10 wt % in sedimentary rocks (Kolker et al. 1997), about 10 wt% in gold deposits (Fleet et al. 1993), 12 wt % in a refractory gold ore (Paktunc et al. 2006) and 20 wt % in a Carlin-type gold deposit in Nevada (Reich et al. 2005) have been reported. Arsenian pyrite is the carrier of gold in hydrothermal Carlin-type gold deposits, and gold concentrations of upmore » to 0.9 wt % have been reported (Reich et al. 2005; Paktunc et al. 2006). In general, high Au concentrations correlate with As-rich zones in pyrite (Paktunc et al. 2006). Pyrite often ends up in mining and metallurgical wastes as an unwanted mineral and consititutes one of the primary sources of As in the wastes. Arsenic can be readily released to the environment due to rapid oxidative dissolution of host pyrite under atmospheric conditions. Pyrite is also the primary source of arsenic in emissions and dust resulting from combustion of bituminous coals. Despite the importance of arsenian pyrite as a primary source of anthropogenic arsenic in the environment and its economic significance as the primary carrier of gold in Carlin-type gold deposits, our understanding of the nature of arsenic in pyrite is limited. There are few papers dealing with the mode of occurrence of arsenic by bulk XAFS in a limited number of pyrite-bearing samples. The present study documents the analysis of pyrite particles displaying different morphologies and a range of arsenic and gold concentrations to determine the nature and speciation of arsenic.« less
An improved pyrite pretreatment protocol for kinetic and isotopic studies
NASA Astrophysics Data System (ADS)
Mirzoyan, Natella; Kamyshny, Alexey; Halevy, Itay
2014-05-01
An improved pyrite pretreatment protocol for kinetic and isotopic studies Natella Mirzoyan1, Alexey Kamyshny Jr.2, Itay Halevy1 1Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 76100, Israel 2Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105, Israel Pyrite is one of the most abundant and widespread of the sulfide minerals with a central role in biogeochemical cycles of iron and sulfur. Due to its diverse roles in the natural and anthropogenic sulfur cycle, pyrite has been extensively studied in various experimental investigations of the kinetics of its dissolution and oxidation, the isotopic fractionations associated with these reactions, and the microbiological processes involved. Pretreatment of pyrite for removal of oxidation impurities to prevent experimental artifacts and inaccuracies is often practiced. While numerous pyrite-cleaning methods have been used in experiments, a common pyrite pretreatment method, often used to investigate pyrite chemistry by the isotopic fractionations associated with it, includes several rinses by HCl, acetone and deionized water. Elemental sulfur (S0) is a common product of incomplete pyrite oxidation. Removal of S0 is desirable to avoid experimental biases associated with its participation in pyrite transformations, but is more complicated than the removal of sulfate. Although rinsing with an organic solvent is in part aimed at removing S0, to the best of our knowledge, the extraction efficiency of S0 in existing protocols has not been assessed. We have developed and tested a new protocol for elemental sulfur removal from the surface of pyrite by ultrasonication with warm acetone. Our data demonstrate the presence of large fractions of S0 on untreated pyrite particle surfaces, of which only approximately 60% was removed by the commonly used pretreatment method. The new protocol described here was found to be more efficient at S0 removal than the commonly used method, and was capable of removing virtually all S0 from the pyrite grains. As pyrite oxidation and dissolution processes are surface-dependent, and even the slightest coating by Fe2+ or sulfide oxidation products can sharply decrease pyrite reactivity, the improved removal of S0 prevents such decreases and allows clearer insights into pyrite reaction mechanisms to be gained from experimental studies. In addition to S0 removal, the suggested method was shown not to introduce any biases in the particle size distribution. The main difference observed between the two protocols is the removal of larger amounts of surface-attached fine particles in the proposed method along with S0. This also removes a potential bias, associated with the surface area of pyrite available for chemical reaction. The suggested pyrite pretreatment protocol is more efficient in removal of S0 contamination from pyrite grains and provides multiple advantages for both kinetic and isotopic investigations of pyrite transformations under various environmental conditions.
Sensitivity of trace element pyritization to pyrite oxidation processes
NASA Astrophysics Data System (ADS)
Moreira, Manuel; Díaz, Rut; Mendoza, Ursula; Capilla, Ramses; Böttcher, Michael; Luiza Albuquerque, Ana; Machado, Wilson
2014-05-01
Total trace elements concentration variability in marine sediments has been widely used as a proxy for redox conditions and marine paleoprodutivity. However, partial extraction procedures reduce influences of detrital sedimentary fractions, and information on trace element geochemical partitioning can contribute to provide comprehensive evidences on elemental sensitivity to particular processes. The potential effect of sedimentary pyrite re-oxidative cycling on the degree of trace metal pyritization (DTMP) has not been previously evaluated. This study investigates this effect in 4 sediment cores from the continental shelf under the influence of a tropical upwelling system (Cabo Frio, Brazil). The relation of DTMP with stable isotope signals (δ34SCRS) of chromium reducible sulfur, which becomes lighter in response to intense pyrite re-oxidative cycling in the study area, suggests high (As, Cd and Mn), low (Cu and Zn) or negligible (Cr and Ni) re-oxidation influences. The oldest, pyrite-richer sediments provide an apparent threshold for intense pyrite re-oxidation, after which most trace elements (As, Cd, Zn and Mn) presented more accentuated pyritization. A middle shelf core presented negative correlations of reactive (HCl-soluble) Mn, Cu and Ni with pyrite iron, suggesting Mn oxide (and associated metals) depletion in reaction with pyrite. Results provided evidences for coupled influences from both aerobic and anaerobic oxidative processes on trace elements incorporation into pyrite. Pyrite δ34S signatures under the oxic bottom water from the study area were similar to those from euxinic sedimentary environments, suggesting that pyrite re-oxidative cycling can affect trace element susceptibility to be incorporated and preserved into pyrite in a wide range of sedimentary conditions. The evaluation of trace elements sensitivity to these processes can contribute to improve the use of multiple DTMP data (e.g., as paleoredox proxies). Considering that S re-oxidative cycling is ubiquitous in many sedimentary conditions, such coupled use of DTMP and δ34SCRS proxies can be possibly applied to a large variety of sedimentary environments.
NASA Astrophysics Data System (ADS)
Yun, Seong-Taek; So, Chil-Sup; Choi, Sang-Hoon; Shelton, Kevin L.; Koo, Ja-Hak
1993-04-01
The Wolyu mine is one of the largest vein-type gold-silver-bearing epithermal systems in the Youngdong district and is the first gold-silver deposit in Korea found to contain significant germanium, in the form of argyrodite (Ag8GeS6). Mineralized veins (78.9 ± 1.2 Ma) crosscutting Late Cretaceous hostrock tuff and quartz porphyry (81.5 ± 1.8 Ma) consist of three stages of quartz and carbonates, the first of which contains pyrite, basemetal sulfides and Au-Ag-minerals. Stage I Au-Ag-Ge-mineralized veins show a systematic variation of mineral assemblage with time: (1) quartz + pyrite; (2) quartz + pyrite + sphalerite + electrum + argentite; (3) carbonate + quartz + sphalerite + electrum + argentite; (4) carbonate + native silver + argentite + Ag-sulfosalts + argyrodite + sphalerite. Calculated values of temperature and sulfur activity are: assemblage (1), 360-280°C and 10-7-10-10; (2), 280-210°C and 10-10-10-14; (3), 210-180°C and 10-14-10-16; (4), 180-155°C and 10-17-10-18. These data, the frequent association of gold with sulfides, and the abundance of pyrite in alteration zones indicate that decreasing sulfur activity and cooling were important in triggering gold deposition. Hydrogen and oxygen isotope compositions of ore fluids display a systematic variation with increasing time. Within the main Ag-Au-Ge mineralization, δD and δ 18O values decrease with the transition from quartz to carbonate deposition (from -78 and -2.8% to -90 and -8.7%., respectively), indicating increasing involvement (mixing) of less evolved meteoric water which resulted in progressive cooling and dilution of ore fluids in the shallow (≈ 370 600 m) Wolyu epithermal system.
NASA Astrophysics Data System (ADS)
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jin, Song
2014-11-18
This project seeks to develop nanostructures of iron pyrite, an earth-abundant semiconductor, to enable their applications in high-performance photovoltaic (PV) devices. Growth of high purity iron pyrite nanostructures (nanowires, nanorods, and nanoplates), as well as iron pyrite thin films and single crystals, has been developed and their structures characterized. These structures have been fundamentally investigated to understand the origin of the low solar energy conversion efficiency of iron pyrite and various passivation strategies and doping approaches have been explored in order to improve it. By taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we fullymore » characterized both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices and show that pyrite is n-type in the bulk and p-type near the surface due to strong inversion, which has important consequences to using nanocrystalline pyrite for efficient solar energy conversion. Furthermore, through a comprehensive investigation on n-type iron pyrite single crystals, we found the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a non-constant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explains the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings suggest new ideas on how to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films to enable them for high performance solar applications.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kalyoncu, R.S.; Boyer, J.P.; Snyder, M.J.
Partial data on the characterization of Well 0-1 (Christian County, Kentucky) shales were first reported in the Fifth Quarterly Technical Progress Report on January 1978. This report presents all the characterization data and its analysis on the 0-1 shales. Coring of Well 0-1 was accomplished in October 1976. A total of 17 samples were obtained, 13 for Battelle and 4 for other DOE Contractors. Methane is almost the sole hydrocarbon gas present in these shales, with higher chain hydrocarbon gases nearly nonexistent. An apparent increase in hydrocarbon gas contents with shale depth is observed. Other organic contents (in the formmore » of carbon and hydrogen) also show an increase with increasing shale depth. An increase in hydrocarbon gas contents with carbon and hydrogen contents is also noticeable. Natural gas, carbon and hydrogen contents all vary inversely with bulk densities. 0-1 shales show low mercury intrusion porosities and very low to negligible gas permeabilities. Lithology of these shales is very similar to those previously reported, quartz being the most abundant single mineral. Illite and kaolin are the major clay minerals with a number of carbonates (nahcolite, sortite, siderite) present in moderate quantities. Pyrite is also observed in significant quantities.« less
48 CFR 2052.211-71 - Technical progress report.
Code of Federal Regulations, 2014 CFR
2014-10-01
... 48 Federal Acquisition Regulations System 6 2014-10-01 2014-10-01 false Technical progress report... Technical progress report. As prescribed at 2011.104-70(b), the contracting officer shall insert the... solicitation. Technical Progress Report (JAN 1993) The contractor shall provide a monthly Technical Progress...
48 CFR 2052.211-71 - Technical progress report.
Code of Federal Regulations, 2013 CFR
2013-10-01
... 48 Federal Acquisition Regulations System 6 2013-10-01 2013-10-01 false Technical progress report... Technical progress report. As prescribed at 2011.104-70(b), the contracting officer shall insert the... solicitation. Technical Progress Report (JAN 1993) The contractor shall provide a monthly Technical Progress...
48 CFR 2052.211-71 - Technical progress report.
Code of Federal Regulations, 2012 CFR
2012-10-01
... 48 Federal Acquisition Regulations System 6 2012-10-01 2012-10-01 false Technical progress report... Technical progress report. As prescribed at 2011.104-70(b), the contracting officer shall insert the... solicitation. Technical Progress Report (JAN 1993) The contractor shall provide a monthly Technical Progress...
48 CFR 2052.211-71 - Technical progress report.
Code of Federal Regulations, 2011 CFR
2011-10-01
... 48 Federal Acquisition Regulations System 6 2011-10-01 2011-10-01 false Technical progress report... Technical progress report. As prescribed at 2011.104-70(b), the contracting officer shall insert the... solicitation. Technical Progress Report (JAN 1993) The contractor shall provide a monthly Technical Progress...
Cerro de Pasco and other massive sulfide deposits of central Peru
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cheney, E.S.
1985-01-01
The famous Cerro de Pasco Pb-Zn-Ag deposit historically has been considered to be hydrothermally derived from an adjacent Tertiary volcanic vent. However, texturally massive pyrite-chert and pyrite-sphalerite-galena in the deposit have the same strike and cross folds as the adjacent pre-Tertiary strata. Both the deposit and the strata are cut by one of the large Longitudinal Faults. Both dikes and pyrite-enargite veins associated with the vent cut the massive sulfides; fragments of massive pyrite occur in the vent. A few examples of laminated pyrite and chert, banded pyrite and chert, banded pyrite and sphalerite, and banded pyrite, sphalerite, and galenamore » are preserved in the massive sulfide portion of the deposit. The deposit has the composition and zoning patterns typical of shale-hosted massive sulfides. Cerro de Pasco probably in part of the pelitic Devonian Excelsior formation. The Colquijirca deposit 8 km to the south and the San Cristobal district 110 km to the south likewise have been considered to be Tertiary volcanic hydrothermal deposits. Colquijirca consists of stratigraphically controlled mantos of layered pyrite, chert and tuff in the Tertiary Calera formation. The mantos of the San Cristobal district are along the upper contact of the pyritic, Permian, Catalina felsic volcanic rocks; some ore consists of laminated pyrite and sphalerite. Tertiary plutons are conspicuously absent at San Cristobal, and the ores are brecciated by Tertiary folding.« less
Mechanism of microbial flotation using Thiobacillus ferrooxidans for pyrite suppression.
Ohmura, N; Kitamura, K; Saiki, H
1993-03-15
Microbial desulfurization might be developed as a new process for the removal of pyrite sulfur from coal sluries such as coal-water mixture (CWM). An application of iron-oxidizing bacterium Thiobacillus ferrooxidans to flotation would shorten the periods of the microbial removal of pyrite from some weeks by leaching methods to a few minutes. The floatability of pyrite in flotation was mainly reduced by T. ferrooxidans itself rather than by other microbial substances in bacterial culture as additive of flotation liquor. Floatability was suppressed within a few seconds by bacterial contact. The suppression was proportional to increasing the number of cells observed between bacterial adhesion and the suppression of floatability. If 25% of the total pyrite surface area covered with the bacteria, pyrite floatability would be completely depressed. Bacteria that lost their iron-oxidizing activities by sodium cyanide treatment were also able to adhere to pyrite and reduced pyrite floatability as much as normal bacteria did. Thiobacillus ferrooxidans ATCC 23270, T-1, 9, and 11, which had different iron-oxidizing abilities, suppressed floatability to similar-levels. The oxidizing ability of bacteria did not influence the suppressing effect. These results showed the mechanism of the suppression of pyrite floatability by bacteria. Quick bacterial adhesion to pyrite induced floatability suppression by changing the surface property from hydrophobic. The quick adhesion of the bacterium was the novel function which worked to change the surface property of pyrite to remove it from coal. (c) 1993 John Wiley & Sons, Inc.
The hidden life of pyrite: how low can it go?
NASA Astrophysics Data System (ADS)
Boyle, Alan; Barrie, Craig; Salter, Michael
2010-05-01
Pyrite is the most abundant sulphide mineral in the Earth's crust, being present in most rock units but only volumetrically important in sulphide ore deposits. Thus, rheological behaviour of pyrite does not have significant implications for crustal deformation as a whole, but it does for deformation of ore deposits. Therefore, understanding pyrite behaviour in ore deposits may help understanding of deformation in rocks where it is of low abundance. Pyrite is a difficult mineral to study because it is both opaque and cubic, two properties that hide most of its microstructure when studied using optical microscopy as well as standard SEM back-scattered electron imaging. Etching can reveal some of the internal secrets of pyrite, but the technique is not universally applicable. The generally accepted view from such studies, coupled with experimental deformation and some TEM studies, is that pyrite is a robust mineral, which, under typical geological strain-rates, deforms by plastic deformation mechanisms above ~425 °C and by brittle or pressure-solution diffusive mechanisms below. Over the last decade or so, the advent of reliable and fast SEM-based electron backscattered diffraction (EBSD) systems, coupled with orientation contrast (OC) imaging techniques, has revolutionised study of microstructure in cubic minerals. Plastic deformation can now be readily identified in pyrite; it is no longer hidden. Freitag et al (2004) documented relatively low temperature (~350 °C) plastic deformation of pyrite from Green's Creek, Alaska, raising the possibility that pyrite deforms plastically at lower temperatures than is generally accepted. In this presentation we describe pyrite microstructures from a series of pyrite-rich polymetallic ore deposits (Parys Mountain, Anglesey; Løkken, Norway; Baia Borsa, Romania), deformed at low temperature metamorphic conditions (~200-420 °C). Our results (Barrie et al. 2009) indicate that pyrite grains in all of the ore deposits studied preserve internal lattice ‘distortion' or ‘bending' indicating plastic deformation mechanisms operated. Many pyrite grains in the ore deposits also contain low-angle (~2°) sub-grain boundaries or ‘dislocation walls', indicating that both dislocation glide and creep deformation mechanisms have operated within the pyrite grains. These results indicate that plastic deformation of pyrite, under geological strain-rates, can go down to as low as ~200 °C suggesting the brittle-ductile transition in pyrite occurs at temperatures potentially as low as ~200 °C; much lower than the generally accepted temperature of ~425 °C. Many pyrite grains in sulphide ore deposits preserve internal chemical zonation of trace elements (e.g. Large et al. 2009). The potential relationship between plastic deformation and trace element distribution in pyrite will be discussed. Barrie, C. D., Boyle, A. P. & Salter, M., 2009. How low can you go? - Extending downwards the limits of plastic deformation in pyrite. Mineralogical Magazine, 73(6), 895-913. Freitag, K., Boyle, A. P., Nelson, E., Hitzman, M., Churchill, J. & Lopez-Pedrosa, M., 2004. The use of electron backscatter diffraction and orientation contrast imaging as tools for sulphide textural studies: example from the Greens Creek deposit (Alaska). Mineralium Deposita, 39, 103-113. 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. 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. Economic Geology, 104(5), 635-668.
Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue
Rolison, John M.; Stirling, Claudine H.; Middag, Rob; ...
2018-02-19
We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 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 shiftmore » 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 FeS 2 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 in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less
Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rolison, John M.; Stirling, Claudine H.; Middag, Rob
We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 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 shiftmore » 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 FeS 2 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 in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less
Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue
NASA Astrophysics Data System (ADS)
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 in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Blackwell, W.H.; Martin, A.J.
Much naturally occurring pyritization is biologically mediated, with specific types of bacteria (sulfate reducers) promoting the reactions. Among the criteria required for pyritization in a marine environment are the presence of: (1) interstitial iron ions, (2) a primarily anaerobic (reducing) environment; (3) an organic-rich substrate, and (4) sulfate-reducing bacteria (releasing sulfide). However, the direct connection between pyritization and bacteria (microfloral remains) is difficult to visualize in the fossil record. This study focuses specifically on pyritized burrow linings that occur in strongly bioturbated wackestones from the Arnheim Formation (Cincinnatian Series, Upper Ordovician). Specific reducing microenvironments (i.e. mucoidal burrow linings) were themore » sites of early diagenetic pyritization in otherwise oxygenated, organic-rich sediments. Material examined under both the light and electron microscopes revealed occasional evidence of pyrite associated with filamentous structures. These structures possess a shape and size consistent with certain types of bacteria. This relationship, bacterialike structures with pyrite, may be more common in the fossil record than previously suspected.« less
Bioleaching of two different types of chalcopyrite by Acidithiobacillus ferrooxidans
NASA Astrophysics Data System (ADS)
Dong, Ying-bo; Lin, Hai; Fu, Kai-bin; Xu, Xiao-fang; Zhou, Shan-shan
2013-02-01
Two different types of chalcopyrite (pyritic chalcopyrite and porphyry chalcopyrite) were bioleached with Acidithiobacillus ferrooxidans ATF6. The bioleaching of the pyritic chalcopyrite and porphyry chalcopyrite is quite different. The copper extraction reaches 46.96% for the pyritic chalcopyrite after 48-d leaching, but it is only 14.50% for the porphyry chalcopyrite. Proper amounts of initial ferrous ions can improve the efficiency of copper extraction for the two different types of chalcopyrite. The optimum dosage of ferrous ions for the pyritic chalcopyrite and porphyry chalcopyrite is different. The adsorption of ATF6 on the pyritic chalcopyrite and porphyry chalcopyrite was also studied in this paper. It is found that ATF6 is selectively adsorbed by the two different types of chalcopyrite; the higher adsorption onto the pyritic chalcopyrite than the porphyry chalcopyrite leads to the higher copper dissolution rate of the pyritic chalcopyrite. In addition, the zeta-potential of chalcopyrite before and after bioleaching further confirms that ATF6 is more easily adsorbed onto the pyritic chalcopyrite.
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.
NASA Astrophysics Data System (ADS)
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 of Au could have been sourced from pyrite and instead point to the role of substructures in pyrite as depositional traps for Au during syn-metamorphic deformation- and fluid-assisted diffusion Au-upgrading.
Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.
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.
NASA Astrophysics Data System (ADS)
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 depositional conditions and sources of both sulfide and uranium mineralization and an improved understanding of pyrite geochemistry can also underpin an effective vector for uranium exploration at Beverley North and other sedimentary systems of the Lake Eyre Basin, as well as in comparable geological environments elsewhere. Average intensity of 32S signal in counts per second × 108.Drift corrected 34S/32S prior to IMF calibration.Two-sigma propagated uncertainty on individual measurements.
NASA Astrophysics Data System (ADS)
Kouzmanov, Kalin; Bailly, Laurent; Ramboz, Claire; Rouer, Olivier; Bény, Jean-Michel
2002-08-01
Pyrite samples from the Radka epithermal, replacement type, volcanic rock-hosted copper deposit, Bulgaria, have been studied using near-infrared (IR) microscopy. Two generations of pyrite based on their textures, composition and behaviour in IR light can be distinguished. Electron microprobe analyses, X-ray elemental mapping and Fourier transform infrared spectroscopy were used to study the relationship between crystal zoning, trace element contents and IR transmittance of pyrite. The observed crystal zoning is related to variable arsenic contents in massive fine-grained and colloform pyrite from the early pyrite-quartz assemblage, and cobalt contents in pyrite crystals from the late quartz-pyrite vein assemblage. There is a negative correlation between trace element content and IR transmittance of pyrite. The IR transparency of pyrite is thus a sensitive indicator of changes in trace element concentrations. Fluid inclusions have only been found in the second pyrite generation. Scanning electron microscopy observations on open fluid inclusion cavities permitted the crystallographic features of vacuoles to be determined. A characteristic feature of primary fluid inclusions in pyrite is a negative crystal habit, shaped mainly by {100}, {111} and {210}. This complicated polyhedral morphology is the reason for the observed opacity of some isometric primary inclusions. Secondary fluid inclusion morphology depends on the nature of the surface of the healed fracture. Recognition of the primary or secondary origin of fluid inclusions is enhanced by using crystallographically oriented sections. Microthermometric measurements of primary inclusions indicate that the second pyrite generation was deposited at maximum P-T conditions of 400 °C and 430 bar and from a fluid of low bulk salinity (3.5-4.6 wt%), possibly KCl-dominant. There are large ranges for homogenisation temperatures in secondary inclusions because of necking-down processes. Decrepitation features of some of pyrite-hosted inclusions and of all inclusions in associated quartz indicate reheating of the veins to 500-550 °C. The late cobalt-rich quartz-pyrite vein assemblage in the Radka deposit may be the shallow manifestation of deeper and genetically related porphyry copper mineralisation. This is a common observation of many intermediate- to high-sulfidation epithermal replacement-type ore bodies in this ore district and possibly the Cretaceous Banat-Srednogorie metallogenic belt in general.
The coupled geochemistry of Au and As in pyrite from hydrothermal ore deposits
NASA Astrophysics Data System (ADS)
Deditius, Artur P.; Reich, Martin; Kesler, Stephen E.; Utsunomiya, Satoshi; Chryssoulis, Stephen L.; Walshe, John; Ewing, Rodney C.
2014-09-01
The ubiquity of Au-bearing arsenian pyrite in hydrothermal ore deposits suggests that the coupled geochemical behaviour of Au and As in this sulfide occurs under a wide range of physico-chemical conditions. Despite significant advances in the last 20 years, fundamental factors controlling Au and As ratios in pyrite from ore deposits remain poorly known. Here we explore these constraints using new and previously published EMPA, LA-ICP-MS, SIMS, and μ-PIXE analyses of As and Au in pyrite from Carlin-type Au, epithermal Au, porphyry Cu, Cu-Au, and orogenic Au deposits, volcanogenic massive sulfide (VHMS), Witwatersrand Au, iron oxide copper gold (IOCG), and coal deposits. Pyrite included in the data compilation formed under temperatures from ∼30 to ∼600 °C and in a wide variety of geological environments. The pyrite Au-As data form a wedge-shaped zone in compositional space, and the fact that most data points plot below the solid solubility limit defined by Reich et al. (2005) indicate that Au1+ is the dominant form of Au in arsenian pyrite and that Au-bearing ore fluids that deposit this sulfide are mostly undersaturated with respect to native Au. The analytical data also show that the solid solubility limit of Au in arsenian pyrite defined by an Au/As ratio of 0.02 is independent of the geochemical environment of pyrite formation and rather depends on the crystal-chemical properties of pyrite and post-depositional alteration. Compilation of Au-As concentrations and formation temperatures for pyrite indicates that Au and As solubility in pyrite is retrograde; Au and As contents decrease as a function of increasing temperature from ∼200 to ∼500 °C. Based on these results, two major Au-As trends for Au-bearing arsenian pyrite from ore deposits are defined. One trend is formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock interactions and/or can be highly perturbed by changes in temperature and alteration by hydrothermal fluids. The second trend consists of pyrites from porphyry Cu and epithermal Au deposits, which are characterised by compositions that preserve the Au/As signature of mineralizing magmatic-hydrothermal fluids, confirming the role of this sulfide in controlling metal ratios in ore systems.
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.
Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.
2008-01-01
Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.
Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite
Sun, Liang; Li, Yan; Li, Aimin
2015-01-01
Wastewater from chemical plants has remarkable antibiotic effects on the microorganisms in traditional biological treatment processes. An enhanced Fenton system catalyzed by natural pyrite was developed to degrade this kind of wastewater. Approximately 30% chemical oxygen demand (COD) was removed within 120 min when 50 mmol/L H2O2 and 10 g/L natural pyrite were used at initial pH from 1.8 to 7. A BOD5/COD enhancement efficiency of 210% and an acute biotoxicity removal efficiency of 84% were achieved. The COD removal efficiency was less sensitive to initial pH than was the classic Fenton process. Excessive amounts of pyrite and H2O2 did not negatively affect the pyrite Fenton system. The amount of aniline generated indicated that nitrobenzene reduction by pyrite was promoted using a low initial concentration of H2O2 (<5 mmol/L). Fluorescence excitation emission matrix analyses illustrated that H2O2 facilitated the reduction by natural pyrite of organic molecules containing an electron-withdrawing group to electron-donating group. Thus, the Fenton-like process catalyzed by pyrite can remediate wastewater containing organic pollutants under mild reaction conditions and provide an alternative environmentally friendly method by which to reuse natural pyrite. PMID:26516893
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.
Tuttle, M.L.W.; Breit, G.N.
2009-01-01
Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.
Silane-based coatings on the pyrite for remediation of acid mine drainage.
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.
Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis
Foley, N.; Ayuso, R.A.; Seal, R.R.
2001-01-01
Auriferous iron sulfide-bearing deposits of the Carolina slate belt have distinctive mineralogical and textural features-traits that provide a basis to construct models of ore deposition. Our identification of paragenetically early types of pyrite, especially remnant colloform, crustiform, and layered growth textures of pyrite containing electrum and pyrrhotite, establishes unequivocally that gold mineralization was coeval with deposition of host rocks and not solely related to Paleozoic tectonic events. Ore horizons at the Haile deposit, South Carolina, contain many remnants of early pyrite: (1) fine-grained cubic pyrite disseminated along bedding; (2) fine- grained spongy, rounded masses of pyrite that may envelop or drape over pyrite cubes; (3) fragments of botryoidally and crustiform layered pyrite, and (4) pyritic infilling of vesicles and pumice. Detailed mineral chemistry by petrography, microprobe, SEM, and EDS analysis of replaced pumice and colloform structures containing both arsenic compositional banding and electrum points to coeval deposition of gold and the volcanic host rocks and, thus, confirms a syngenetic origin for the gold deposits. Early pyrite textures are present in other major deposits of the Carolina slate belt, such as Ridgeway and Barite Hill, and these provide strong evidence for models whereby the sulfide ores formed prior to tectonism. The role of Paleozoic metamorphism was to remobilize and concentrate gold and other minerals in structurally prepared sites. Recognizing the significance of paragenetically early pyrite and gold textures can play an important role in distinguishing sulfide ores that form in volcanic and sedimentary environments from those formed solely by metamorphic processes. Exploration strategies applied to the Carolina slate belt and correlative rocks in the eastern United States in the Avalonian basement will benefit from using syngenetic models for gold mineralization.
NASA Astrophysics Data System (ADS)
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 is a refined search tool with straightforward application in the search for early life on Earth and distant life recorded in meteorites, returned samples, and in situ measurements.
Microbial acceleration of aerobic pyrite oxidation at circumneutral pH.
Percak-Dennett, E; He, S; Converse, B; Konishi, H; Xu, H; Corcoran, A; Noguera, D; Chan, C; Bhattacharyya, A; Borch, T; Boyd, E; Roden, E E
2017-09-01
Pyrite (FeS 2 ) is the most abundant sulfide mineral on Earth and represents a significant reservoir of reduced iron and sulfur both today and in the geologic past. In modern environments, oxidative transformations of pyrite and other metal sulfides play a key role in terrestrial element partitioning with broad impacts to contaminant mobility and the formation of acid mine drainage systems. Although the role of aerobic micro-organisms in pyrite oxidation under acidic-pH conditions is well known, to date there is very little known about the capacity for aerobic micro-organisms to oxidize pyrite at circumneutral pH. Here, we describe two enrichment cultures, obtained from pyrite-bearing subsurface sediments, that were capable of sustained cell growth linked to pyrite oxidation and sulfate generation at neutral pH. The cultures were dominated by two Rhizobiales species (Bradyrhizobium sp. and Mesorhizobium sp.) and a Ralstonia species. Shotgun metagenomic sequencing and genome reconstruction indicated the presence of Fe and S oxidation pathways in these organisms, and the presence of a complete Calvin-Benson-Bassham CO 2 fixation system in the Bradyrhizobium sp. Oxidation of pyrite resulted in thin (30-50 nm) coatings of amorphous Fe(III) oxide on the pyrite surface, with no other secondary Fe or S phases detected by electron microscopy or X-ray absorption spectroscopy. Rates of microbial pyrite oxidation were approximately one order of magnitude higher than abiotic rates. These results demonstrate the ability of aerobic microbial activity to accelerate pyrite oxidation and expand the potential contribution of micro-organisms to continental sulfide mineral weathering around the time of the Great Oxidation Event to include neutral-pH environments. In addition, our findings have direct implications for the geochemistry of modern sedimentary environments, including stimulation of the early stages of acid mine drainage formation and mobilization of pyrite-associated metals. © 2017 John Wiley & Sons Ltd.
Mechanisms of arsenic-containing pyrite oxidation by aqueous arsenate under anoxic conditions
NASA Astrophysics Data System (ADS)
Qiu, Guohong; Gao, Tianyu; Hong, Jun; Tan, Wenfeng; Liu, Fan; Zheng, Lirong
2017-11-01
Adsorption and redox reactions occur between arsenic-containing pyrite and arsenate, which affect the migration and conversion of arsenic in soils and waters. However, the influence of arsenic incorporated in pyrite on the interaction processes is still enigmatic. In this work, arsenic-containing pyrites were hydrothermally synthesized with composition similar to naturally surface-oxidized pyrites in supergene environments. The effects of arsenic incorporation on the chemical composition and physicochemical properties were analyzed, and the interaction mechanism between arsenic-containing pyrites and aqueous arsenate was also studied within pH 3.0-11.0. Arsenic-containing pyrites with the arsenic contents of 0 (Apy0), 4.4 (Apy5) and 9.9 wt.% (Apy10) were produced in hydrothermal systems. As(III) and As(-I) respectively substituted Fe(II) and S2(-II) in the pyrite, and their relative contents respectively reached 76.6% and 17.2% in Apy5, and 91.0% and 8.0% in Apy10. Arsenic substitution resulted in a high content of Fe(III) in the form of Fe(III)sbnd S and a decrease in pyrite crystallinity. During the redox processes of arsenic-containing pyrites and arsenate, elemental S0, SO42- and goethite were formed as the main products with the adsorption of As(III,V), and As(III) was released due to the collapse of the crystal structure of pyrite and the oxidation of As(-I). Different redox mechanisms were achieved with pH increasing from 3.0 to 11.0 in the reaction system. At pH 3.0-6.0, Fe(III) contributed much to the oxidation of arsenic-containing pyrites, and arsenate and released As(III) were adsorbed on the surface of solid products. At pH 7.0-11.0, aqueous arsenate worked as the major oxidant, and its oxidation capacity increased with increasing pH. When the pH was increased from 3.0 to 7.0 and 11.0, the release ratio of incorporated arsenic from Apy10 particles increased from 34.1% to 45.0% and 56.8%, respectively. The present study facilitates a better understanding about the interaction mechanisms between arsenic-containing pyrite and arsenate in supergene environments.
Selective flotation of inorganic sulfides from coal
Miller, Kenneth J.; Wen, Wu-Wey
1989-01-01
Pyritic sulfur is removed from coal or other carbonaceous material through the use of humic acid as a coal flotation depressant. Following the removal of coarse pyrite, the carbonaceous material is blended with humic acid, a pyrite flotation collector and a frothing agent within a flotation cell to selectively float pyritic sulfur leaving clean coal as an underflow.
Oxidation of pyrite in coal to magnetite
Thorpe, A.N.; Senftle, F.E.; Alexander, C.C.; Dulong, F.T.
1984-01-01
When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393-455 ??C, pyrite (FeS2) in coal is partially converted to magnetite (Fe304). The maximum amount of Fe304 formed during the time of heating corresponds to 5-20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample. ?? 1984.
Chemosynthetic microbial activity at Mid-Atlantic Ridge hydrothermal vent sites
NASA Astrophysics Data System (ADS)
Wirsen, Carl O.; Jannasch, Holger W.; Molyneaux, Stephen J.
1993-06-01
Chemosynthetic production of microbial biomass, determined by 14CO2 fixation and enzymatic (RuBisCo) activity, at the Mid-Atlantic Ridge (MAR) 23° and 26°N vent sites was found in various niches: warm water emissions, loosely rock-attached flocculent material, dense morphologically diverse bacterial mats covering the surfaces of polymetal sulfide deposits, and filamentous microbes on the carapaces of shrimp (Rimicaris exoculata). The bacterial mats on polymetal sulfide surfaces contained unicellular and filamentous bacteria which appeared to use as their chemolithotrophic electron or energy source either dissolved reduced minerals from vent emissions, mainly sulfur compounds, or solid metal sulfide deposits, mainly pyrite. Moderately thermophilic Chemosynthetic activity was observed in carbon dioxide fixation experiments and in enrichments, but no thermophilic aerobic sulfur oxidizers could be isolated. Both obligate and facultative chemoautotrophs growing at mesophilic temperatures were isolated from all chemosynthetically active surface scrapings. The obligate autotrophs could oxidize sterilized MAR natural sulfide deposits as well as technical pyrite at near neutral pH, in addition to dissolved reduced sulfur compounds. While the grazing by shrimp on the surface mats of MAR metal sulfide deposits was observed and deemed important, the animals' primary occurrence in dense swarms near vent emissions suggests that they were feeding at these sites, where conditions for Chemosynthetic growth of their filamentous microbial epiflora were optimal. The data show that the transformation of geothermal energy at the massive polymetal sulfide deposits of the MAR is based on the lithoautotrophic oxidation of soluble sulfides and pyrites into microbial biomass.
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.
An Investigation Of The Effect Of Particle Size On Oxidation Of Pyrites In Coal.
NASA Astrophysics Data System (ADS)
Chan, Paul K.; Frost, David C.
1986-08-01
We have used X-ray photoelectron spectroscopy (XPS) to study the variation of surface pyrite density with coal particle size (53 4m - 250 4μm). We also detect and monitor pyrite oxidation to sulfate, an important process influencing the surface-dependency of coal-cleansing methods such as flotation. It is very likely that as coal is crushed as part of the processes employed to rid it of prospective pollutants one eventually reaches a pyrite size which may be called "characteristic". It is this parameter that we examine here. Good correlations are established between (i) the liberation of pyrite and particle size, (ii) surface pyrite/sulfate ratio, and (iii) oxidized and non-oxidized sulfur in a typical Canadian coal. For "non-oxidized", or "fresh" coal, the dispersion of pyrite on the coal surface is inversely proportional to coal particle radius, and the tangents of this curve intersect at a particular particle size (106±5 4μm). Although, for the oxidized coal, the appearance of the curves depend on oxidation time intervals at low temperature with humid air, there is an "optimum" particle size which exhibits maximum surface pyrite. Notably, this "optimum" size corresponds to the tangent's intersection for the non-oxidized coal, and hence the "characteristic" size of constituent pyrite. This should allow prediction of pyrite occurrence, a parameter of paramount interest in coal processing and cleaning technology. Coal surface characterization obtained by XPS after various conditioning steps and during flotation, allow both a functional analysis via the study of chemical shifts and a semi-quantitative analysis based on relative intensity measurements.
Surface Behavior of Iron Sulfide Ore during Grinding with Alumina Media
NASA Astrophysics Data System (ADS)
Martín, Reyes P.; Elia, Palácios B.; Patiño, Francisco C.; Escudero, Ramiro G.; Mizraim, Uriel Flores G.; Reyes, Iván A. D.; Palazuelos, Laura Angeles
This research was conducted to study the oxidation and surface modification of pyrite in an inert mill and alumina grinding media at different pH values. The extent and progress of the oxidation function of milling time, by measuring some physicochemical variables, zeta potential (ZP), infrared analysis and monitoring. The results indicate pyrite oxidation during grinding, releasing iron and sulfur ions to the solution increasing its concentration with the initial pH and the milling time, the ORP and DO decrease the grinding time, on the other hand presents negative values ZP pH of 9, 11 and 12, whereas at pH 5, 7 and 13, the ZP is positive, FTIR generally detect the presence of free sulfate ion molecule 1084 cm-1, goethite with the absorption band at about 794 cm-1, also occurs in a band assigned to 470 cm-1 lepidocrocite oxy iron hydroxide γ- FeOOH, nucleated species or formed during milling.
Lyons, P.C.; Whelan, J.F.; Dulong, F.T.
1989-01-01
The amount, kind, distribution, and genesis of pyrite in the Lower Bakerstown coal bed in a 150 ?? 15 m area of the Bettinger mine, Castleman coal field, Maryland, were studied by various analytical techniques. The mined coal, which had a nonmarine roof rock, contained 1.4-2.8 wt.% total sulfur, generally much lower than the high-sulfur coal (> 3.0 wt.% total S) to the north, which is associated with marine roof rocks. Small-scale systematic and nonsystematic variations in total sulfur and pyrite distribution were found in the mined area. In the column sample, most of the pyrite was found in the upper 9 cm of the 69-cm-thick mined coal and occurred mainly as a pyrite lens containing cell fillings in seed-fern tissue (coal ball). As-bearing pyrite was detected by laser microprobe techniques in the cell walls of this tissue but not elsewhere in the column sample. This may indicate that the As was derived from decomposition of organic matter in the cell walls. The sulfur isotopic composition and distribution of pyrite in the coal are consistent with introduction of marine sulfate shortly after peat deposition, followed by bacterial reduction and pyrite precipitation. Epigenetic cleat pyrite in the coal is isotopically heavy, implying that later aqueous sulfate was 34S-enriched. ?? 1989.
Selective flotation of inorganic sulfides from coal
Miller, K.J.; Wen, Wu-Wey
1988-05-31
Pyritic sulfur is removed from coal or other carbonaceous material through the use of humic acid as a coal flotation depressant. Following the removal of coarse pyrite, the carbonaceous material is blended with humic acid, a pyrite flotation collector and a frothing agent within a flotation cell to selectively float pyritic sulfur leaving clean coal as an underflow. 1 fig., 2 tabs.
Farahat, Mohsen; Hirajima, Tsuyoshi; Sasaki, Keiko
2010-09-15
The adhesion behavior of Ferroplasma acidiphilum archaeon to pyrite mineral was investigated experimentally and theoretically. F. acidiphilum showed high affinity to adhere to pyrite surface at acidic regions, however low affinity was observed at neutral and alkaline regions. The microbe-mineral adhesion was assessed by the extended DLVO theory. Hamaker constants, electron donors, electron acceptors and surface charges for the microbe and the mineral were experimentally determined. The extended DLVO theory was used to explain the adhesion results. Significant changes to the pyrite surface properties after being treated with the microbial cells were observed. Pyrite lost its hydrophobic nature and became hydrophilic, the contact angle of untreated pyrite was 61 degrees and this decreased to 36 degrees after the treatment. As a consequence, the flotation experiment results showed that F. acidiphilum strain could act as a good depressant for pyrite in xanthat flotation; where in absence of F. acidiphilum cells, over 95% of pyrite can be recovered as a float. However, when the mineral was pretreated with F. acidiphilum cells, less than 20% can be recovered as a float. Copyright 2010 Elsevier Inc. All rights reserved.
Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.
Wu, Deli; Liu, Yanxia; Zhang, Zhiyong; Ma, Luming; Zhang, Yalei
2015-01-01
A pyrite-catalyzed reaction was used to degrade chloramphenicol. Chloramphenicol could be almost 100% removed within 60 minutes when 1 mM H2O2 and 0.1 g/L pyrite were added at an initial pH=3. During oxidation, intermediates such as nitrobenzaldehyde and dichloroacetamide were identified by gas chromatography/mass spectrometry (GC/MS). The •OH was identified by electron spin-resonance spectroscopy. Pyrite was digested to determine elements by ICP (inductive coupled plasma emission spectrometer). To understand the reaction mechanism and the role of natural pyrite in these processes, techniques including scanning electron microscopy and energy dispersive spectrometry were employed to characterize the solid sample. The results explain that pyrite acts as a 'bond' between Fe3+ and H2O2, and this pathway continues to form •OH and inhibit the quenching reaction. Therefore, pyrite-catalyzed reactions would proceed even in low concentrations of H2O2.
NASA Astrophysics Data System (ADS)
Bauer, A.; Ono, S.; Romaniello, S. J.; Anbar, A. D.
2017-12-01
Using combined iron and sulfur isotopic data from black shale-hosted pyrite grains of 2.5 Ga samples from the GKP-01 drill core of the Griqualand West Basin, South Africa, we untangle the pathways of pyrite formation for distinct morphologies of pyrite and evaluate the role of these pyrites as recorders of atmospheric S-MIF signals. The analysis of subsamples at stratigraphic intervals allows us to document the characteristic time scale of change in S-MIF signatures resulting from atmospheric photochemical reactions with respect to residence time of the seawater sulfate reservoir. Disseminated pyrite grains are characterized by a range of Δ33S (-1 to +8‰) and 56Fe (-2.5 to 0‰) values. Pyrite laminae are predominantly characterized by relatively homogeneous and negative Δ33S (-2 to 0 ‰) and 56Fe (-2 to -1‰) isotope signatures. These correlated Fe-S systematics suggest distinct pathways of pyrite formation: 1) pyrite laminae formed below the sediment-water interface via diffusion of dissolved oceanic Fe2+ and sulfate; and 2) disseminated pyrite formed at the chemocline by reaction of reduced and elemental sulfur with a reservoir of Fe2+ affected by removal of Fe oxides. Recognition of distinct mechanisms of pyrite formation for these morphologies is a critical step in deconstructing the pathways for S-MIF production, transfer, and preservation in the Archean sedimentary record. Our results have implications for mass balance and atmospheric modeling studies that rely on the Δ33S record as well as for studies attempting to document larger-scale, lithofacies-specific trends in sulfur isotopic signals. Finally, our results are consistent with locally increasing sulfate concentrations along this Archean continental shelf and may correspond to an increase in low-level O2 production prior to the Great Oxygenation Event.
NASA Astrophysics Data System (ADS)
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-water interface.
Le Pape, Pierre; Blanchard, Marc; Brest, Jessica; Boulliard, Jean-Claude; Ikogou, Maya; Stetten, Lucie; Wang, Shuaitao; Landrot, Gautier; Morin, Guillaume
2017-01-03
Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As -I is usually assigned to the occupation of tetrahedral S -I sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of As III and As II have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for As II,III incorporation into pyrite at octahedral Fe II sites and for As -I at tetrahedral S -I sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As -I incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of As II,III for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.
NASA Astrophysics Data System (ADS)
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.
Importance of Extracellular Polymeric Substances from Thiobacillus ferrooxidans for Bioleaching
Gehrke, Tilman; Telegdi, Judit; Thierry, Dominique; Sand, Wolfgang
1998-01-01
Leaching bacteria such as Thiobacillus ferrooxidans attach to pyrite or sulfur by means of extracellular polymeric substances (EPS) (lipopolysaccharides). The primary attachment to pyrite at pH 2 is mediated by exopolymer-complexed iron(III) ions in an electrochemical interaction with the negatively charged pyrite surface. EPS from sulfur cells possess increased hydrophobic properties and do not attach to pyrite, indicating adaptability to the substrate or substratum. PMID:9647862
A novel mineral flotation process using Thiobacillus ferrooxidans.
Nagaoka, T; Ohmura, N; Saiki, H
1999-08-01
Oxidative leaching of metals by Thiobacillus ferrooxidans has proven useful in mineral processing. Here, we report on a new use for T. ferrooxidans, in which bacterial adhesion is used to remove pyrite from mixtures of sulfide minerals during flotation. Under control conditions, the floatabilities of five sulfide minerals tested (pyrite, chalcocite, molybdenite, millerite, and galena) ranged from 90 to 99%. Upon addition of T. ferrooxidans, the floatability of pyrite was significantly suppressed to less than 20%. In contrast, addition of the bacterium had little effect on the floatabilities of the other minerals, even when they were present in relatively large quantities: their floatabilities remained in the range of 81 to 98%. T. ferrooxidans thus appears to selectively suppress pyrite floatability. As a consequence, 77 to 95% of pyrite was removed from mineral mixtures while 72 to 100% of nonpyrite sulfide minerals was recovered. The suppression of pyrite floatability was caused by bacterial adhesion to pyrite surfaces. When normalized to the mineral surface area, the number of cells adhering to pyrite was significantly larger than the number adhering to other minerals. These results suggest that flotation with T. ferrooxidans may provide a novel approach to mineral processing in which the biological functions involved in cell adhesion play a key role in the separation of minerals.
A Novel Mineral Flotation Process Using Thiobacillus ferrooxidans
Nagaoka, Toru; Ohmura, Naoya; Saiki, Hiroshi
1999-01-01
Oxidative leaching of metals by Thiobacillus ferrooxidans has proven useful in mineral processing. Here, we report on a new use for T. ferrooxidans, in which bacterial adhesion is used to remove pyrite from mixtures of sulfide minerals during flotation. Under control conditions, the floatabilities of five sulfide minerals tested (pyrite, chalcocite, molybdenite, millerite, and galena) ranged from 90 to 99%. Upon addition of T. ferrooxidans, the floatability of pyrite was significantly suppressed to less than 20%. In contrast, addition of the bacterium had little effect on the floatabilities of the other minerals, even when they were present in relatively large quantities: their floatabilities remained in the range of 81 to 98%. T. ferrooxidans thus appears to selectively suppress pyrite floatability. As a consequence, 77 to 95% of pyrite was removed from mineral mixtures while 72 to 100% of nonpyrite sulfide minerals was recovered. The suppression of pyrite floatability was caused by bacterial adhesion to pyrite surfaces. When normalized to the mineral surface area, the number of cells adhering to pyrite was significantly larger than the number adhering to other minerals. These results suggest that flotation with T. ferrooxidans may provide a novel approach to mineral processing in which the biological functions involved in cell adhesion play a key role in the separation of minerals. PMID:10427053
NASA Astrophysics Data System (ADS)
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-ray maps and SIMS depth vs. isotope concentration profiles reveal that pyrites from the TGS are characterized by chemical zoning where the studied elements occur in different mineralogical forms. Arsenic and Co occur as structurally bound elements in pyrite, Cu and Au in pyrite can occur as both solid solution and submicron-sized particles of chalcopyrite and native Au (or Au tellurides), respectively. 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 inclusions in quartz and calcite veins (high Cu/As ratios) and borehole fluid (low Cu/As ratios) reported at the TGS, showing a clear correspondence between Cu and As concentrations in pyrite-forming fluids and chemical zonation in pyrite. These observations provide direct evidence supporting the selective partitioning of metals into pyrite as a result of changes in ore-forming fluid composition, most likely due to separation of a single-phase fluid into a low-density vapor and a denser brine, capable of fractionating Cu and As.
NASA Astrophysics Data System (ADS)
Sanchez-Arenillas, M.; Galvez-Martinez, S.; Mateo-Marti, E.
2017-08-01
This paper describes the first successful adsorption of the cysteine, cystine, methionine and alanine amino acids on the pyrite (100) surface under ultra-high vacuum conditions with crucial chemical adsorption parameters driving the process. We have demonstrated by X-ray photoemission spectroscopy (XPS) that the surface pretreatment annealing process on pyrite surfaces is a critical parameter driving surface reactivity. The presence of enriched monosulfide species on the pyrite (100) surface favours the amino acid NH2 chemical form, whereas a longer annealing surface pretreatment of over 3 h repairs the sulfur vacancies in the pyrite, enriching disulfide species on the pyrite surface, which promotes NH3+ adsorption due to the sulfur vacancies in the pyrite being replaced by sulfur atom dimers (S22-) on the surface. Furthermore, even if the surface chemistry (monosulfide or disulfide species enrichment) is the main factor promoting a partial conversion from NH2 to NH3+ species, the unique chemical structure of each amino acid provides a particular fingerprint in the process.
Chemical Interactions of Hydraulic Fracturing Biocides with Natural Pyrite
NASA Astrophysics Data System (ADS)
Consolazio, Nizette A.
In conjunction with horizontal drilling, hydraulic fracturing or fracking has enabled the recovery of natural gas from low permeable shale formations. In addition to water, these fracking fluids employ proppants and up to 38 different chemical additives to improve the efficiency of the process. One important class of additives used in hydraulic fracturing is biocides. When applied appropriately, they limit the growth of harmful microorganisms within the well, saving energy producers 4.5 billion dollars each year. However, biocides or their harmful daughter products may return to the surface in produced water, which must then be appropriately stored, treated and disposed of. Little is known about the effect of mineral-fluid interactions on the fate of the biocides employed in hydraulic fracturing. In this study, we employed laboratory experiments to determine changes in the persistence and products of these biocides under controlled environments. While many minerals are present in shale formations, pyrite, FeS2(s) is particularly interesting because of its prevalence and reactivity. The FeII groups on the face of pyrite may be oxidized to form FeIII phases. Both of these surfaces have been shown to be reactive with organic compounds. Chlorinated compounds undergo redox reactions at the pyrite-fluid interface, and sulfur-containing compounds undergo exceptionally strong sorption to both pristine and oxidized pyrite. This mineral may significantly influence the degradation of biocides in the Marcellus Shale. Thus, the overall goal of this study was to understand the effect of pyrite on biocide reactivity in hydraulic fracturing, focusing on the influence of pyrite on specific functional groups. The first specific objective was to demonstrate the effect of pyrite and pyrite reaction products on the degradation of the bromine-containing biocide, DBNPA. On the addition of pyrite to DBNPA, degradation rates of the doubly brominated compound were found to increase 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 (-Br) group is easily reduced. For methylene bis(thiocyanate), hydrolysis was a noteworthy elimination mechanism since the thiocyanate (-SCN) functionality is a good leaving group. Benzisothiazolinone and methyl isothiazolinone were stable at low pH due to the stabilizing donor-acceptor interactions between the organic biocides' carbonyl (-C=O) groups and salts in the solution. This body of work has illustrated that pristine pyrite can undergo redox reactions with brominated biocides used in hydraulic fracturing, reducing their persistence and altering the product distribution. This will change the efficacy and the risks associated with the use of these biocides in shales containing pyrite, particularly at lower pH where organic compounds are more stable to hydrolysis. However, at higher pH hydrolysis becomes more important, and additional studies will need to be conducted to investigate the pyrite contribution under these conditions. Conversely, the FeIII surface groups on oxidized pyrite can catalyze the hydrolysis of dazomet and may do so for other labile, sulfur-containing biocides as well. Overall, this research has shown that the physicochemical properties (such as the acid dissociation constant and the standard reduction potential) that govern the environmental reactivity of a molecule can be used to anticipate its reactivity in hydraulic fracturing.
NASA Astrophysics Data System (ADS)
Dubosq, Renelle; Rogowitz, Anna; Lawley, Christopher; Schneider, David; Jackson, Simon
2017-04-01
Pyrite is an important and ubiquitous gold-bearing phase in many orogenic gold deposits making the study of its deformation behaviour under metamorphic conditions crucial to the understanding of gold (re)mobilization. However, pyrite deformation mechanisms and their influence on the retention or release of trace elements during deformation and metamorphism remain poorly understood. We propose a syn- to post-peak metamorphic and deformation driven gold upgrading model where gold is remobilized through deformation-induced diffusion pathways in the form of substructures in pyrite. The middle amphibolite facies assemblage (actinolite-biotite-plagioclase-almandine) of the Detour Lake deposit (Canada) makes it an ideal study area due to maximum temperatures reaching 550°C, exceeding the conditions for plastic deformation in pyrite (450°C). The world-class Detour Lake deposit, containing 16.4 Moz of Au at 1 g/t, is a Neoarchean orogenic gold ore body located in the northern Abitibi district within the Superior Province. The mine is situated along the high strain, sub-vertical ductile-brittle Sunday Lake Deformation Zone (SLDZ) parallel to the broadly E-W trending Abitibi greenstone belt. Herein we combine orientation contrast (OC) forescatter imaging, electron backscatter diffraction (EBSD) and 2D laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) trace element pyrite mapping to evaluate the influence of pyrite brittle and plastic deformation on the release of trace elements during syn-metamorphic gold remobilization. Local misorientation patterns in pyrite exhibit parallel bands that can be described by continuous rotation around one of the <100> axes, whereas higher strain areas reveal more heterogeneous misorientation patterns and the development of low-angle grain boundaries with late fractures indicative of dislocation creep and strain hardening. These late fractures are an important micro-structural setting for gold and clusters of precious-metal mineral inclusions (telluride minerals). Minor recrystallization processes can also be observed along phase boundaries between pyrite and more competent amphibole crystals. LA-ICP-MS trace element maps document primary, syn-metamorphic oscillatory zoning of some chalcophile and siderophile elements during crystallization of pyrite porphyroblasts. These primary pyrite features are cut by late metal-rich fractures suggesting that remobilization of gold occurred with trace element enrichment of other chalcophile and siderophile elements (Cu, Pb, Zn, Ag, Bi, Te), which post-dates the main period of syn-metamorphic pyrite crystallization at the margins of pre- to syn-deformation, high-grade gold veins. Pyrite grain boundaries and subgrains are also base and precious metal rich, suggesting that late gold remobilization also occurred during pyrite recrystallization. Additional trace element mapping will help determine to what extent pyrite plastic deformation facilitates the diffusion of gold and other trace elements during gold precipitation and remobilization, which, in turn, will inform the source to sink pathways of ore deposition.
Selective separation of pyrite and chalcopyrite by biomodulation.
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.
NASA Astrophysics Data System (ADS)
Wan, Moli; Schröder, Christian; Peiffer, Stefan
2017-11-01
The formation of pyrite has been extensively studied because of its abundance in many anoxic environments. Yet, there is no consensus on the underlying pathways and kinetics of its formation. We studied the formation of pyrite during the reaction between reactive ferric hydroxides (goethite and lepidocrocite) and aqueous sulfide in an anoxic glove box at neutral pH. The formation of pyrite was monitored with Mössbauer spectroscopy using 57Fe isotope-enriched ferric (hydr)oxides. The initial molar ratios of Fe(III):S(-II) were adjusted to be 'high' with Fe(III) concentrations in excess of sulfide (HR) and 'low' (LR) with excess of sulfide. Approximately the same surface area was applied in all HR runs in order to compare the mineral reactivity of ferric hydroxides. Electron transfer between aqueous sulfide and ferric hydroxides in the first 2 h led to the formation of ferrous iron and methanol-extractable oxidized sulfur (MES). Metastable FeSx formed in all of the experiments. Pyrite formed at a different rate in HR and LR runs although the MES and ferrous iron concentrations were rather similar. In all HR runs, pyrite formation started after 48 h and achieved a maximum concentration after 1 week. In contrast, pyrite started to form only after 2 months in LR runs (Fe(III):S(-II) ∼ 0.2) with goethite and no pyrite formation was observed in LR with lepidocrocite after 6 months. Rates in LR runs were at least 2-3 orders of magnitude slower than in HR runs. Sulfide oxidation rates were higher with lepidocrocite than with goethite, but no influence of the mineral type on pyrite formation rates in HR runs could be observed. Pyrite formation rates in HR runs could not be predicted by the classical model of Rickard (1975). We therefore propose a novel ferric-hydroxide-surface (FHS) pathway for rapid pyrite formation that is based on the formation of a precursor species >FeIIS2-. Its formation is competitive to FeSx precipitation at high aqueous sulfide concentrations and requires that a fraction of the ferric hydroxide surface not be covered by a surface precipitate of FeSx. Hence, pyrite formation rate decreases with decreasing Fe(III):S(-II)aq ratio. In LR runs, pyrite formation appears to follow the model of Rickard (1975) and to be kinetically controlled by the dissolution of FeS. The FHS-pathway will be prominent in many aquatic systems with terrestrial influence, i.e. abundance of ferric iron. We propose that the Fe(III):S(-II)aq ratio can be used as an indicator for rapid pyrite formation during early diagenesis in anoxic/suboxic aquatic systems.
Pyrite Stability Under Venus Surface Conditions
NASA Astrophysics Data System (ADS)
Kohler, E.; Craig, P.; Port, S.; Chevrier, V.; Johnson, N.
2015-12-01
Radar mapping of the surface of Venus shows areas of high reflectivity in the Venusian highlands, increasing to 0.35 ± 0.04 to 0.43 ± 0.05 in the highlands from the planetary average of 0.14 ± 0.03. Iron sulfides, specifically pyrite (FeS2), can explain the observed high reflectivity. However, several studies suggest that pyrite is not stable under Venusian conditions and is destroyed on geologic timescales. To test the stability of pyrite on the Venusian surface, pyrite was heated in the Venus simulation chamber at NASA Goddard Space Flight Center to average Venusian surface conditions, and separately to highland conditions under an atmosphere of pure CO2 and separately under an atmosphere of 96.5% CO2, 3.5% N2 and 150 ppm SO2. After each run, the samples were weighed and analyzed using X-Ray Diffraction (XRD) to identify possible phase changes and determine the stability of pyrite under Venusian surface conditions. Under a pure CO2 atmosphere, the Fe in pyrite oxidizes to form hematite which is more stable at higher temperatures corresponding to the Venusian lowlands. Magnetite is the primary iron oxide that forms at lower temperatures corresponding to the radar-bright highlands. Our experiments also showed that the presence of atmospheric SO2 inhibits the oxidation of pyrite, increasing its stability under Venusian conditions, especially those corresponding to the highlands. This indicates that the relatively high level of SO2 in the Venusian atmosphere is key to the stability of pyrite, making it a possible candidate for the bright radar signal in the Venusian highlands.
Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite.
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.
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.
NASA Astrophysics Data System (ADS)
Basori, Mohd Basril Iswadi; Gilbert, Sarah; Large, Ross Raymond; Zaw, Khin
2018-06-01
The Bukit Botol volcanic-hosted massive sulphide (VHMS) deposit is located in the Central Belt of Peninsular Malaysia. The deposit occurs in a package of Permian-aged coherent felsic volcanic and volcaniclastic rocks which have a geochemical signature indicative of a volcanic arc tectonic setting. Mineralisation shows distinct ore zonation, forming a stringer to massive sulphide zone at the footwall followed by barite lenses and exhalite layers (Fe-Mn ore) at the top. Mineralogy is characterised by pyrite as the major sulphide mineral, with minor chalcopyrite, sphalerite, and rare galena; traces of gold, silver- and tin-bearing minerals also occur in the massive sulphide and barite ores. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis combined with the textural characteristics of pyrite provides evidence for significant variations of trace elements in different pyrite types at Bukit Botol, having three types of pyrite in the paragenetic sequence. The concentrations of As, Se, Te, Cu, Zn and Pb decrease from the early pyrite 1 to the late stage pyrite 3, and the Co/Ni ratios vary for the three pyrite types. The combined textural and compositional data of pyrite suggest that the hydrothermal fluid responsible for mineralisation evolved from an early, high temperature, reduced, low pH and desulphurized fluid to more S-rich, oxidized, high pH and cooler fluid. Available sulphur isotope data from the Bukit Botol deposit point to reduced seawater, along with a possible magmatic contribution, as the most probable sources for the ore-forming fluids.
Zhang, Jiahua; Ren, D.; Zheng, C.; Zeng, R.; Chou, C.-L.; Liu, J.
2002-01-01
Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
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 sedimentation rates. The Styliolina Horizon is distinguished by the overall highest portion of syngenetic pyrite, which suggests that in this marker layer most of the pyrite precipitated from euxinic bottom waters.
Cu-As Decoupling in Hydrothermal Systems: A Link Between Pyrite Chemistry and Fluid Composition
NASA Astrophysics Data System (ADS)
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 zonation in pyrite. These observations provide direct evidence supporting the selective partitioning of metals into pyrite as a result of changes in ore-forming fluid composition, most likely due to separation of a single-phase fluid into a low-density vapor and a denser brine, capable to fractionate Cu and As.
Mineralogy, chemical composition and structure of the MIR Mound, TAG Hydrothermal Field
NASA Astrophysics Data System (ADS)
Stepanova, T. V.; Krasnov, S. G.; Cherkashev, G. A.
The study of samples collected from the surface of the MIR mound (TAG Hydrothermal Field) by video-controlled hydraulic grab allowed identification of a number of mineralogical types. These include pyrite-chalcopyrite (Py-Cp), bornite-chalcopyrite-opaline (Bn-Cp-Op) and sphalerite-opaline (Sp-Op) sulfide chimneys, massive sulfides composed of pyrite (Py), chalcopyrite-pyrite (Cp-Py), marcasite-pyrite-opaline (Mc-Py-Op), sphalerite-pyrite-opaline (Sp-Py-Op) and sphalerite-chalcopyrite-pyrite-opaline (Sp-Cp-Py-Op), as well as siliceous and Fe-Mn oxide hydrothermal deposits. Most of the minor elements (Ag, Au, Cd, Ga, Hg, Sb and Pb) are associated with Zn-rich massive sulfides, Co Bi, Pb, and As with Ferich ones, while Cu-rich sulfides are depleted of trace metals. Cu-enriched assemblages are concentrated in the northern part, Zn-enriched in the center, and siliceous rocks in the south of the MIR mound. According to paragenetic relations, the development of the mound started with the formation of quartz (originally opaline) rocks and dendritic assemblages of melnikovite-pyrite, followed by deposition of chalcopyrite and recrystallization of primary pyrite, subsequent generation of sphalerite-rich assemblages and final deposition of opaline rocks. The late renewal of hydrothermal activity led to local formation of Cu-rich chimneys enriched in Au, Ag, Hg and Pb probably due to their remobilization from inner parts of the deposit.
Method of synthesizing pyrite nanocrystals
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.
Evaluation of flotation for purification of pyrite for use in thermal batteries
NASA Astrophysics Data System (ADS)
Guidotti, R. A.; Reinhardt, F. W.
1992-07-01
The purification of pyrite (FeS2) used in Li-alloy/FeS2 thermal batteries by the physical process of flotation was evaluated for reduction of the quartz impurity. The process was compared to the standard process of leaching with concentrated hydrofluoric acid. Flotation was an attractive alternative because it avoided many of the safety and environmental concerns posed by the use of concentrated HF. The effects of particle size and initial purity of the pyrite feed material upon the final purity and yield of the product concentrate were examined for batch sizes from 3.5 to 921 kg. Feed materials as coarse as 8 mm and as fine as -325 mesh were treated; the coarse pyrite was ground wet in a rod mill or dry in a vibratory mill to -230 mesh prior to flotation. Both the HF-leached and the flotation-treated pyrite were leached with HCI (1:1 v/v) to remove acid-soluble impurities. The flotation-purified pyrite concentrates were formulated into catholytes; their electrochemical performance was evaluated in both single cells and 5-cell batteries for comparison to data generated under the same discharge conditions for catholytes formulated with HF/HCI purified pyrite.
Effect of thiamine hydrochloride on the redox reactions of iron at pyrite surface
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pesic, B.; Oliver, D.J.
1990-01-01
The present investigation is a part of our studies on the electro chemical aspects of pyrite bioleaching involving Thiobacillus ferrooxidans. Previously (1,2) we have examined the effect of T. ferrooxidans and their metabolic products on the redox reactions of Fe[sup 2+]/Fe[sup 3+] couple at the pyrite surface. Results obtained suggest that beyond 1. 5 days during their growth in a batch fermenter, the bacteria and their metabolic products completely cover the pyrite surface and shut down all electron transfer across the electrode-solution interface. In addition, it has been observed that the bacteria serve as the nucleation site for jarosite formation,more » which is found detrimental to bioleaching. In the present work we have focussed on the effect of the presence of vitamins on the redox chemistry of iron. Our examination of the effect of the presence of thiamine hydrochloride in the redox behavior of Fe[sup 2+]/Fe[sup 3+] at the pyrite surface has revealed that thiamine hydrochloride does not undergo chemical interaction with ferrous or ferric iron. However, it may adsorb onto the pyrite surface causing polarization of the pyrite electrode.« less
King, A.G.
1956-01-01
A texture was observed in a sample of ore in 'Which pyrite and uraninite occurred as thin alternate layers paralleling crystal faces of a pyrite nucleus. This texture could be formed either by replacement or by syntaxis. Although syntactic growth forming polyerystals of two chemically dissimilar minerals has not been previously described, this explanation fits the observed data better than the explanation offered by replacement. It is proposed, therefore, that this occurrence is an example of a polycrystal of uraninite and pyrite and that the mechanism of formation is syntaxis.
Desulfurization of coal by microbial column flotation.
Ohmura, N; Saiki, H
1994-06-05
Twenty-three strains capable of oxidizing iron were isolated from coal and ore storage sites as well as coal and ore mines, volcanic areas, and hot spring. Four strains were found to have high iron-oxidizing activity. One strain (T-4) was selected for this experiment since the strain showed the fastest leaching rate of iron and sulfate from pyrite among the four strains. The T-4 strain was assigned for Thiobacillus ferrooxidans from its cultural and morphological characteristics.Bacterial treatment was applied to column flotation. An increase of cell density in the microbial column flotation resulted in the increase of pyrite removal from a coal-pyrite mixture (high sulfur imitated coal) with corresponding decrease of coal recovery. The addition of kerosene into the microbial column flotation increased the recovery of the imitated coal from 55% (without kerosene) to 81% (with 50 microL/L kerosene) with the reduction of pyrite sulfur content from 11% (feed coal) to 3.9% (product coal). The kerosene addition could reduce the pyritic sulfur content by collecting the coal in the recovery. However, the addition could not enhance separation of pyrite from the coal-pyrite mixture, since pyrite rejection was not affected by the increase of the kerosene addition. An excellent separation was obtained by the microbial flotation using a long column which had a length-diameter (L/D) ratio of 12.7. The long column flotation reduced the pyritic sulfur content from 11% (feed coal) to 1.8% (product coal) when 80% of the feed coal was recovered without the kerosene addition. The long column flotation not only attained an excellent separation but also reduced the amount of cells for desulfurization to as little as one-tenth of the reported amount.
Structure of selenium incorporated in pyrite and mackinawite as determined by XAFS analyses
NASA Astrophysics Data System (ADS)
Diener, A.; Neumann, T.; Kramar, U.; Schild, D.
2012-05-01
Selenium has a toxic potential leading to diseases by ingestion and a radiotoxic potential as 79Se radionuclide if discharged from a high-level nuclear waste repository in deep geological formations into the biosphere. Selenium is often associated with sulfides, such as pyrite, the most important near-surface iron sulfide and constituent of host rocks and bentonite backfills considered for radioactive waste disposal. This study was aimed at investigating the incorporation of Se2- and Se4+ into pyrite and mackinawite to determine the relevance of iron sulfides to Se retention and the type of structural bonding. The syntheses of pyrite and mackinawite occurred via direct precipitation in batches and also produced coatings on natural pyrite in mixed-flow reactor experiments (MFR) under anoxic conditions at Se concentrations in the solutions of up to 10- 3 mol/L. Mineralogical analyses by SEM and XRD reveal the formation of pyrite and mackinawite phases. The average Se2- uptake in pyrite in batch experiments amounts to 98.6%. In MFR syntheses, it reaches 99.5%, both suggesting a high potential for retention. XAFS results indicate a substitution of sulfur by selenide during instantaneous precipitation in highly supersaturated solutions only. In selenide-doted mackinawite S2- was substituted by Se2-, resulting in a mackinawite-type compound. S- is substituted by Se- in selenide-doted pyrite, yielding a FeSSe compound as a slightly distorted pyrite structure. Under slighter supersaturated conditions, XAFS results indicate an incorporation of Se2- and Se4+ predominantly as Se0. This study shows that a substitution of S by Se in iron sulfides is probable only for highly supersaturated solutions under acidic and anoxic conditions. Under closer equilibrium conditions, Se0 is expected to be the most stable species.
Enhanced bioleaching on attachment of indigenous acidophilic bacteria to pyrite surface
NASA Astrophysics Data System (ADS)
Wi, D. W.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.
2012-04-01
In recent years, bioleaching has been widely applied on an industrial scale due to the advantages of low cost and environment friendliness. The direct contact mechanism of bioleaching assumes the action of a metal sulfide-attached cell oxidizing the mineral by an enzyme system with oxygen to sulfate and metal cations. Fundamental surface properties of sulfide particles and leaching-bacteria in bioleaching play the key role in the efficiency of this process. The aim of this work is to investigate of direct contact bioleaching mechanism on pyrite through attachment properties between indigenous acidophilic bacteria and pyrite surfaces. The bacteria were obtained from sulfur hot springs, Hatchobaru thermal electricity plant in Japan. And pyrite was collected from mine waste from Gwang-yang abandoned gold mines, Korea. In XRD analyses of the pyrite, x-ray diffracted d-value belong to pyrite was observed. The indigenous acidophilic bacteria grew well in a solution and over the course of incubation pH decreased and Eh increased. In relation to a bacterial growth-curve, the lag phase was hardly shown while the exponential phase was very fast. Bioleaching experiment result was showed that twenty days after the indigenous acidophilic bacteria were inoculated to a pyrite-leaching medium, the bacterial sample had a greater concentration of Fe and Zn than within the control sample. In SEM-EDS analyses, rod-shaped bacteria and round-shaped microbes were well attached to the surface of pyrite. The size of the rod-shaped bacteria ranged from 1.05~1.10 ? to 4.01~5.38 ?. Round-shaped microbes were more than 3.0 ? in diameter. Paired cells of rod-shaped bacteria were attached to the surface of pyrite linearly.
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.
The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances
Evans, B.J.; Johnson, R.G.; Senftle, F.E.; Cecil, C.B.; Dulong, F.
1982-01-01
The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.
A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting
2011-01-01
One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials. PMID:21299877
Arsenic Incorporation Into Authigenic Pyrite, Bengal Basin Sediment, Bangladesh
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lowers, H.A.; Breit, G.N.; Foster, A.L.
2007-07-10
Sediment from two deep boreholes ({approx}400 m) approximately 90 km apart in southern Bangladesh was analyzed by X-ray absorption spectroscopy (XAS), total chemical analyses, chemical extractions, and electron probe microanalysis to establish the importance of authigenic pyrite as a sink for arsenic in the Bengal Basin. Authigenic framboidal and massive pyrite (median values 1500 and 3200 ppm As, respectively), is the principal arsenic residence in sediment from both boreholes. Although pyrite is dominant, ferric oxyhydroxides and secondary iron phases contain a large fraction of the sediment-bound arsenic between approximately 20 and 100 m, which is the depth range of wellsmore » containing the greatest amount of dissolved arsenic. The lack of pyrite in this interval is attributed to rapid sediment deposition and a low sulfur flux from riverine and atmospheric sources. The ability of deeper aquifers (>150 m) to produce ground water with low dissolved arsenic in southern Bangladesh reflects adequate sulfur supplies and sufficient time to redistribute the arsenic into pyrite during diagenesis.« less
Arsenic incorporation into authigenic pyrite, Bengal Basin sediment, Bangladesh
Lowers, H.A.; Breit, G.N.; Foster, A.L.; Whitney, J.; Yount, J.; Uddin, Md. N.; Muneem, Ad. A.
2007-01-01
Sediment from two deep boreholes (???400 m) approximately 90 km apart in southern Bangladesh was analyzed by X-ray absorption spectroscopy (XAS), total chemical analyses, chemical extractions, and electron probe microanalysis to establish the importance of authigenic pyrite as a sink for arsenic in the Bengal Basin. Authigenic framboidal and massive pyrite (median values 1500 and 3200 ppm As, respectively), is the principal arsenic residence in sediment from both boreholes. Although pyrite is dominant, ferric oxyhydroxides and secondary iron phases contain a large fraction of the sediment-bound arsenic between approximately 20 and 100 m, which is the depth range of wells containing the greatest amount of dissolved arsenic. The lack of pyrite in this interval is attributed to rapid sediment deposition and a low sulfur flux from riverine and atmospheric sources. The ability of deeper aquifers (>150 m) to produce ground water with low dissolved arsenic in southern Bangladesh reflects adequate sulfur supplies and sufficient time to redistribute the arsenic into pyrite during diagenesis.
The effect of lizardite surface characteristics on pyrite flotation
NASA Astrophysics Data System (ADS)
Feng, Bo; Feng, Qiming; Lu, Yiping
2012-10-01
The effect of lizardite surface characteristics on pyrite flotation has been investigated through flotation tests, adsorption tests, zeta potential measurements, FTIR study, X-ray photoelectron spectroscopy (XPS) and sedimentation tests. The flotation results show that at pH value 9, where flotation of nickel sulfide ores is routinely performed, two kinds of lizardite samples (native lizardite and leached lizardite) have different effects on the flotation of pyrite. The native lizardite adheres to the surface of pyrite and reduces pyrite flotation recovery while the leached lizardite does not interfere with pyrite flotation. Infrared analyses and XPS tests illustrate that acid leaching changed the surface characteristics of lizardite mineral and the leached lizardite has less magnesium on its surface. It has been determined that the electro-kinetic behavior of lizardite aqueous suspensions is mainly a function of the Mg/Si atomic ratio on lizardite surface. So, the low isoelectric point observed in the leached sample has been linked to values of this ratio lower than that of the native lizardite.
Surface Chemical Studies on Pyrite in the Presence of Polysaccharide-Based Flotation Depressants.
Rath; Subramanian; Pradeep
2000-09-01
The interaction of dextrin and guar gum with pyrite has been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of the polysaccharides onto pyrite reveal a region of higher adsorption density in the pH range 7.5-11, with a maximum around pH 10 for both polymers. The isotherms exhibit Langmuirian behavior. The adsorption density of guar gum onto pyrite is higher than that of dextrin. Electrokinetic measurements indicate a decrease in the electrophoretic mobility values in proportion to the concentration of the polymer added. Co-precipitation tests confirm polymer-ferric species interaction in the bulk solution, especially in the pH range 5.5-8.5. The pH range for higher adsorption, significant co-precipitation, and appreciable depression of pyrite encompass each other. XPS and FTIR spectroscopic studies provide evidence in support of chemical interaction between hydroxylated pyrite and the hydroxyl groups of the polymeric depressants. Copyright 2000 Academic Press.
Kinetics and mechanisms of iron sulfide reductions in hydrogen and in carbon monoxide
Wiltowski, T.; Hinckley, C.C.; Smith, Gerard V.; Nishizawa, T.; Saporoschenko, Mykola; Shiley, R.H.; Webster, J.R.
1987-01-01
The reduction of iron sulfides by hydrogen and by carbon monoxide has been studied using plug flow and thermogravimetric methods. The reactions were studied in the 523-723??K temperature range and were found to be first-order processes. Plug flow studies were used to correlate reaction rates between pyrite and the gases as a function of the surface area of the pyrite. The rate of H2S formation increases with the surface area of the pyrite sample. The results of thermogravimetric experiments indicate that the reactions consist of several steps. Rate constants for the pyrite reduction by H2 and by CO were obtained. The activation energies increased with degree of reduction. Values of Ea were 113.2 (step I) and 122.5 kJ/mole (step II) for pyrite reduction with CO and 99.4 (step I), 122.4 (step II), 125.2 (step III), and 142.6 kJ/mole (step IV) for pyrite reduction with hydrogen. ?? 1987.
Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments
Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.
1993-01-01
Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a ??34S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the "front" of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation. ?? 1993.
The Russell gold deposit, Carolina Slate Belt, North Carolina
Klein, T.L.; Cunningham, C.G.; Logan, M.A.V.; Seal, R.R.
2007-01-01
Gold deposits have been mined in the Carolina slate belt from the early 1800s to recent times, with most of the production from large mines in South Carolina. The Russell mine, one of the larger producers in North Carolina, is located in the central Uwharrie Mountains, and produced over 470 kg of gold. Ore grades averaged about 3.4 grams per tonne (g/ t), with higher-grade zones reported. The Russell deposit is interpreted to be a sediment-hosted, gold-rich, base-metal poor, volcanogenic massive sulfide deposit in which gold was remobilized, in part, during Ordovician metamorphism. The ore was deposited syngenetically with laminated siltstones of the late Proterozoic Tillery Formation that have been metamorphosed to a lower greenschist facies. The Tillery Formation regionally overlies subaerial to shallow marine rhyolitic volcanic and volcaniclastic rocks of the Uwharrie Formation and underlies the marine volcanic and sedimentary rocks of the Cid Formation. Recent mapping has shown that a rhyolitic dome near the Russell mine was extruded during the deposition of the lower part of the Tillery Formation, at about the same time as ore deposition. Relict mafic, rock fragments present in the ore zones suggest contemporaneous bimodal (rhyolite-basalt) volcanism. The maximum formation age of the Russell deposit is younger than 558 Ma, which is similar to that of the larger, well known Brewer, Haile, and Ridgeway deposits of South Carolina. Gold was mined from at least six zones that are parallel to the regional metamorphic foliation. These strongly deformed zones consist of northeast-trending folds, high-angle reverse faults, and asymmetric doubly plunging folds overturned to the southeast. The dominant structure at the mine is an asymmetric doubly plunging anticline with the axis trending N 45?? E, probably related to late Ordovician (456 ?? 2 Ma) regional metamorphism and deformation. Two stages of pyrite growth are recognized. Stage 1, primary, spongy pyrite, is present in thin massive sulfide layers parallel to bedding and intergrown with pyrrhotite, chalcopyrite, sphalerite, and sparse arsenopyrite. Stage 2, secondary pyrite, is present as euhedral, idiomorphic rims on spongy pyrite and as veinlets that parallel the regional foliation. Stage 1 pyrite was deposited syngenetically or diagenetically during or soon after sedimentation. Stage 2 pyrite overgrowths and veins resulted from recrystallization or remobilization of stage 1 pyrite, probably during deformation related to Ordovician regional metamorphism. It is proposed that the spongy texture of the stage 1 pyrite represents nucleation and growth of pyrite on organic matter, possibly of bacterial origin. Other textures, such as geometric voids in spongy pyrite, As-rich zones surrounding central voids, 60-??m ring structures composed of spongy pyrite, and layers of spongy pyrite interlayered with bedding laminations, also appear to indicate replacement of organic matter by pyrite. Stage 1 pyrite contains up to 0.06 wt percent gold. The ??34S values of pyrite in and near pyritic ore (3.5-4.5???), in the rhyolite dome (5.1-5.4???) and in the Tillery Formation (5.9-6.2???) are interpreted to reflect mixing of sulfur derived from igneous and seawater sources. Whole-rock ??18O values of nearby unaltered mudstone are about 11 per mil whereas those from altered mudstone at the deposit are 7.4 to 10.6 per mil. The lower ?? 18O values are interpreted to indicate possible high-temperature exchange between relatively low ??18O hydrothermal fluids and the wall rocks. Gold, As, K, and Mo are enriched relative to the regional background in both the ore zones and in pyrite veins and disseminations in the nearby rhyolite dome, suggesting a possible genetic link between the rhyolitic volcanism and the gold mineralization. ?? 2007 Society of Economic Geologists, Inc.
Geothermal Potential of Adak Island, Alaska
1985-10-01
alteration of the Andrew Bay Hot Springs is essentially propylitic , with the introduction of pyrite and the conversion of magnetite to pyrite. This pyritic...features: Goethite coats the walls of a 1-mm fracture in this rock. Classification: Propylitically altered andesite porphyry breccia. 71 NWC TP 6676 Date: 20
NASA Astrophysics Data System (ADS)
Gregory, Daniel D.; Lyons, Timothy W.; Large, Ross R.; Jiang, Ganqing; Stepanov, Aleksandr S.; Diamond, Charles W.; Figueroa, Maria C.; Olin, Paul
2017-11-01
The trace element content of pyrite is a recently developed proxy for metal abundance in paleo-oceans. Previous studies have shown that the results broadly match those of whole rock studies through geologic time. However, no detailed study has evaluated the more traditional proxies for ocean chemistry for comparison to pyrite trace element data from the same samples. In this study we compare pyrite trace element data from 14 samples from the Wuhe section of the Ediacaran-age Doushantuo Formation, south China, measured by laser ablation inductively coupled plasma mass spectrometry with new and existing whole rock trace element concentrations; total organic carbon; Fe mineral speciation; S isotope ratios; and pyrite textural relationships. This approach allows for comparison of data for individual trace elements within the broader environmental context defined by the other chemical parameters. The results for discrete pyrite analyses show that several chalcophile and siderophile elements (Ag, Sb, Se, Pb, Cd, Te, Bi, Mo, Ni, and Au) vary among the samples with patterns that mirror those of the independent whole rock data. A comparison with existing databases for sedimentary and hydrothermal pyrite allows us to discriminate between signatures of changing ocean conditions and those of known hydrothermal sources. In the case of the Wuhe samples, the observed patterns for trace element variation point to primary marine controls rather than higher temperature processes. Specifically, our new data are consistent with previous arguments for pulses of redox sensitive trace elements interpreted to be due to marine oxygenation against a backdrop of mostly O2-poor conditions in the Ediacaran ocean-with important implications for the availability of bioessential elements. The agreement between the pyrite and whole rock data supports the use of trace element content of pyrite as a tracer of ocean chemistry in ways that complement existing approaches, while also opening additional windows of opportunity. For example, unlike the potential vulnerability of whole rock data to secondary alteration, the pyrite record may survive greenschist facies metamorphism. Furthermore, early-formed pyrite can be identified through textural relationships as a proxy of primary marine chemistry even in the presence of hydrothermal overprints on whole rock chemistry via secondary fluids. Finally, pyrite analyses may allow for the possibility of more quantitative interpretations of the ancient ocean once the elemental partitioning between the mineral and host fluids are better constrained. Collectively, these advances can greatly increase the number of basins that may be investigated for early ocean chemistry, especially those of Precambrian age.
Vikre, Peter G.; Poulson, S.R.; Koenig, Alan E.
2011-01-01
The thick (≤8 km), regionally extensive section of Neoproterozoic siliciclastic strata (terrigenous detrital succession, TDS) in the central and eastern Great Basin contains sedimentary pyrite characterized by mostly high δ34S values (−11.6 to 40.8‰, >70% exceed 10‰; 51 analyses) derived from reduction of seawater sulfate, and by markedly radiogenic Pb isotopes (207Pb/204Pb >19.2; 15 analyses) acquired from clastic detritus eroded from Precambrian cratonal rocks to the east-southeast. In the overlying Paleozoic section, Pb-Zn-Cu-Ag-Au deposits associated with Jurassic, Cretaceous, and Tertiary granitic intrusions (intrusion-related metal deposits) contain galena and other sulfide minerals with S and Pb isotope compositions similar to those of TDS sedimentary pyrite, consistent with derivation of deposit S and Pb from TDS pyrite. Minor element abundances in TDS pyrite (e.g., Pb, Zn, Cu, Ag, and Au) compared to sedimentary and hydrothermal pyrite elsewhere are not noticeably elevated, implying that enrichment in source minerals is not a precondition for intrusion-related metal deposits.Three mechanisms for transferring components of TDS sedimentary pyrite to intrusion-related metal deposits are qualitatively evaluated. One mechanism involves (1) decomposition of TDS pyrite in thermal aureoles of intruding magmas, and (2) aqueous transport and precipitation in thermal or fluid mixing gradients of isotopically heavy S, radiogenic Pb, and possibly other sedimentary pyrite and detrital mineral components, as sulfide minerals in intrusion-related metal deposits. A second mechanism invokes mixing and S isotope exchange in thermal aureoles of Pb and S exsolved from magma and derived from decomposition of sedimentary pyrite. A third mechanism entails melting of TDS strata or assimilation of TDS strata by crustal or mantle magmas. TDS-derived or assimilated magmas ascend, decompress, and exsolve a mixture of TDS volatiles, including isotopically heavy S and radiogenic Pb from sedimentary pyrite, and volatiles acquired from deeper crustal or mantle sources.In the central and eastern Great Basin, the wide distribution and high density of small to mid-sized vein, replacement, and skarn intrusion-related metal deposits in lower Paleozoic rocks that contain TDS sedimentary pyrite S and Pb reflect (1) prolific Jurassic, Cretaceous, and Tertiary magmatism, (2) a regional, substrate reservoir of S and Pb in permeable and homogeneous siliciclastic strata, and (3) relatively small scale concentration of substrate and magmatic components. Large intrusion-related metal deposits in the central and eastern Great Basin acquired S and most Pb from thicker lithospheric sections.
Håkan Tarras-Wahlberg, N; Nguyen, Lan T
2008-03-01
The causes for the failure in enforcement of environmental regulations at the Giap Lai pyrite mine in northern Vietnam are considered and the environmental impacts that are associated with this mine are evaluated. It is shown that sulphide-rich tailings and waste rock in the mining area represent significant sources of acid rock drainage (ARD). The ARD is causing elevated metal levels in downstream water bodies, which in turn, represent a threat to both human health and to aquatic ecosystems. Metal concentrations in impacted surface waters have increased after mine closure, suggesting that impacts are becoming progressively more serious. No post-closure, remediation measures have been applied at the mine, in spite of the existence of environmental legislation and both central and regional institutions charged with environmental supervision and control. The research presented here provides further emphasis for the recommendation that, while government institutions may need to be strengthened, and environmental regulations need to be in place, true on the ground improvement in environmental quality in Vietnam and in many other developing countries require an increased focus on promoting public awareness of industrial environmental issues.
Atmospheric-Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films
DOE Office of Scientific and Technical Information (OSTI.GOV)
Berry, Nicholas; Cheng, Ming; Perkins, Craig L.
2012-10-23
Iron pyrite (cubic FeS{sub 2}) is a promising candidate absorber material for earth-abundant thin-film solar cells. In this report, single-phase, large-grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum-coated glass substrates by atmospheric-pressure chemical vapor deposition (AP-CVD) using the reaction of iron(III) acetylacetonate and tert-butyl disulfide in argon at 300 C, followed by sulfur annealing at 500--550 C to convert marcasite impurities to pyrite. The pyrite-marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized bymore » X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X-ray photoelectron spectroscopy. The in-plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p-type, thermally activated transport with a small activation energy ({approx}30 meV), a room- temperature resistivity of {approx}1 {Omega} cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.« less
Release of Particulate Iron Sulfide during Shale-Fluid Interaction.
Kreisserman, Yevgeny; Emmanuel, Simon
2018-01-16
During hydraulic fracturing, a technique often used to extract hydrocarbons from shales, large volumes of water are injected into the subsurface. Although the injected fluid typically contains various reagents, it can become further contaminated by interaction with minerals present in the rocks. Pyrite, which is common in organic-rich shales, is a potential source of toxic elements, including arsenic and lead, and it is generally thought that for these elements to become mobilized, pyrite must first dissolve. Here, we use atomic force microscopy and environmental scanning electron microscopy to show that during fluid-rock interaction, the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment, and mobilization, of embedded pyrite grains. In experiments carried out over a range of pH, salinity, and temperature we found that in all cases pyrite particles became detached from the shale surfaces. On average, the amount of pyrite detached was equivalent to 6.5 × 10 -11 mol m -2 s -1 , which is over an order of magnitude greater than the rate of pyrite oxidation expected under similar conditions. This result suggests that mechanical detachment of pyrite grains could be an important pathway for the mobilization of arsenic in hydraulic fracturing operations and in groundwater systems containing shales.
Minor element distribution in iron disulfides in coal: a geochemical review
Kolker, Allan
2012-01-01
Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.
NASA Astrophysics Data System (ADS)
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 (<0.45mm) resulted in a favorable nitrate removal. The nitrate removal rate increased from 0.26 to 0.34 mg L-1h-1 and then to 0.86 mg L-1h-1, approaching that of the sulfur oxidizing denitrification (SOD) rate of 1.19 mg L-1h-1. Based on Box-Behnken design (BBD) and response surface methodology (RSM), the optimal amount of biomass concentration, pyrite dose, and pyrite particle size were 1,250 mg VSS L-1, 125 g L-1, and 0.815-1.015 mm, respectively. PPAD 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.
Demir, I.; Harvey, R.D.; Hackley, Keith C.
1993-01-01
Two samples of the Herrin (Illinois No. 6) Coal and one sample of the Colchester (Illinois No. 2) Coal from the Illinois Basin were studied to evaluate the spatial distribution of organic sulfur within macerals occurring next to pyrite grains, both in the raw coal and their chars. The chars were produced by pyrolysing the coal at 250-550??C in a nitrogen atmosphere. Representative splits of the coals and their chars were mounted in epoxy and polished for optical microscopy and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX). Determinations of organic sulfur concentrations were made at 996 locations within macerals, mostly vitrinite, around 115 grains of pyrite and at 50 locations around 5 pores in chars. The pyrite considered here is restricted to the disseminated type within macerals. On the average, the organic sulfur content increased near pyrite grains after the coals were charred at 550??C, indicating that some of the pyritic sulfur released during charring was retained within the organic matrix rather than being emitted to the atmosphere. One of the coal samples and its chars were isotopically characterized by chemically separating the pyritic and organic sulfur fractions, followed by analyzing the isotopes of the sulfur forms with a Nuclide 6-60 ratio mass spectrometer. The sulfur isotope (??34S) data confirmed the movement of pyritic sulfur into the macerals after charring to 550??C. About 18% of the organic sulfur that remained in the 550??C char had originally been pyritic sulfur in the untreated coal. ?? 1993.
NASA Astrophysics Data System (ADS)
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.
Pyrite discs in coal: evidence for fossilized bacterial colonies
Southam, G.; Donald, R.; Rostad, A.; Brock, C.
2001-01-01
Discs of pyrite from 1 to 3 mm in diameter and ∼100 μm thick were observed within fracture planes in coal from the Black Mesa coal deposit in northeastern Arizona. The pyrite discs were composed of aggregates of crystals, which suggested that sulfide mineral diagenesis had initiated at multiple nucleation sites and occurred prior to the compaction forces occurring during coal formation. Stable sulfur isotope analysis of the discs (δ34S = −31.7‰) supports a bacterial origin resulting from dissimilatory sulfate reduction. Fossilized bacteria on the disc surfaces (average = 27/100 μm2) appeared as halos when viewed using reflected light microscopy, but were lenticular by scanning electron microscopy, each microfossil being 2–3 μm in length. A fossilized bacterial colony (pyrite disc), 1 mm in diameter, would contain ∼2.1 × 107 microfossils. These microfossils were not observed on hydrothermal pyrite. Coating and in-filling of sulfate-reducing bacteria with iron disulfide during in vitro sulfide mineral diagenesis provide mechanisms to explain the preservation of the three-dimensional lenticular microfossils observed on the pyrite discs.
NASA Technical Reports Server (NTRS)
Ripley, E. M.; Nicol, D. L.
1979-01-01
Sulfur isotopic studies of pyrite from metasediments in the 2.6 b.y. old Deer Lake greenstone sequence, Minnesota, were conducted in order to evaluate the possible importance of sulfate reducing bacteria in sulfide formation. Pyrite occurs as ovules up to 2 cm in diameter within graphitic slates, and as fine disseminations in metagraywacke units. SEM studies indicate the pyrite is framboidal in morphology. Delta notation values of pyrite from the Deer Lake sediments range from -2.3 to 11.1 0/00, with a peak at approximately +2 o/oo. Isotopic data is consistent with either high temperature inorganic reduction of circulating seawater sulfate, or low temperature bacterial reduction. However, the lack of sulfide bands or massive occurrences in the sediments, the restriction of pyrite mineralization to the sediments, and the absence of evidence for hot spring activity suggest that a diagenetic origin of pyrite is more feasible. Sulfide in such an environment would be produced principally by the action of sulfate reducing bacteria.
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.
Niu, Xiaopeng; Ruan, Renman; Xia, Liuyin; Li, Li; Sun, Heyun; Jia, Yan; Tan, Qiaoyi
2018-02-27
When it comes to Pb-Zn ores with high amounts of pyrite, the major problem encountered is the low separation efficiency between galena and pyrite. By virtue of high dosage of lime and collector sodium diethyl dithiocarbamate (DDTC), pyrite and zinc minerals are depressed, allowing the galena to be floated. However, there have been significant conflicting reports on the flotation behavior of galena at high pH. In this context, correlation of the surface adsorption and oxidation with the floatability difference of galena and pyrite in high-alkaline lime systems would be a key issue for process optimization. Captive bubble contact angle measurements were performed on freshly polished mineral surfaces in situ exposed to lime solutions of varying pH as a function of immersion time. Furthermore, single mineral microflotation tests were conducted. Both tests indicated that the degree of hydrophobicity on the surfaces of galena and pyrite increased in the presence of DDTC at natural or mild pulp pH. While in a saturated lime solution, at pH 12.5, DDTC only worked for galena, but not for pyrite. Surface chemistry analysis by time-of-flight secondary ion mass spectrometry (Tof-SIMS) confirmed the preference of DDTC on the galena surface at pH 12.5, which contributed to a merit recovery. Further important evidence through measurements of Tof-SIMS, ion chromatography, and high-performance liquid chromatography indicated that in high-alkaline lime systems, the merit floatability of galena could exclude the insignificant contribution of elemental sulfur (S 8 ) and was dominantly attributed by the strong adsorption of DDTC. In contrast, the poor flotation response of pyrite at high pH was due to the prevailing adsorption of CaOH + species. This study provides an important surface chemistry evidence for a better understanding of the mechanism on the better selectivity in the galena-pyrite separation adopting high-alkaline lime systems.
Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite
Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.
2008-01-01
We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations. ?? 2008 Elsevier Ltd. All rights reserved.
Gallagher, M; Turner, E C; Kamber, B S
2015-07-01
Pre-Cambrian atmospheric and oceanic redox evolutions are expressed in the inventory of redox-sensitive trace metals in marine sedimentary rocks. Most of the currently available information was derived from deep-water sedimentary rocks (black shale/banded iron formation). Many of the studied trace metals (e.g. Mo, U, Ni and Co) are sensitive to the composition of the exposed land surface and prevailing weathering style, and their oceanic inventory ultimately depends on the terrestrial flux. The validity of claims for increased/decreased terrestrial fluxes has remained untested as far as the shallow-marine environment is concerned. Here, the first systematic study of trace metal inventories of the shallow-marine environment by analysis of microbial carbonate-hosted pyrite, from ca. 2.65-0.52 Ga, is presented. A petrographic survey revealed a first-order difference in preservation of early diagenetic pyrite. Microbial carbonates formed before the 2.4 Ga great oxygenation event (GOE) are much richer in pyrite and contain pyrite grains of greater morphological variability but lesser chemical substitution than samples deposited after the GOE. This disparity in pyrite abundance and morphology is mirrored by the qualitative degree of preservation of organic matter (largely as kerogen). Thus, it seems that in microbial carbonates, pyrite formation and preservation were related to presence and preservation of organic C. Several redox-sensitive trace metals show interpretable temporal trends supporting earlier proposals derived from deep-water sedimentary rocks. Most notably, the shallow-water pyrite confirms a rise in the oceanic Mo inventory across the pre-Cambrian-Cambrian boundary, implying the establishment of efficient deep-ocean ventilation. The carbonate-hosted pyrite also confirms the Neoarchaean and early Palaeoproterozoic ocean had higher Ni concentration, which can now more firmly be attributed to a greater proportion of magnesian volcanic rock on land rather than a stronger hydrothermal flux of Ni. Additionally, systematic trends are reported for Co, As, and Zn, relating to terrestrial flux and oceanic productivity. © 2015 John Wiley & Sons Ltd.
NASA Astrophysics Data System (ADS)
Gomes, M. L.; Fike, D. A.; Bergmann, K.; Knoll, A. H.
2015-12-01
Sulfur (S) isotope signatures of sedimentary pyrite preserved in marine rocks provide a rich suite of information about changes in biogeochemical cycling associated with the evolution of microbial metabolisms and oxygenation of Earth surface environments. Conventionally, these S isotope records are based on bulk rock measurements. Yet, in modern microbial mat environments, S isotope compositions of sulfide can vary by up to 40‰ over a spatial range of ~ 1 mm. Similar ranges of S isotope variability have been found in Archean pyrite grains using both Secondary Ion Mass Spectrometry and other micro-analytical techniques. These micron-scale patterns have been linked to changes in rates of microbial sulfate reduction and/or sulfide oxidation, isotopic distillation of the sulfate reservoir due to microbial sulfate reduction, and post-depositional alteration. Fine-scale mapping of S isotope compositions of pyrite can thus be used to differentiate primary environmental signals from post-depositional overprinting - improving our understanding of both. Here, we examine micron-scale S isotope patterns of pyrite in microbialites from the Mesoproterozoic-Neoproterozoic Sukhaya Tunguska Formation and Neoproterozoic Draken Formation in order to explore S isotope variability associated with different mat textures and pyrite grain morphologies. A primary goal is to link modern observations of how sulfide spatial isotope distributions reflect active microbial communities present at given depths in the mats to ancient processes driving fine-sale pyrite variability in microbialites. We find large (up to 60‰) S isotope variability within a spatial range of less than 2.5cm. The micron-scale S isotope measurements converge around the S isotope composition of pyrite extracted from bulk samples of the same microbialites. These micron-scale pyrite S isotope patterns have the potential to reveal important information about ancient biogeochemical cycling in Proterozoic mat environments with implications for interpreting S isotope signatures from the geological record.
Application of fuel cell for pyrite and heavy metal containing mining waste
NASA Astrophysics Data System (ADS)
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.
Ammar, Salah; Oturan, Mehmet A; Labiadh, Lazhar; Guersalli, Amor; Abdelhedi, Ridha; Oturan, Nihal; Brillas, Enric
2015-05-01
Tyrosol (TY) is one of the most abundant phenolic components of olive oil mill wastewaters. Here, the degradation of synthetic aqueous solutions of 0.30 mM TY was studied by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder was the source of Fe(2+) catalyst instead of a soluble iron salt used in classical EF. Experiments were performed with a cell equipped with a boron-doped diamond anode and a carbon-felt cathode, where TY and its products were destroyed by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between Fe(2+) and H2O2 generated at the cathode. Addition of 1.0 g L(-1) pyrite provided an easily adjustable pH to 3.0 and an appropriate 0.20 mM Fe(2+) to optimize the EF-pyrite treatment. The effect of current on mineralization rate, mineralization current efficiency and specific energy consumption was examined under comparable EF and EF-pyrite conditions. The performance of EF-pyrite was 8.6% superior at 50 mA due to self-regulation of soluble Fe(2+) by pyrite. The TY decay in this process followed a pseudo-first-order kinetics. The absolute rate constant for TY hydroxylation was 3.57 × 10(9) M(-1) s(-1), as determined by the competition kinetics method. Aromatic products like 3,4-dihydroxyphenylethanol, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and catechol, as well as o-benzoquinone, were identified by GC-MS and reversed-phase HPLC. Short-chain aliphatic carboxylic acids like maleic, glycolic, acetic, oxalic and formic were quantified by ion-exclusion HPLC. Oxalic acid was the major and most persistent product found. Based on detected intermediates, a plausible mineralization pathway for TY by EF-pyrite was proposed. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Kaur, Jasmeet; Schoonen, Martin A.
2017-06-01
The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and exposure to dust containing the two metal sulfides may present a health burden.
Suppression of pyritic sulphur during flotation tests using the bacterium Thiobacillus ferrooxidans.
Townsley, C C; Atkins, A S; Davis, A J
1987-07-01
Environmental concern about sulphur dioxide emissions has led to the examination of the possibility of removing pyritic sulphur from coal prior to combustion during froth flotation, a routine method for coal cleaning at the pit-head. The bacterium Thiobacillus ferrooxidans was effective in leaching 80% and 63% -53 mum pyrite at 2% and 6% pulp density in shake flasks in 240 and 340 h, respectively.The natural floatability of pyrite was significantly reduced in the Hallimond tube following 2.5 min of conditioning in membrane-filtered bacterial liquor prior to flotation. The suppression effect was greatly enhanced in the presence of Thiobacillus ferrooxidans. A bacterial suspension in pH 2.0 distilled water showed 85% suppression, whereas in spent growth liquor this value was 95%. The optimum bacterial density was 3.25 x 10(10) cells/g pyrite in 230-ml distilled water (2% pulp density) in the Hallimond tube. The degree of suppression by the cells was related to particle size but not to pH or temperature. The sulphur content of a synthetic coal/pyrite mixture was reduced from 10.9 to 2.1% by flotation after bacterial preconditioning. It is postulated that pyrite removal in coals which are cleaned by froth flotation could be significantly reduced using a bacterial preconditioning stage with a short residence time of 2.5 min.
Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions
Sebol, L.A.; Robertson, W.D.; Busenberg, E.; Plummer, Niel; Ryan, M.C.; Schiff, S.L.
2007-01-01
A detailed local-scale monitoring network was used to assess CFC distribution in an unconfined sand aquifer in southwestern Ontario where the zone of 1-5-year-old groundwater was known with certainty because of prior use of a bromide tracer. Groundwater ???5 years old was confined to an aerobic zone at ???5 m depth and had CFC concentrations consistent with modern atmospheric mixing ratios at recharge temperatures of 7-11 ??C, as was observed in the 3-m thick vadose zone at the site. At depths below 6 m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6-7 m depth, and a Mn and Fe reducing zone below 7 m depth. In the anaerobic zone, 3H/3He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13 m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3H/3He ages. Noble gas data indicated that the apparent CFC mass loss was not likely the result of gas stripping from possible bubble formation; thus, CFC degradation was indicated in the anoxic zone. The field data are consistent with first-order degradation rates of 0.3 yr-1 for CFC-12, 0.7 yr-1 for CFC-11, and 1.6 yr-1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO3 and dissolved oxygen (DO). Similar behavior has been observed at other sites [Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrification in an agricultural watershed: electron and mass balance along groundwater flow path. Water Resour. Res. 36 (6), 1545-1559; Hinsby, K., Hojberg, A.L., Engesgaard, P., Jensen, K.H., Larsen, F., Plummer, L.N., Busenberg, E., Accepted for publication. Transport and degradation of chlorofluorocarbons (CFCs) in a pyritic aquifer, Rabis Creek, Denmark. Water Resour. Res.], further demonstrating that the use of CFCs for age-dating anaerobic groundwater should be approached with caution, particularly if the sediment contains pyrite. ?? 2007 Elsevier B.V. All rights reserved.
Kettler, R.M.; Rye, R.O.; Kesler, S.E.; Meyers, P.A.; Polanco, J.; Russell, N.
1992-01-01
The Pueblo Viejo district, located in the Cordillera Central of the Dominican Republic, contains large Au-Ag deposits associated with acid-sulfate alteration within spilites, conglomerates and carbonaceous sedimentary rocks that were deposited in a maar-diatreme complex. Much of the Au mineralization occurs in pyritic, carbonaceous siltstones of the Pueblo Viejo Maar-Diatreme Member of the Cretaceous Los Ranchos Formation. Pyrite is the only Fe-bearing phase in mineralized rock, whereas siderite is the dominant Fe-bearing phase in siltstones distal to mineralization. Disseminated pyrite occurs as framboids, cubes, pyritohedra, concretions and cement. Early framboids occur throughout the district. Au occurs as inclusions in later non-framboid disseminated pyrite (NFDP); an occurrence that is interpreted to be indicative of contemporaneous deposition. Pyrite framboids exhibit a wide range of ??34Scdt-values (-17.5 to +4.8???) and are interpreted to have formed during biogenic reduction of pore-water sulfate. The NFDP yield restricted ??34Scdt-values ( x ?? = -5.2???, s = ??2.4???, n = 43) similar to those obtained from later vein pyrite ( x ?? = -6.4???, s = ??1.5???, n = 12). Alunite and barite have ??34S-values ranging from +18.8 to +21.6???. The interpretation that the NFDP, vein pyrite, alunite and barite, and possibly even the framboidal pyrite share a common source of igneous sulfur is supported by the ??34S data. Siderite occurs as concretions and cement, contains abundant Mg (Fe0.75Mg0.19Mn0.03Ca0.02CO3) and has ??13Cpdb- and ??18Osmow-values ranging from -2.5 to +1.1%. and +14.6 to +19.5???, respectively. These data are consistent with the interpretation that the siderite formed in lacustrine sediments and that the carbonate in the siderite is probably methanogenic, although contributions from oxidation of organic matter during biogenic sulfate reduction, thermal decarboxylation of organic matter, or magmatic vapor cannot be ruled out. Disseminated Au mineralization in the sedimentary rocks formed when a hydrothermal fluid encountered reactive Fe2+ in diagenetic siderite. The ensuing pyrite deposition consumed H2S and destabilized the Au (HS)-2 complex, leading to precipitation of Au. The capacity of the sedimentary rocks to consume H2S and precipitate Au was controlled by the amount of non-pyrite Fe present as siderite. The abundance of siderite was controlled by the extent of pyrite formation during diagenesis. ?? 1992.
Sulfur variability and petrology of the Lower Block Coal Member (Pennsylvanian) in Southwest Indiana
Padgett, P.L.; Rimmer, S.M.; Ferm, J.C.; Hower, J.C.; Eble, C.F.; Mastalerz, Maria
1999-01-01
The Lower Block Coal Member (Pennsylvanian-Atokan, Westphalian C) is an economic low-to medium-sulfur, low-ash coal resource in the Illinois Basin. Sulfur content is generally low (averaging 1.0%) in the study area, but varies over short distances. Higher sulfur areas occur as isolated pods and epigenetic pyrite increases significantly in the upper third of the selected columns in higher sulfur areas. Sulfur variations cannot be predicted by typical geologic characteristics such as roof lithology, seam thickness, or seam elevation. Petrographic analysis shows that pyrite is generally associated with brighter microlithotypes, except in higher sulfur areas where infilling pyrite forms are associated with inertite. Higher sulfur areas reflect the water chemistry of the paleomire during and shortly after peat accumulation. Locally, abundant pyrofusinite provided additional pore space for pyrite precipitation.The Lower Block Coal Member (Pennsylvanian-Atokan, Westphalian C) is an economic low- to medium-sulfur, low-ash coal resource in the Illinois Basin. Sulfur content is generally low (averaging 1.0%) in the study area, but varies over short distances. Higher sulfur areas occur as isolated pods and epigenetic pyrite increases significantly in the upper third of the selected columns in higher sulfur areas. Sulfur variations cannot be predicted by typical geologic characteristics such as roof lithology, seam thickness, or seam elevation. Petrographic analysis shows that pyrite is generally associated with brighter microlithotypes, except in higher sulfur areas where infilling pyrite forms are associated with inertite. Higher sulfur areas reflect the water chemistry of the paleomire during and shortly after peat accumulation. Locally, abundant pyrofusinite provided additional pore space for pyrite precipitation.
Electron Transfer Between Electrically Conductive Minerals and Quinones
NASA Astrophysics Data System (ADS)
Taran, Olga
2017-07-01
Long-distance electron transfer in marine environments couples physically separated redox half-reactions, impacting biogeochemical cycles of iron, sulfur and carbon. Bacterial bio-electrochemical systems that facilitate electron transfer via conductive filaments or across man-made electrodes are well known, but the impact of abiotic currents across naturally occurring conductive and semiconducitve minerals is poorly understood. In this paper I use cyclic voltammetry to explore electron transfer between electrodes made of common iron minerals (magnetite, hematite, pyrite, pyrrhotite, mackinawite and greigite), and hydroquinones - a class of organic molecules found in carbon-rich sediments. Of all tested minerals, only pyrite and magnetite showed an increase in electric current in the presence of organic molecules, with pyrite showing excellent electrocatalytic performance. Pyrite electrodes performed better than commercially available glassy carbon electrodes and showed higher peak currents, lower overpotential values and a smaller separation between oxidation and reduction peaks for each tested quinone. Hydroquinone oxidation on pyrite surfaces was reversible, diffusion controlled, and stable over a large number of potential cycles. Given the ubiquity of both pyrite and quinones, abiotic electron transfer between minerals and organic molecules is likely widespread in Nature and may contribute to several different phenomena, including anaerobic respiration of a wide variety of microorganisms in temporally anoxic zones or in the proximity of hydrothermal vent chimneys, as well as quinone cycling and the propagation of anoxic zones in organic rich waters. Finally, interactions between pyrite and quinones make use of electrochemical gradients that have been suggested as an important source of energy for the origins of life on Earth. Ubiquinones and iron sulfide clusters are common redox cofactors found in electron transport chains across all domains of life and interactions between quinones and pyrite might have been an early analogue of this ubiquitous systems.
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.
Effect of inversion layer at iron pyrite surface on photovoltaic device
NASA Astrophysics Data System (ADS)
Uchiyama, Shunsuke; Ishikawa, Yasuaki; Uraoka, Yukiharu
2018-03-01
Iron pyrite has great potential as a thin-film solar cell material because it has high optical absorption, low cost, and is earth-abundant. However, previously reported iron pyrite solar cells showed poor photovoltaic characteristics. Here, we have numerically simulated its photovoltaic characteristics and band structures by utilizing a two-dimensional (2D) device simulator, ATLAS, to evaluate the effects of an inversion layer at the surface and a high density of deep donor defect states in the bulk. We found that previous device structures did not consider the inversion layer at the surface region of iron pyrite, which made it difficult to obtain the conversion efficiency. Therefore, we remodeled the device structure and suggested that removing the inversion layer and reducing the density of deep donor defect states would lead to a high conversion efficiency of iron pyrite solar cells.
Process for removing pyritic sulfur from bituminous coals
Pawlak, Wanda; Janiak, Jerzy S.; Turak, Ali A.; Ignasiak, Boleslaw L.
1990-01-01
A process is provided for removing pyritic sulfur and lowering ash content of bituminous coals by grinding the feed coal, subjecting it to micro-agglomeration with a bridging liquid containing heavy oil, separating the microagglomerates and separating them to a water wash to remove suspended pyritic sulfur. In one embodiment the coal is subjected to a second micro-agglomeration step.
NASA Astrophysics Data System (ADS)
Borda, Michael J.; Elsetinow, Alicia R.; Schoonen, Martin A.; Strongin, Daniel R.
2001-09-01
The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.
Aqueous pyrite oxidation by dissolved oxygen and by ferric iron
Moses, Carl O.; Nordstrom, D. Kirk; Herman, Janet S.; Mills, Aaron L.
1987-01-01
Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.
Pyrite oxidation under simulated acid rain weathering conditions.
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.
48 CFR 742.1170-4 - Progress reporting requirements and contract clause.
Code of Federal Regulations, 2010 CFR
2010-10-01
... progress. (b) Because the cognizant technical officer is the individual most familiar with the contractor's performance, the contractor must submit the progress reports directly to the cognizant technical officer. The cognizant technical officer must review the reports and advise the contracting officer, in writing, of any...
Research on genesis of pyrite near the Permian-Triassic boundary in meishan, Zhejiang, China
Jiang, Y.-F.; Tang, Y.-G.; Chou, C.-L.
2006-01-01
The content and crystal forms of pyrite and sulfur isotope composition of pyrite sulfur as well as its vertical distribution near the Permian-Triassic (P/T) boundary in the Meishan section, Changxing county, Zhejiang province, China were studied using geological, petrological, mineralogical and geochemical methods (techniques). The result showed that the genesis of abundant pyrites in bed 24e2 at the uppermost part of the Changxing Formation in the Meishan section may be related to volcanic activity. In bed 24e2 of the Meishan section, pyrite has its highest content of 1.84% and the sulfur isotope composition has the highest ??34S value at + 2.2??? which is very similar to that of the average value of volcanic gas. There are some volcanic products such as ??-quartz, siliceous cylinders and siliceous spherules which coexisted with pyrites in beds 24e2 and 24f. It can be concluded that a large quantity of volcanic ash fell into the South China Sea and was incorporated into marine sediments during the formation of limestone at the uppermost part of the Changxing Formation. The volcanic eruption with massive amounts of H2S and S02 gas at the end of the Permian period resulted in the enrichment of H2S in the South China Sea areas. The reaction of H2S with reactive iron minerals formed the mass of abundant pyrites.
Spectral Induced Polarization of Disseminated Pyrite Particles in Soil
NASA Astrophysics Data System (ADS)
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.
Ramírez-Aldaba, Hugo; Valles, O Paola; Vazquez-Arenas, Jorge; Rojas-Contreras, J Antonio; Valdez-Pérez, Donato; Ruiz-Baca, Estela; Meraz-Rodríguez, Mónica; Sosa-Rodríguez, Fabiola S; Rodríguez, Ángel G; Lara, René H
2016-10-01
Bioleaching of arsenopyrite presents a great interest due to recovery of valuable metals and environmental issues. The current study aims to evaluate the arsenopyrite oxidation by Acidithiobacillus thiooxidans during 240h at different time intervals, in the presence and absence of supplementary arsenic. Chemical and electrochemical characterizations are carried out using Raman, AFM, SEM-EDS, Cyclic Voltammetry, EIS, electrophoretic and adhesion forces to comprehensively assess the surface behavior and biooxidation mechanism of this mineral. These analyses evidence the formation of pyrite-like secondary phase on abiotic control surfaces, which contrast with the formation of pyrite (FeS2)-like, orpiment (As2S3)-like and elementary sulfur and polysulfide (Sn(2-)/S(0)) phases found on biooxidized surfaces. Voltammetric results indicate a significant alteration of arsenopyrite due to (bio)oxidation. Resistive processes determined with EIS are associated with chemical and electrochemical reactions mediated by (bio)oxidation, resulting in the transformation of arsenopyrite surface and biofilm direct attachment. Charge transfer resistance is increased when (bio)oxidation is performed in the presence of supplementary arsenic, in comparison with lowered abiotic control resistances obtained in its absence; reinforcing the idea that more stable surface products are generated when As(V) is in the system. Biofilm structure is mainly comprised of micro-colonies, progressively enclosed in secondary compounds. A more compact biofilm structure with enhanced formation of secondary compounds is identified in the presence of supplementary arsenic, whereby variable arsenopyrite reactivity is linked and attributed to these secondary compounds, including Sn(2-)/S(0), pyrite-like and orpiment-like phases. Copyright © 2016 Elsevier B.V. All rights reserved.
Kelly, Karen; Slack, John; Selby, David
2009-01-01
The Brooks Range contains enormous accumulations of zinc and copper, either as VMS or sediment-hosted deposits. The Ruby Creek and Omar deposits are Cu-Co stratabound deposits associated with dolomitic breccias. Numerous volcanogenic Cu-Zn (+/-Ag, Au) deposits are situated ~20 km north of the Ruby Creek deposit. The carbonate-hosted deposits consist of chalcopyrite and bornite that fill open spaces, replace the matrix of the breccias, and occur in later cross-cutting veins. Cobaltiferous pyrite, chalcocite, minor tennantite-tetrahedrite, galena, and sphalerite are also present. At Ruby Creek, phases such as carrollite, renierite, and germanite occur rarely. The deposits have undergone post-depositional metamorphism (Ruby Creek, low greenschist facies; Omar, blueschist facies). The unusual geochemical signature includes Cu-Co +/- Ag, As, Au, Bi, Ge, Hg, Sb, and U with sporadic high Re concentrations (up to 2.7 ppm). New Re-Os data were obtained for chalcopyrite, bornite, and pyrite from the Ruby Creek deposit (analyses of sulfides from Omar are in progress). The data show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the Ruby Creek deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization occurred at 384 +/-4.2 Ma, which coincides with zircon U-Pb ages from igneous rocks that are spatially and genetically associated with VMS deposits. This suggests a temporal link between regional magmatism and hydrothermal mineralization.
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 resolution are needed to precisely verify surface structures formed after copper activation. Sphalerite and pyrite surfaces are characterised by varying amounts of steps and defects, and this heterogeneity suggests co-existence of more than one copper-sulfide structure after activation.
NASA Astrophysics Data System (ADS)
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 associated with OAE2 impacted environmental redox states, which in turn drove major changes in microbial energy cycling and sulfur and carbon burial fluxes during this critical period of Earth history.
Education, Technical Progress, and Economic Growth: The Case of Taiwan.
ERIC Educational Resources Information Center
Lin, T.-C.
2003-01-01
Investigates the effect of education and the role of technical progress on economic growth in Taiwan from 1965-2000. Finds that education has a positive and significant effect on growth, but the role of technical progress does not appear to be extraordinarily important. Furthermore, no markedly significant relationships exist between capital and…
NASA Astrophysics Data System (ADS)
Kelley, Karen D.; Selby, David; Falck, Hendrik; Slack, John F.
2017-03-01
Stratiform Zn-Pb deposits hosted in unmetamorphosed carbonaceous and siliceous mudstones of the Ordovician to Silurian Duo Lake Formation define the Howards Pass district in Yukon Territory and Northwest Territories, western Canada. Collectively, the deposits are amongst the largest in the world, containing drill-indicated and inferred resources of 423 Mt at 4.84 % Zn and 1.59 % Pb. Sulphide textures include (a) fine-scale laminations of sphalerite, galena, and pyrite from <0.05 mm to 1 cm thick, interbedded with carbonaceous sedimentary rock; (b) layers of coarse sulphide that are structurally controlled by microfolds; and (c) veins that cut bedding and sulphide laminations. The finely interlaminated nature of sulphides with mudstone has been used as evidence for syngenetic mineralizing processes, whereas paleomagnetic data determined on coarse layered sulphides suggest a Middle Jurassic age of mineralization. Here, we present new rhenium-osmium (Re-Os) isotopic data for 12 pyrite separates obtained from 4 laminated sulphide-rich samples from the XY Central (XYC) and Don (DON) deposits and for 1 unmineralized organic-rich mudstone ˜20 m stratigraphically below the sulphide-bearing zone. Pyrite separates that lack mudstone inclusions ("pure") from the XYC deposit contain 2.2 to 4.0 ppb Re and 93.4 to 123.4 ppt Os; pure pyrite from the DON deposit is significantly more enriched in Re and Os (34-37 ppb Re; 636.8-694.9 ppt Os). The 187Re/188Os values of pure pyrite separates from the XYC and DON deposits range from 137.6 to 197 and 182.1 to 201.4, respectively. Regression of all pure pyrite Re-Os data from both deposits yields an isochron age of 442 ± 14 Ma (MSWD = 7.4) and an initial 187Os/188Os (Osi) value of 0.71 ± 0.07. The Re-Os age indicates that the early phase of pyrite precipitation (and by inference, sphalerite and galena) occurred during the early Silurian, consistent with biostratigraphic ages of the host rocks. The Osi value of ˜0.8 for earliest Silurian seawater recorded from organic-rich shale in the basal Silurian Global Stratotype Section and Point (GSSP) at Dobs Linn, Scotland is very similar to that provided by the Howards Pass pyrite regression and hence suggests a hydrogenous (seawater) source of Os for the pyrite. Therefore, two possible sources of Os are (1) the Zn- and Pb-bearing hydrothermal fluid that leached Os from footwall sedimentary rocks, which were deposited in seawater, or (2) directly from seawater during precipitation of the pyrite, which suggests that the Os content of the hydrothermal fluid was minor relative to that of seawater.
NASA Astrophysics Data System (ADS)
Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Gong, Junli; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn
2017-08-01
Multiple sulfur isotope signatures and secondary ion mass spectroscopy (SIMS) sulfur isotope compositions of pyrite from two seafloor sites (DH-CL11 and HD109) in seepage areas of the South China Sea were measured in order to study isotope effects of sulfate-driven anaerobic oxidation of methane (SO4-AOM). The multiple sulfur isotopes of pyrite reveal variable ranges for both sites (δ34S: between -44.1‰ and -2.9‰ for DH-CL11 and between -43.8‰ and -1.6‰ for HD109; Δ33S: between 0.02‰ and 0.17‰ for DH-CL11 and between -0.03‰ and 0.14‰ for HD109). SIMS analysis reveals an extreme variability of δ34S values (between -50.3‰ and -2.7‰ in DH-CL11; between -50.1 and 52.4‰ in HD109) for three types of pyrite: (1) framboids, (2) zoned aggregates with radial overgrowth surrounding a framboidal core, and (3) euhedral pyrite crystals. The synchronous changes of geochemical proxies (sulfate and methane concentrations, δ34Ssulfate and δ18Osulfate, δ34Spyrite, and pyrite content) at the sulfate-methane transition zone (SMTZ) at site DH-CL11 are interpreted to be induced by SO4-AOM under steady state conditions. In contrast, pyrite content and δ34S value fluctuations throughout core HD109 suggest that the sediment at this site was affected by multiple pyritization events during diagenesis. Multiple sulfur isotope signatures of early diagenetic pyrite (i.e., with low and high δ34S values, the latter above 315 cmbsf in DH-CL11; above 70 cmbsf in HD109) in the upper sediment column suggest that organoclastic sulfate reduction (OSR) and sulfur disproportionation generated the observed isotopic signatures. In contrast to the early diagenetic 34S depleted framboids, the higher SIMS δ34S values of overgrowth and euhedral crystals suggest a late diagenetic 34S enriched pool of dissolved sulfide derived from SO4-AOM at the current and paleo-SMTZs. Interestingly, pyrite resulting from SO4-AOM in the SMTZ at site DH-CL11 reveals a distinct pattern with higher Δ33S values, different from pyrite resulting from OSR and sulfur disproportionation. Therefore, paired δ34S and Δ33S values may allow to differentiate OSR and SO4-AOM, although a full understanding of the isotope effects associated with SO4-AOM is hampered by uncertainties on the actual electron transfer mechanism in the syntrophic SO4-AOM consortium.
Pyrite in contact with supercritical water: the desolation of steam.
Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco
2015-07-14
The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.
Effects of Surfactants on Chlorobenzene Absorption on Pyrite Surface
NASA Astrophysics Data System (ADS)
Hoa, P. T.; Suto, K.; Inoue, C.; Hara, J.
2007-03-01
Recently, both surfactant extraction of chlorinated compounds from contaminated soils and chemical reduction of chlorinated compounds by pyrite have had received a lot of attention. The reaction of the natural mineral pyrite was found as a surface controlling process which strongly depends on absorption of contaminants on the surface. Surfactants were not only aggregated into micelle which increase solubility of hydrophobic compounds but also tend to absorb on the solid surface. This study investigated effects of different kinds of Surfactants on absorption of chlorobenzene on pyrite surface in order to identify coupling potential of surfactant application and remediation by pyrite. Surfactants used including non-ionic, anionic and cationic which were Polyoxyethylene (23) Lauryl Ether (Brij35), Sodium Dodecyl Sulfate (SDS) and Cetyl TrimethylAmmonium Bromide (CTAB) respectively were investigated with a wide range of surfactant concentration up to 4 times of each critical micelle concentration (CMC). Chlorobenzene was chosen as a representative compound. The enhancement or competition effects of Surfactants on absorption were discussed.
Formation of pyrite (FeS{sub 2}) thin films by thermal sulfurization of dc magnetron sputtered iron
DOE Office of Scientific and Technical Information (OSTI.GOV)
Soukup, R. J.; Prabukanthan, P.; Ianno, N. J.
2011-01-15
Iron films deposited by direct current magnetron sputtering onto glass substrates were converted into FeS{sub 2} films by thermal sulfurization. Experiments were carried out to optimize the sulfurization process, and the formation of FeS{sub 2} thin films was investigated under different annealing temperatures and times. High quality FeS{sub 2} films were fabricated using this process, and single phase pyrite films were obtained after sulfurization in a sulfur and nitrogen atmosphere at 450 deg. C for 1 h. Film crystallinity and phase identification were determined by using x-ray diffraction. The cubic phase pyrite films prepared were p-type, and scanning electron microscopymore » studies exhibited a homogeneous surface of pyrite. The authors have found that the best Ohmic contact for their pyrite thin films, using inexpensive metals, was Ni. The following were chosen for the study: Al, Mo, Fe, and Ni, and the one that led to the lowest resistance, 333 {Omega}, was Ni.« less
NASA Astrophysics Data System (ADS)
Liu, C.; Jiang, S. Y.; Su, X.
2017-12-01
Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.
[Study on structure and phase transformation laws of natural FeS2 whisker by Raman spectroscopy].
Huang, Fei; Kou, Da-Ming; Yao, Yu-Zeng; Ni, Pei; Ding, Jun-Ying
2009-08-01
FeS2 belongs to sulfide, including pyrite of isometric system and marcasite of orthorhombic system. The FeS2 discovered in Gengzhuang, Shanxi Province, was growing in the form of whisker. The study with scanning electron microscopy and electron probe show that the mineral components of FeS2 vary regularly. The structure of natural nano-micron FeS2 whisker was determined by micro-Raman spectroscopy. The results show that there exist two types of structure in FeS2 whiskers: pyrite and marcasite. Marcasite presents irregular shapes, such as coarse lotus root joints, crude columnar or beaded. Pyrite exists in the shape of straight line and smooth surface. In the early growing stage, Gengzhuang FeS2 whisker was mainly marcasite-type structure; in the middle stage it was coexistent structure of pyrite- and marcasite-type; in the late stage it was mainly pyrite-type. The growing stages of the whisker FeS2 show the phase transformation laws. Moreover, during the growing process marcasite was growing with pyrite coated on. Study on FeS2 whisker structure shows that there are correlations between phase transformation laws of the structure and forms, and between the forming time and the composition characteristics.
Selective Adhesion of Thiobacillus ferrooxidans to Pyrite
Ohmura, Naoya; Kitamura, Keiko; Saiki, Hiroshi
1993-01-01
Bacterial adhesion to mineral surfaces plays an important role not only in bacterial survival in natural ecosystems, but also in mining industry applications. Selective adhesion was investigated with Thiobacillus ferrooxidans by using four minerals, pyrite, quartz, chalcopyrite, and galena. Escherichia coli was used as a control bacterium. Contact angles were used as indicators of hydrophobicity, which was an important factor in the interaction between minerals and bacteria. The contact angle of E. coli in a 0.5% sodium chloride solution was 31°, and the contact angle of T. ferrooxidans in a pH 2.0 sulfuric acid solution was 23°. E. coli tended to adhere to more hydrophobic minerals by hydrophobic interaction, while T. ferrooxidans selectively adhered to iron-containing minerals, such as pyrite and chalcopyrite. Ferrous ion inhibited the selective adhesion of T. ferrooxidans to pyrite competitively, while ferric ion scarcely inhibited such adhesion. When selective adhesion was quenched by ferrous ion completely, adhesion of T. ferrooxidans was controlled by hydrophilic interactions. Adhesion of E. coli to pyrite exhibited a liner relationship on langmuir isotherm plots, but adhesion of T. ferrooxidans did not. T. ferrooxidans recognized the reduced iron in minerals and selectively adhered to pyrite and chalcopyrite by a strong interaction other than the physical interaction. PMID:16349106
Webinar May 17: Fuel Cell Electric Bus Progress Toward Meeting Technical
Targets | News | NREL Webinar May 17: Fuel Cell Electric Bus Progress toward Meeting Technical Targets Webinar May 17: Fuel Cell Electric Bus Progress toward Meeting Technical Targets May 14, 2018 The U.S. Department of Energy's (DOE's) Fuel Cell Technologies Office will present a live webinar titled
Interactions of Oxygen and Water Molecules with Pyrite Surface: A New Insight.
Li, Yuqiong; Chen, Jianhua; Chen, Ye; Zhao, Cuihua; Zhang, Yibing; Ke, Baolin
2018-02-06
Pyrite is the most common sulfide in nature, and it is well-known for its roles in acid mine drainage, flotation separation of useful metal (Cu, Pb, Zn, and Mo) sulfide minerals, optoelectronic and photovoltaic application, pneumoconiosis, and even in the origin of life. However, the detailed oxidation behaviors of pyrite are still unclear and not well-understood. New oxidation pathways by O 2 on the pyrite (100) surface have been found in this work for the first time using density functional theory simulation; that is, besides Fe sites, S sites are also possible oxidation sites in the initial oxidation state of pyrite, where easier and stronger oxidation may occur. This is the first time to confirm the other researchers' conjecture on the direct oxidation of S sites, which explains the isotopic composition experiments that a minor amount of O 2 is permanently incorporated into SO 4 2- during pyrite oxidation (O in SO 4 2- is mainly derived from water). We constructed various H 2 O-O 2 coadsorption models on the pyrite surface by considering the adsorption sequence of H 2 O and O 2 . It is found that the H 2 O molecule undergoes step-wise dissociation in the presence of the O 2 molecule. Hydroxyl radical •OH is the reactive oxygen species during H 2 O dissociation. Cyclic voltammetric measurements confirm the presence of •OH. In addition, H 2 O 2 may also be formed on the surface in terms of H 2 O-then-O 2 sequence adsorption.
Genesis of the Permian karstic Pingguo bauxite deposit, western Guangxi, China
NASA Astrophysics Data System (ADS)
Liu, Xuefei; Wang, Qingfei; Zhang, Qizuan; Yang, Shujuan; Liang, Yayun; Zhang, Ying; Li, Yan; Guan, Tao
2017-10-01
More than 0.5 billion tons of late Permian bauxite overlies the karstic topography of the Maokou Formation of western Guangxi in China. Here, we provide new mineralogical, geochemical, Sr-Nd-Pb isotopic, and pyrite S isotope and trace element compositional data for the Pingguo bauxite deposit, aiming to further our understanding of the genesis of Permian bauxite. The Pingguo bauxite contains three distinct layers: a lower layer dominated by ferric clay or weathered iron ore, a middle layer of cryptocrystalline and oolitic bauxite ore, and an upper layer dominated by argillaceous bauxite. The bauxite ore is mainly diaspore, pyrite, chamosite, and anatase, whereas the argillaceous bauxite contains diaspore, kaolinite, pyrophyllite, pyrite, and anatase. Two types of pyrite have been identified within the bauxite: fine-grained and framboidal pyrite (Py1) occurring in aggregates and coarse-grained and euhedral pyrite (Py2). Py1 is enriched in trace elements and is thought to have a diagenetic origin, whereas Py2 is deficient in trace elements and is considered to have formed by later recrystallization. The S isotopic composition of pyrite (-34.11 to -18.91‰) and visible ovoid microorganisms within the bauxite provide evidences of microbial activity during bauxite formation. The Sr-Nd-Pb isotopic composition of the bauxite indicates that these ores were generated by the weathering of basalts belonging to the Emeishan Large Igneous Province (LIP) and limestones of the Maokou Formation. Microorganisms were likely to have enhanced the dissolution and weathering of the parent rock and facilitated the precipitation of diaspore under near-surface conditions.
NASA Astrophysics Data System (ADS)
Swanner, Elizabeth; Cates, Nicole; Pecoits, Ernesto; Bekker, Andrey; Konhauser, Kurt O.; Mojzsis, Stephen J.
2013-04-01
Sediments of the ca. 2400 Ma Turee Creek Group of Western Australia span the oxygenation of Earth's surface resulting from the 'Great Oxidation Event' (GOE). Diamictite within the Boolgeeda Iron Formation from the Boundary Ridge section at Duck Creek Syncline have been correlated to the glaciogenic Meteorite Bore Member of the Turee Creek Group at Hardey Syncline (Martin, 1999). The Meteorite Bore Member is thought to be correlative and time-equivalent with the Paleoproterozoic glacial diamictites of North America. If diamictite units at Boundary Ridge represent worldwide Paleoproterozoic glaciations, they should record the disappearance of mass independently fractionated (MIF) sulfur. Triple S-isotope compositions for pyrites from the Boundary Ridge sections measured by in situ multi-collector ion microprobe yielded both mass-dependent and mass-independently fractionated (MIF) S isotope values (Δ33S values from -0.65 to 6.27). Trace element heterogeneities were found by measurements at multiple spatial scales within rounded pyrites in the Boundary Ridge section, signifying multiple generations of pyrite from sulfur processed in an anoxic atmosphere. S-isotope data from pyrite in the Boundary Ridge diamictites analyzed in this study and previous work (Williford et al., 2011) define multiple δ34S vs. δ33S arrays, linked to a source of detrital pyrite from the overlying Hamersley and Fortescue groups. Authigenic pyrite in an overlying shale unit from Boundary Ridge plot along the terrestrial fractionation line but retain positive MIF-S and detrital pyrite, results that are incompatible with a correlation to North American Paleoproterozoic glacially-influenced successions where the MIF-S signal permanently disappears. The diamictites at the Duck Creek Syncline are older than the Meteorite Bore Member because of their stratigraphic position within the Boolgeeda Iron Formation underlying the Turee Creek Group, which is separated from the Meteorite Bore Member by nearly 1000 m of Kungarra shale at Hardey Syncline.
NASA Astrophysics Data System (ADS)
Dill, H. G.; Eberhard, E.; Hartmann, B.
1997-01-01
Fe disulphides are common opaque accessories in sedimentary rocks. Both marcasite and pyrite may shed some light on the depositional environment and help determine the diagenesis of their host rocks. Quantitative ore microscopy (reflectance measurements, Vickers hardness numbers) and X-ray diffraction methods, supplemented with scanning electron microscopy and chemical analyses, were applied to pyrite (and some marcasite) hosted by sedimentary rocks spanning the interval from the Devonian to the Pliocene, and formed in various marine and continental environments. Quantitative ore microscopy of pyrites of sedimentary origin does not seem to be an efficient tool for analyzing the environment owing to the inhomogeneous nature of sulphide aggregates when viewed under the ore microscope, and the variable amounts of minor elements (e.g., As, Ni, and Co) that control the reflectance values (RV) and Vickers hardness numbers (VHN) of the host sulphides. However, such parameters as crystal habit and unit cell length of pyrite, which correlate with FeS x, are useful for environmental analysis. The redox conditions and the presence of organic remains during formation are the main factors determining these crystallographic parameters. Differences in these parameters from those of pure, ideal FeS 2 can be related to substitution of, e.g., wustite in the pyrite lattice, reflecting moderate oxidation (i.e. in the microenvironment). As far as crystal habit and length of the cell edge are concerned, late stage diagenesis is obviously less important than the microenvironment attending initial formation. The environment of deposition (i.e. the macroenvironment) of pyrite-bearing rocks has no influence on the crystal morphology or the length of the unit cell of Fe disulphide. X-ray diffraction measurements demonstrate that this method provides useful evidence on the microenvironment of sulphide precipitation around a single, equant pyrite, as well as around pyritized fossils.
NASA Astrophysics Data System (ADS)
Höhn, S.; Frimmel, H. E.; Debaille, V.; Pašava, J.; Kuulmann, L.; Debouge, W.
2017-12-01
The stratiform Cu-Zn sulfide deposit at Kupferberg in Germany represents Bavaria's largest historic base metal producer. The deposit is hosted by Early Paleozoic volcano-sedimentary strata at the margin of a high-grade allochthonous metamorphic complex. The present paper reports on the first Cu and S isotope data as well as trace element analyses of pyrite from this unusual deposit. The new data point to syn-orogenic mineralization that was driven by metamorphic fluids during nappe emplacement. Primary Cu ore occurs as texturally late chalcopyrite within stratiform laminated pyrite in black shale in two different tectonostratigraphic units of very low and low metamorphic grade, respectively, that were juxtaposed during the Variscan orogeny. Trace element contents of different pyrite types suggest the presence of at least one hydrothermal pyrite generation (mean Co/Ni = 35), with the other pyrite types being syn-sedimentary/early diagenetic (mean Co/Ni = 3.7). Copper isotope analyses yielded a narrow δ65Cu range of -0.26 to 0.36‰ for all ore types suggesting a hypogene origin for the principal chalcopyrite mineralization. The ore lenses in the two different tectonostratigraphic units differ with regard to their δ34S values, but little difference exists between poorly and strongly mineralized domains within a given locality. A genetic model is proposed in which syn-sedimentary/early diagenetic pyrite with subordinate chalcopyrite and sphalerite formed in black shale beds in the two different stratigraphic units, followed by late-tectonic strata-internal, hydrothermal mobilization of Fe, Cu, and Zn during syn-orogenic thrusting, which concentrated especially Cu to ore grade. In agreement with this model, Cu distribution in stream sediments in this region shows distinct enrichments bound to the margin of the allochthonous complex. Thus, Kupferberg can be considered a rare example of a syn-orogenic Cu deposit with the Cu probably being derived from syn-sedimentary/early diagenetic pyrite contained in Early Paleozoic shale units.
NASA Astrophysics Data System (ADS)
Brunner, Benjamin; Yu, Jae-Young; Mielke, Randall E.; MacAskill, John A.; Madzunkov, Stojan; McGenity, Terry J.; Coleman, Max
2008-06-01
The solution chemistry during the initial (slow increase of dissolved iron and sulfate) and main stage (rapid increase of dissolved iron and sulfate) of pyrite leaching by Acidithiobacillus ferrooxidans (Af) at a starting pH of 2.05 shows significant differences. During the initial stage, ferrous iron (Fe2+) is the dominant iron species in solution and the molar ratio of produced sulfate (SO42-) and total iron (Fetot) is 1.1, thus does not reflect the stoichiometry of pyrite (FeS2). During the main stage, ferric iron (Fe3+) is the dominant iron species in solution and the SO42-:Fetot ratio is with 1.9, close to the stoichiometry of FeS2. Another difference between initial and main stage is an initial trend to slightly higher pH values followed by a drop during the main stage to pH 1.84. These observations raise the question if there are different modes of bioleaching of pyrite, and if there are, what those modes imply in terms of leaching mechanisms. Different oxygen and sulfur isotope trends of sulfate during the initial and main stages of pyrite oxidation confirm that there are two pyrite bioleaching modes. The biochemical reactions during initial stage are best explained by the net reaction FeS2 + 3O2 ⇒ Fe2+ + SO42- + SO2(g). The degassing of sulfur dioxide (SO2) acts as sink for sulfur depleted in 34S compared to pyrite, and is the cause of the SO42-:Fetot ratio of 1.1 and the near constant pH. During the exponential phase, pyrite sulfur is almost quantitatively converted to sulfate, according to the net reaction FeS2 + 15/4O2 + 1/2H2O ⇒ Fe3+ + 2SO42- + H+. We hypothesize that the transition between the modes of bioleaching of pyrite is due to the impact of the accumulation of ferrous iron, which induces changes in the metabolic activity of Af and may act as an inhibitor for the oxidation of sulfur species. This transition defines a fundamental change in the growth strategy of Af. A mode, where bacteria gain energy by oxidation of elemental sulfur to sulfite but show little growth is switched into a mode, where bacteria gain a smaller amount of energy by the oxidation of ferrous iron, but induce much faster pyrite leaching rates due to the production of ferric iron.
Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.
1994-01-01
A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.
Bove, Dana J.; Caine, Jonathan S.; Lowers, Heather
2012-01-01
The surface and subsurface geology, hydrothermal alteration, and mineralogy of the Handcart Gulch area was studied using map and drill core data as part of a multidisciplinary approach to understand the hydrology and affects of geology on acid-rock drainage in a mineralized alpine watershed. Handcart Gulch was the locus of intense hydrothermal alteration that affected an area of nearly 3 square kilometers. Hydrothermal alteration and accompanied weak mineralization are spatially and genetically associated with small dacite to low-silica rhyolite stocks and plugs emplaced about 37-36 Ma. Felsic lithologies are commonly altered to a quartz-sericite-pyrite mineral assemblage at the surface, but alteration is more variable in the subsurface, ranging from quartz-sericite-pyrite-dominant in upper core sections to a propylitic variant that is more typical in deeper drill core intervals. Late-stage, hydrothermal argillic alteration [kaolinite and(or) smectite] was superimposed over earlier-formed alteration assemblages in the felsic rocks. Smectite in this late stage assemblage is mostly neoformed resulting from dissolution of chlorite, plagioclase, and minor illite in more weakly altered rocks. Hydrothermally altered amphibolites are characterized by biotitic alteration of amphibole, and subsequent alteration of both primary and secondary biotite to chlorite. Whereas pyrite is present both as disseminations and in small veinlets in the felsic lithologies, it is mostly restricted to small veinlets in the amphibolites. Base-metal sulfides including molybdenite, chalcopyrite, sphalerite, and galena are present in minor to trace amounts in the altered rocks. However, geologic data in conjunction with water geochemical studies indicate that copper mineralization may be present in unknown abundance in two distinct areas. The altered rocks contain an average of 8 weight percent fine pyrite that is largely devoid of metals in the crystal structure, which can be a significant source of trace metals in other areas with acid rock drainage. Thus, elevated base-metal concentrations in the trunk stream and discrete springs in the study area, as determined in previous studies, are likely derived from discrete metal-rich sources, rather than the abundant pyrite veins or disseminations. Pyrite is oxidized in nearly all outcrops examined. Drill core data show that zones of pyrite oxidation range in depth from 100 meters below the surface at higher elevations to just a few meters depth at the lowest elevations in the study area. However, discrete pyrite oxidation zones are present in drill core to depths of several hundred meters below the pervasive near-surface oxidation zones. These deeper discrete oxidation zones, which are present where fresh pyrite predominates, are spatially associated with fractures, small faults, and breccias. Quartz-sericite-pyrite-altered rocks containing unoxidized pyrite likely have the highest acid-generating capacity of all alteration assemblages in the study area. Hydrothermal alteration has left these rocks base-cation leached and thus acid-neutralizing potential is negligible. In contrast, propylitic-altered felsic rocks commonly contain trace to minor calcite and abundant chlorite, which provide some amount of acid-neutralization despite the presence of a few percent pyrite.
An Evaluation of Coal Water Slurry Fuel Burners and Technology
1992-11-01
treatment) processes, such as froth flotation , which reduce ash and pyritic sulphur content (4). Unlike pulverized coal, there is no need for expensive drying...physical beneficiation (froth flotation ) to reduce pyrite , biotechnological and other methods to remove more sulfur (especially the organic portion...of limited effectiveness since only some of the pyritic sulfur (about 40 to 60 percent of the total sulfur) is removed for some coals, since 90 to 95
25 CFR 30.111 - When should the tribal governing body or school board request technical assistance?
Code of Federal Regulations, 2011 CFR
2011-04-01
... request technical assistance? 30.111 Section 30.111 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR EDUCATION ADEQUATE YEARLY PROGRESS Defining Adequate Yearly Progress Technical Assistance § 30.111 When should the tribal governing body or school board request technical assistance? In order to...
NASA Astrophysics Data System (ADS)
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(II)-citrate- oxidation. Most soluble Fe3+ that is produced from pyrite oxidation hydrolyzes to Fe(III) hydroxide. Kinetic models that were developed according to the proposed mechanisms identified the relative importance of each reaction for radOH production. Using the kinetic model, the oxidation efficiencies of the redox-active substances that react with radOH at different reaction-rate constants were estimated in the presence of 1 mM citrate. This study presents on the overlooked role of LMWOAs in enhancing radOH production from pyrite oxidation by O2 in pyrite-rich circumneutral environments, such as marine and estuarine sediments and salt marshes.
Senior, C.L.; Zeng, T.; Che, J.; Ames, M.R.; Sarofim, A.F.; Olmez, I.; Huggins, Frank E.; Shah, N.; Huffman, G.P.; Kolker, A.; Mroczkowski, S.; Palmer, C.; Finkelman, R.
2000-01-01
Trace elements in coal have diverse modes of occurrence that will greatly influence their behavior in many coal utilization processes. Mode of occurrence is important in determining the partitioning during coal cleaning by conventional processes, the susceptibility to oxidation upon exposure to air, as well as the changes in physical properties upon heating. In this study, three complementary methods were used to determine the concentrations and chemical states of trace elements in pulverized samples of four US coals: Pittsburgh, Illinois No. 6, Elkhorn and Hazard, and Wyodak coals. Neutron Activation Analysis (NAA) was used to measure the absolute concentration of elements in the parent coals and in the size- and density-fractionated samples. Chemical leaching and X-ray absorption fine structure (XAFS) spectroscopy were used to provide information on the form of occurrence of an element in the parent coals. The composition differences between size-segregated coal samples of different density mainly reflect the large density difference between minerals, especially pyrite, and the organic portion of the coal. The heavy density fractions are therefore enriched in pyrite and the elements associated with pyrite, as also shown by the leaching and XAFS methods. Nearly all the As is associated with pyrite in the three bituminous coals studied. The sub-bituminous coal has a very low content of pyrite and arsenic; in this coal arsenic appears to be primarily organically associated. Selenium is mainly associated with pyrite in the bituminous coal samples. In two bituminous coal samples, zinc is mostly in the form of ZnS or associated with pyrite, whereas it appears to be associated with other minerals in the other two coals. Zinc is also the only trace element studied that is significantly more concentrated in the smaller (45 to 63 ??m) coal particles.
Chemistry and phase evolution during roasting of toxic thallium-bearing pyrite.
Lopez-Arce, Paula; Garcia-Guinea, Javier; Garrido, Fernando
2017-08-01
In the frame of a research project on microscopic distribution and speciation of geogenic thallium (Tl) from contaminated mine soils, Tl-bearing pyrite ore samples from Riotinto mining district (Huelva, SW Spain) were experimentally fired to simulate a roasting process. Concentration and volatility behavior of Tl and other toxic heavy metals was determined by quantitative ICP-MS, whereas semi-quantitative mineral phase transitions were identified by in situ thermo X-Ray Diffraction (HT-XRD) and Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) analyses after each firing temperature. Sample with initial highest amount of quartz (higher Si content), lowest quantity of pyrite and traces of jarosite (lower S content) developed hematite and concentrated Tl (from 10 up to 72 mg kg -1 ) after roasting at 900 °C in an oxidizing atmosphere. However, samples with lower or absent quartz content and higher pyrite amount mainly developed magnetite, accumulating Tl between 400 and 500 °C and releasing Tl from 700 up to 900 °C (from 10-29 mg kg -1 down to 4-1 mg kg -1 ). These results show the varied accumulative, or volatile, behaviors of one of the most toxic elements for life and environment, in which oxidation of Tl-bearing Fe sulfides produce Fe oxides wastes with or without Tl. The initial chemistry and mineralogy of pyrite ores should be taken into account in coal-fired power stations, cement or sulfuric acid production industry involving pyrite roasting processes, and steel, brick or paint industries, which use iron ore from roasted pyrite ash, where large amounts of Tl entail significant environmental pollution. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
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.
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.
Site Synthesis Report of DSDP Sites 417 and 418
1989-06-01
radmolarsan sands including pyrite . chert and organics (black-clay facites) VII Pale to dark red brown, pink Upper Aptian to 291.5-324.0e -32,5 418A... pyrite , pyrrhotite, chalcopyrite, and pentlaudite. Plasse (1980) and Bleil and Smith (1980b) show that titanomaghemite, the primary magnetic mineral at...Hole 418A where it occurs as a rare phenocryst. Pyrite is the most common secondary opaque mineral. Except in Hole 417A, alteration products generally
Pyrite cathode material for a thermal battery
NASA Astrophysics Data System (ADS)
Pemsler, J. P.; Litchfield, J. K.
1991-02-01
The present invention relates in general to a synthetic cathode material for a molten salt battery and, more particularly, to a process of providing and using synthetic pyrite for use as a cathode in a thermal battery. These batteries, which have been successfully used in a number of military applications, include iron disulfide cathode material obtained as benefacted or from natural occurring pyrite deposits, or as a byproduct of flotation concentrate from the processing of base or noble metal ores.
Bellenberg, Sören; Díaz, Mauricio; Noël, Nanni; Sand, Wolfgang; Poetsch, Ansgar; Guiliani, Nicolas; Vera, Mario
2014-11-01
Bioleaching of metal sulfides is an interfacial process where biofilm formation is considered to be important in the initial steps of this process. Among the factors regulating biofilm formation, molecular cell-to-cell communication such as quorum sensing is involved. A functional LuxIR-type I quorum sensing system is present in Acidithiobacillus ferrooxidans. However, cell-to-cell communication among different species of acidophilic mineral-oxidizing bacteria has not been studied in detail. These aspects were the scope of this study with emphasis on the effects exerted by the external addition of mixtures of synthetic N-acyl-homoserine-lactones on pure and binary cultures. Results revealed that some mixtures had inhibitory effects on pyrite leaching. Some of them correlated with changes in biofilm formation patterns on pyrite coupons. We also provide evidence that A. thiooxidans and Acidiferrobacter spp. produce N-acyl-homoserine-lactones. In addition, the observation that A. thiooxidans cells attached more readily to pyrite pre-colonized by living iron-oxidizing acidophiles than to heat-inactivated or biofilm-free pyrite grains suggests that other interactions also occur. Our experiments show that pre-cultivation conditions influence A. ferrooxidans attachment to pre-colonized pyrite surfaces. The understanding of cell-to-cell communication may consequently be used to develop attempts to influence biomining/bioremediation processes. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.
History of water-column anoxia in the Black Sea indicated by pyrite framboid size distributions
Wilkin, R.T.; Arthur, M.A.; Dean, W.E.
1997-01-01
A detailed study of size distributions of framboidal pyrite in Holocene Black Sea sediments establishes the timing of a change from deposition under an oxic water column to deposition under an anoxic and sulfidic water column. In the most recent carbonate-rich sediments (Unit I) and in the organic carbon-rich sapropel (Unit II), framboid size distributions are remarkably uniform (mean diameter= 5 ??m); over 95% of the framboids in Unit I and Unit II are < 7 ??m in diameter. These properties of framboidal pyrite are consistent with framboid nucleation and growth within an anoxic and sulfidic water column, followed by transport to the sediment-water interface, cessation of pyrite growth due to the exhaustion of reactive iron, and subsequent burial. In contrast, the organic carbon-poor sediments of lacustrine Unit III contain pyrite framboids that are generally much larger in size (mean diameter = 10 ??m). In Unit III, over 95% of the framboids are < 25 ??m in diameter, 40% of framboids are between 7 ??m and 25 ??m, and framboids up to 50 ??m in diameter are present. This distribution of sizes suggests framboid nucleation and growth within anoxic sediment porewaters. These new data on size distributions of framboidal pyrite confirm that the development of water-column anoxia in the Black Sea coincided with the initiation of deposition of laminated Unit II sapropels.
FTIR studies of xanthate adsorption on chalcopyrite, pentlandite and pyrite surfaces
NASA Astrophysics Data System (ADS)
Zhang, Yahui; Cao, Zhao; Cao, Yongdan; Sun, Chuanyao
2013-09-01
The Fourier transform infrared (FTIR) spectra of sodium butyl xanthate, dibutyl dixanthogen, metal xanthate compounds and surfaces of chalcopyrite, pentlandite and pyrite treated with sodium butyl xanthate solution were systematically studied. The products of xanthate adsorpted on the three different minerals were characterized by comparing their FTIR spectra to those of dixanthogen and metal xanthate. Both metal xanthate and dixanthogen are formed on the surfaces of these minerals. However, the relative proportions of metal xanthate to dixanthogen on the minerals are different. In the cases of chalcopyrite and pentlandite, the quantity of metal xanthate is larger than that of dixanthogen. For pyrite, on the contrary, the quantity of dixanthogen is much greater than that of ferric xanthate. Therefore, the formation of dixanthogen is more essential for the flotation of pyrite.
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 fugacities from stage A to stage B, while temperature and oxygen fugacities decrease from stage B to stage C. The Co/Ni ratio of pyrite depends discriminates between the different mineralizing stages in the Yuleken porphyry copper deposit: Py II, associated with the deformation stage B and Cu-enrichment, shows higher Co/Ni ratios and enrichments of Pb, Zn, Mo, Te and Sb than the pyrites formed during the other two stages. The Co/Ni ratio of pyrite can not only apply to discriminate the submarine exhalative, magmatic or sedimentary origins for ore deposits but also can distinguish different ore-forming stages in a single porphyry Cu deposit. Thus, Co/Ni ratio of pyrites may act as an important exploration tool to distinguish pyrites from Cu-rich versus barren area. Furthermore, the distribution of Cu, Mo, Pb, Au, Bi, Sb and Zn in the variably deformed pyrite is proportional to the extent of deformation of the pyrites, indicating in accordance with variable physicochemical conditions different element migration behavior during the different stages of deformation and, thus, mineralisation.
Code of Federal Regulations, 2011 CFR
2011-04-01
..., DEPARTMENT OF THE INTERIOR EDUCATION ADEQUATE YEARLY PROGRESS Defining Adequate Yearly Progress Technical Assistance § 30.110 What is the process for requesting technical assistance to develop an alternative... 25 Indians 1 2011-04-01 2011-04-01 false What is the process for requesting technical assistance...
Code of Federal Regulations, 2010 CFR
2010-04-01
... 25 Indians 1 2010-04-01 2010-04-01 false What is the process for requesting technical assistance..., DEPARTMENT OF THE INTERIOR EDUCATION ADEQUATE YEARLY PROGRESS Defining Adequate Yearly Progress Technical Assistance § 30.110 What is the process for requesting technical assistance to develop an alternative...
Chen, Lei; Li, Xian-hua; Li, Jian-wei; Hofstra, Albert H.; Liu, Yu; Koenig, Alan E.
2015-01-01
High spatial resolution textural (scanning electron microscope (SEM)), chemical (electron microprobe (EMP)) and laser ablation-inductively coupled plasma-mass spec- trometry (LA-ICP-MS)), and sulfur isotopic (secondary ion mass spectrometry (SIMS)) analyses of pyrite from the Qiuling sediment-hosted gold deposit (232±4 Ma) in the West Qinling orogen, central China were conducted to distinguish pyrite types and gain insights into the source and evolution of sulfur in hydrothermal fluids. The results reveal an enormous variation (−27.1 to +69.6‰) in sulfur isotopic composition of pyrite deposited during three paragenetic stages. Pre-ore framboidal pyrite, which is characterized by low concentra- tions of As, Au, Cu, Co, and Ni, has negative δ34S values of −27.1 to −7.6‰ that are interpreted in terms of bacterial re- duction of marine sulfate during sedimentation and diagenesis of the Paleozoic carbonate and clastic sequences, the predom- inant lithologies in the deposit area, and the most important hosts of many sediment-hosted gold deposits throughout the West Qinling orogen. The ore-stage hydrothermal pyrite con- tains high concentrations of Au, As, Cu, Sb, Tl, and Bi and hasa relatively narrow range of positive δ34S values ranging from +8.1 to +15.2‰. The sulfur isotope data are comparable to those of ore pyrite from many Triassic orogenic gold deposits and Paleozoic sedimentary exhalative (SEDEX) Pb-Zn de- posits in the West Qinling orogen, both being hosted mainly in the Devonian sequence. This similarity indicates that sulfur, responsible for the auriferous pyrite at Qiuling, was largely derived from the metamorphic devolatization of Paleozoic marine sedimentary rocks. Post-ore-stage pyrite, which is sig- nificantly enriched in Co and Ni but depleted in Au and As, has unusually high δ34S values ranging from +37.4 to +69.6 ‰, that are interpreted to result from thermochemical reduc- tion of evaporite sulfates in underlying Cambrian sedimentary rocks with very high δ34S values. The variations in Au content and sulfur isotopic compositions across a single ore-stage py- rite grain may reflect displacement of indigenous groundwater with low δ34S values by auriferous metamorphic fluids with high δ34S values. The very low-grade metamorphism of the host rocks and the metamorphic derivation of sulfur for the ore pyrite indicate that the Qiuling sediment-hosted gold deposit is an epizonal manifestation of an orogenic gold system in the West Qinling orogen.
The mechanisms of pyrite oxidation and leaching: A fundamental perspective
NASA Astrophysics Data System (ADS)
Chandra, A. P.; Gerson, A. R.
2010-09-01
Pyrite is the earth's most abundant sulfide mineral. Its frequent undesirable association with minerals of economic value such as sphalerite, chalcopyrite and galena, and precious metals such as gold necessitates costly separation processes such as leaching and flotation. Additionally pyrite oxidation is a major contributor to the environmental problem of acid rock drainage. The surface oxidation reactions of pyrite are therefore important both economically and environmentally. Significant variations in electrical properties resulting from lattice substitution of minor and trace elements into the lattice structure exist between pyrite from different geographical locations. Furthermore the presence of low coordination surface sites as a result of conchoidal fracture causes a reduction in the band gap at the surface compared to the bulk thus adding further electrochemical variability. Given the now general acceptance after decades of research that electrochemistry dominates the oxidation process, the geographical location, elemental composition and semi-conductor type (n or p) of pyrite are important considerations. Aqueous pyrite oxidation results in the production of sulfate and ferrous iron. However other products such as elemental sulfur, polysulfides, hydrogen sulfide, ferric hydroxide, iron oxide and iron(III) oxyhydroxide may also form. Intermediate species such as thiosulfate, sulfite and polythionates are also proposed to occur. Oxidation and leach rates are generally influenced by solution Eh, pH, oxidant type and concentration, hydrodynamics, grain size and surface area in relation to solution volume, temperature and pressure. Of these, solution Eh is most critical as expected for an electrochemically controlled process, and directly correlates with surface area normalised rates. Studies using mixed mineral systems further indicate the importance of electrochemical processes during the oxidation process. Spatially resolved surface characterisation of fresh and reacted pyrite surfaces is needed to identify site specific chemical processes. Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) are two synchrotron based surface spectromicroscopic and microspectroscopic techniques that use XPS- and XANES-imaging to correlate chemistry with topography at a submicron scale. Recent data collected with these two techniques suggests that species are heterogeneously distributed on the surface and oxidation to be highly site specific.
14 CFR 1274.701 - Suspension or termination.
Code of Federal Regulations, 2010 CFR
2010-01-01
... Agreement if the recipient is not making anticipated technical progress, if the recipient materially changes...) Similarly, the recipient may terminate the agreement if, for example, technical progress is not being made, if the commercial recipient shifts its technical emphasis, or if other technological advances have...
14 CFR 1274.701 - Suspension or termination.
Code of Federal Regulations, 2011 CFR
2011-01-01
... Agreement if the recipient is not making anticipated technical progress, if the recipient materially changes...) Similarly, the recipient may terminate the agreement if, for example, technical progress is not being made, if the commercial recipient shifts its technical emphasis, or if other technological advances have...
In situ characterization of natural pyrite bioleaching using electrochemical noise technique
NASA Astrophysics Data System (ADS)
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.
Post-pyrite transition in SiO2
NASA Astrophysics Data System (ADS)
Ho, K.; Wu, S.; Umemoto, K.; Wentzcovitch, R. M.; Ji, M.; Wang, C.
2010-12-01
Here we propose a new phase of SiO2 beyond the pyrite-type phase. SiO2 is one of the most important minerals in Earth and planetary sciences. So far, the pyrite-type phase has been identified experimentally as the highest-pressure form of SiO2. In solar giants and extrasolar planets whose interior pressures are considerably higher than that on Earth, a post-pyrite transition in SiO2 may occur at ~ 1 TPa as a result of the dissociation of MgSiO3 post-perovskite into MgO and SiO2 [Umemtoto et al., Science 311, 983 (2006)]. Several dioxides considered to be low-pressure analogs of SiO2 have a phase with cotunnite-type (PbCl2-type) structure as the post-pyrite phase. However, a first-principles structural search using a genetic algorithm shows that SiO2 should undergo a post-pyrite transition to a hexagonal phase, not to the cotunnite phase. The hexagonal phase is energetically very competitive with the cotunnite-type one. This work was supported by the U.S. Department of Energy, Office of Basic Energy Science, Division of Materials Sciences and Engineering and NSF under ATM-0428774 (VLab), EAR-0757903, and EAR-1019853. Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DE-AC02-07CH11358. The computations were performed at the National Energy Research Supercomputing Centre (NERSC) and the Minnesota Supercomputing Institute (MSI).
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.
Castro, Camila; Zhang, Ruiyong; Liu, Jing; Bellenberg, Sören; Neu, Thomas R; Donati, Edgardo; Sand, Wolfgang; Vera, Mario
2016-09-01
The understanding of biofilm formation by bioleaching microorganisms is of great importance for influencing mineral dissolution rates and to prevent acid mine drainage (AMD). Thermo-acidophilic archaea such as Acidianus, Sulfolobus and Metallosphaera are of special interest due to their ability to perform leaching at high temperatures, thereby enhancing leaching rates. In this work, leaching experiments and visualization by microscopy of cell attachment and biofilm formation patterns of the crenarchaeotes Sulfolobus metallicus DSM 6482(T) and the Acidianus isolates DSM 29038 and DSM 29099 in pure and mixed cultures on sulfur or pyrite were studied. Confocal laser scanning microscopy (CLSM) combined with fluorescent dyes as well as fluorescently labeled lectins were used to visualize different components (e.g. DNA, proteins or glycoconjugates) of the aforementioned species. The data indicate that cell attachment and the subsequently formed biofilms were species- and substrate-dependent. Pyrite leaching experiments coupled with pre-colonization and further inoculation with a second species suggest that both species may negatively influence each other during pyrite leaching with respect to initial attachment and pyrite dissolution rates. In addition, the investigation of binary biofilms on pyrite showed that both species were heterogeneously distributed on pyrite surfaces in the form of individual cells or microcolonies. Physical contact between the two species seems to occur, as revealed by specific lectins able to specifically bind single species within mixed cultures. Copyright © 2016 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.
NASA Astrophysics Data System (ADS)
Mason, P. R. D.; Roerdink, D. L.; Galic, A.; Martin, W.
2014-12-01
The Archean oceans are thought to have been depleted in sulfate, reflecting widespread anoxic conditions and limited input of oxidized sulfur species from atmospheric photolysis. This is supported by the paucity of sulfate-bearing minerals and the relatively limited mass-dependent sulfur isotope fractionation in the majority of the Archean geological record. An exception to this is the occurrence of barite deposits in the Palaeoarchean (3.5-3.2 Ga) which indicate spatial or temporal increases in sulfate concentration. The origin and extent of these enrichments remains controversial and has been difficult to assess due to limited and highly variable data. Here we compile an extensive new database of SIMS multiple sulfur isotope data for pyrite and barite from across the Barberton Greenstone Belt in South Africa in order to further investigate the extent and origin of any sulfate enrichment. Individual pyrites were measured with good stratigraphic and petrographic control. Pyrite δ56Fe was used to further delineate pyrite populations and pathways of pyrite formation. Our new sulfur isotope data support conventional models where a positive Δ33S was derived from heterogeneous photolytic elemental S, with negative Δ33S capturing a homogenized marine sulfate reservoir. Pyrite multiple S isotope data closely track the abundance of barite, suggesting that marine sulfate levels were generally low and that sulfate increases were sporadic and localized. We speculate that the subsequent Neoarchean scarcity was controlled by biological evolution.
Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.
1987-01-01
A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 ??C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 ??C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur. ?? 1987.
Oxidation of pyrite in an anoxic atmosphere
Thorpe, A.N.; Senftle, F.E.; Alexander, Corrine; Dulong, F.T.; LaCount, R.B.; Friedman, S.
1987-01-01
Pyrite (FeS2) inclusions in coal, when heated in an oxygen deficient atmosphere (approximately 1% oxygen), become coated with magnetic Fe3O4 due to oxidation. Most of the FeS2 can thus be removed from the coal by magnetic separation to reduce the sulphur concentration. The oxidation products have been studied in greater detail by measuring the SO2 and O2 in the effluent gas during the heating process and by performing further magnetic measurements. At 582 K, the pyrite surface was oxidized to FeSO4. Significant oxidation of FeSO4 and FeS2 to Fe3O4 was observed starting at 677 K. At about 681 K, the Fe3O4 is further oxidized to ??-Fe2O3. At 681 K, under isothermal conditions, the oxidation is impeded by the ??-Fe2O3 formed on the surfaces of the grains. If the temperature is rapidly increased, the oxygen penetrates the ??-Fe2O3 veneer to the FeS2 core of the pyrite grains and oxidizes essentially the whole pyrite mass to Fe3O4 before ??-Fe2O3 can be formed. ?? 1987.
Phase equilibria in the KFeS2-Fe-S system at 300-600 °C and bartonite stability
NASA Astrophysics Data System (ADS)
Osadchii, Valentin O.; Voronin, Mikhail V.; Baranov, Alexander V.
2018-05-01
The article deals with phase relations in the KFeS2-Fe-S system studied by the dry synthesis method in the range of 300-600 °C and at a pressure of 1 bar. At the temperature below 513 ± 3 °C, pyrite coexists with rasvumite and there are pyrite-rasvumite-KFeS2 and pyrite-rasvumite-pyrrhotite equilibria established. Above 513 ± 3 °C pyrite and rasvumite react to form KFeS2 and pyrrhotite, limiting the pyrite-rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K x Fe2- y S2) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K-Fe-S-Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium-iron sulfides in nature were discussed.
Progress in Scientific and Technical Communications, 1968 Annual Report.
ERIC Educational Resources Information Center
Federal Council for Science and Technology, Washington, DC. Committee on Scientific and Technical Information.
This sixth annual report describes progress achieved by the Federal Government in improving the communication of scientific and technical information to support and enhance national science and technology. Included in the report are details regarding the scientific and technical activities of individual Federal Agencies, such as the Atomic Energy…
NASA Astrophysics Data System (ADS)
Lebrun, Erwann; Thébaud, Nicolas; Miller, John; Roberts, Malcolm; Evans, Noreen
2017-04-01
Siguiri is a world-class orogenic gold district hosted in the weakly metamorphosed Upper Birimian to Lower Tarkwa Group sedimentary rocks of the Siguiri Basin (Guinea). The district is characterised by a protracted deformation history associated with four main deformation events: D1S is a N-S compression; D2S is an E-W compression progressively evolving into an early-D3S transpression and then into a late-D3S NNW-SSE transtension and D4S is a NE-SW compression. Field observations, petrography and geochemistry at three key deposits of the Siguiri district (Bidini, Sintroko PB1 and Kosise) suggest a polyphase hydrothermal history that can be subdivided into four hydrothermal events. The first hydrothermal event was associated with the development of barren bedding-parallel and en-echelon V2S quartz-dominated-(pyrite) veins. The second hydrothermal event is characterised by the development of V3A pyrite-ankerite veins late during D3S. Laser ablation-ICP-MS data show that this vein set contains high gold contents of up to 43.3 ppm, in substitution in pyrite crystal lattice, representing a minor first gold mineralisation event. The third and most prominently developed hydrothermal event is late D3S and represents the second and principal gold mineralisation event. This mineralisation event led to two distinct mineralisation textures. The first texture is best exposed in the Kosise deposit and is characterised by gold-bearing quartz-ankerite-arsenopyrite conjugate V3B veins. Although the bulk of the gold is hosted in native gold grains in V3B veins, LA-ICP-MS analyses show that gold also substitutes in the arsenopyrite crystal lattice (up to 55.5 ppm). The second mineralisation texture is best expressed in the Sanu Tinti deposit and consists of disseminated barren pyrite hosted in a polymict conglomerate. The second and third hydrothermal events are both structurally controlled by a series of early-D3S N-S, NE-SW, WNW-ESE and E-W sub-vertical incipient structures expressed as fracture zones of higher V3S vein density. A composite geochemical cross section across fracture zones from the Kosise deposit indicates that gold mineralisation in the Siguiri district is associated with enrichments in Ag, Au, As, Bi, Co, Mo, (Sb), S, Te and W relative to background. Geochemical variations associated with the ore shoots in the Siguiri district are consistent with petrographic observations and highlight an albite-carbonate-sulphide-sericite alteration. The fourth and last hydrothermal event is associated with the development of a late penetrative S4S cleavage during D4S deformation, which overprints all pre-existing hydrothermal features and is associated with the deposition of free gold, chalcopyrite and galena along fractures in V3A pyrite and V3B pyrite and arsenopyrite. Mineralogical and geochemical footprints as well as timing of the gold-mineralising events in the Siguiri district, when compared with other deposits of the West African Craton, highlight the synchronicity of gold mineralisation in Siguiri (syn-D3S and syn-D4S events) with other similar events in this part of the craton, such as the early Au-Sb-Bi-(Te-W) mineralisation at the Morila deposit in Southeast Mali. Our results support the hypothesis that late Eburnean-age gold mineralisation in the Siguiri district and in the West African Craton as a whole was polyphase.
Pollastro, R.M.
1981-01-01
Cores from the Smoky Hill Chalk Member of the Cretaceous Niobrara Formation have several zones containing authigenic kaolinite as spherical, moldic, polycrystalline aggregates that occur within single or multichambered foraminiferal tests and are commonly associated with framboidal pyrite. Such kaolinite is inferred to result from volcanic ash deposited during chalk sedimentation. Shortly after burial, a colloidal aluminous gel or solution formed from the unstable ash and moved into organic-rich foraminiferal tests, where sulfate-reducing bacteria created a favorable microenvironment for the simultaneous crystallization of kaolinite and pyrite. -Author
Romar-Gasalla, Aurora; Santás-Miguel, Vanesa; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino; Fernández-Sanjurjo, María J
2018-05-22
Using batch-type experiments, chromium (Cr(VI)) and fluoride (F - ) sorption/desorption were studied in forest and vineyard soil samples, pyritic material, pine bark, oak ash, hemp waste and mussel shell, as well as on samples of forest and vineyard soil, and of pyritic material, individually treated with 48 t ha -1 of pine bark, oak ash, and mussel shell. Pine bark showed the highest Cr(VI) sorption (always > 97% of the concentration added) and low desorption (<1.5%). Pyritic material sorbed between 55 and 98%, and desorbed between 0.6 and 9%. Forest and vineyard soils, oak ash, mussel shell and hemp waste showed Cr(VI) sorption always < 32%, and desorption between 22 and 100%. Pine bark also showed the highest F - retention (sorption between 62 and 73%, desorption between 10 and 15%), followed by oak ash (sorption 60-69%, desorption 11-14%), forest soil (sorption 60-73%, desorption 19-36%), and pyritic material (sorption 60-67%, desorption 13-15%), whereas in vineyard sorption was 49-64%, and desorption 24-27%, and in hemp waste sorption was 26-36%, and desorption 41-59%. Sorption data showed better fitting to the Freundlich than to the Langmuir model, especially in the case of Cr(VI), indicating that multilayer sorption dominated. The addition of by-products to the forest and vineyard soils, and to the pyritic material, caused an overall increase in F - sorption, and decreased desorption. Furthermore, the pine bark amendment resulted in increases in Cr(VI) retention by both soils and the pyritic material. These results could be useful to favor the recycling of the by-products studied, aiding in the management of soils and degraded areas affected by Cr(VI) and F - pollution, and in the removal of both anions from polluted waters. Copyright © 2018 Elsevier Ltd. All rights reserved.
Geology of the Wood and East Calhoun mines, Central City District, Gilpin County, Colorado
Drake, Avery Ala
1955-01-01
The Wood-East Calhoun mine area is underlain by complexly folded Precambrian gneiss and pegmatite. The major fold in the area is an anticline that trends about N. 60° E. The Precambrian rocks are intruded by bostonite porphyry dikes of Tertiary age. All the rocks are cut by east- to northeast - trending faults that have been filled by precious metal-sulfide veins which have been worked chiefly for gold. The Wood vein occurs in an east-trending fault; the Calhoun vein occurs in a northeast-trending fault. Much of the uranium production of the Central City district has come from the Wood vein on Quartz Hill. The veins consist chiefly of quartz; pyrite is the chief metallic mineral and chalcopyrite is next in abundance. Sphalerite, galena, tetrahedrite-tennantite, and pitchblende are locally present. Deposition began with alteration-stage quartz and pyrite followed in order by pitchblend, light-yellow pyrite, massive quartz, yellow pyrite, shalerite, comb quartz, chalcopyrite, tetrahedrite-tennantite, galena, chalcopyrite, pyrite, and gray to light-brown fine-grained quartz. The veins of the Central City district are zoned, with quartz-pyrite veins near the center and galena-sphalerite veins on the periphery. The known pitchblende bodies are in the transition between these, but paragenetically, the pitchblende is earlier than all other metallic minerals. A trace element study of the ore indicates an association of zirconium and molybdenum with uranium, of bismuth, antimony, and arsenic with copper, and of cadmium with zinc. The pitchblende and other ore minerals are concentrated in ore shoots. The shoots are in open spaces controlled by the competency of the wall rocks, the presence of a prevailing direction of weakness in the rocks, and changes in strike and dip of the vein. The pitchblende is thought to be a local constituent of the quartz-pyrite ores and to owe its origin to residual solutions from the quartz bostonite magma.
Barahona, Sergio; Dorador, Cristina; Zhang, Ruiyong; Aguilar, Pablo; Sand, Wolfgang; Vera, Mario; Remonsellez, Francisco
2014-11-01
Microorganisms are used to aid the extraction of valuable metals from low-grade sulfide ores in mines worldwide, but relatively little is known about this process in cold environments. This study comprises a preliminary analysis of the bacterial diversity of the polyextremophilic acid River Aroma located in the Chilean Altiplano, and revealed that Betaproteobacteria was the most dominant bacterial group (Gallionella-like and Thiobacillus-like). Taxa characteristic of leaching environments, such Acidithiobacillus and Leptospirillum, were detected at low abundances. Also, bacteria not associated with extremely acidic, metal-rich environments were found. After enrichment in iron- and sulfur-oxidizing media, we isolated and identified a novel psychrotolerant Acidithiobacillus ferrivorans strain ACH. This strain can grow using ferrous iron, sulfur, thiosulfate, tetrathionate and pyrite, as energy sources. Optimal growth was observed in the presence of pyrite, where cultures reached a cell number of 6.5 · 10(7) cells mL(-1). Planktonic cells grown with pyrite showed the presence of extracellular polymeric substances (10 °C and 28 °C), and a high density of cells attached to pyrite grains were observed at 10 °C by electron microscopy. The attachment of cells to pyrite coupons and the presence of capsular polysaccharides were visualized by using epifluorescence microscopy, through nucleic acid and lectin staining with Syto(®)9 and TRITC-Con A, respectively. Interestingly, we observed high cell adhesion including the formation of microcolonies within 21 days of incubation at 4 °C, which was correlated with a clear induction of capsular polysaccharides production. Our data suggests that attachment to pyrite is not temperature-dependent in At. ferrivorans ACH. The results of this study highlight the potential of this novel psychrotolerant strain in oxidation and attachment to minerals under low-temperature conditions. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.
48 CFR 2452.242-71 - Contract management system.
Code of Federal Regulations, 2011 CFR
2011-10-01
..., concise summary of technical progress made and the costs incurred for each task during the reporting... technical progress made for each task during the reporting period; and (B) Identifies problems, or potential... and progress reporting as described herein. (b) The contract management system shall consist of two...
Minkin, J.A.; Finkelman, R.B.; Thompson, C.L.; Chao, E.C.T.; Ruppert, L.F.; Blank, H.; Cecil, C.B.
1984-01-01
Optical and scanning electron microscope as well as electron and proton microprobe techniques have been used in a detailed investigation of the modes of occurrence of arsenic and selenium in pyrite in Upper Freeport coal from the Homer City area, Indiana County, Pennsylvania. Polished blocks were prepared from columnar samples of the coal bed to represent particular zones continuously from top to bottom. Initial selection of zones to be studied was based on chemical analysis of bench-channel samples. Microprobe data indicate that the highest concentrations of arsenic (as great as 1. 5 wt. %) are apparently in solid solution in pyrite within a limited stratigraphic interval of the coal bed. Smaller amounts of arsenic and selenium (concentrations up to approximately 0. 1 and 0. 2 wt. % respectively) were detected at isolated points within pyrite grains in various strata of the coal bed.
Iron disulfide minerals and the genesis of roll-type uranium deposits.
Reynolds, R.L.; Goldhaber, M.B.
1983-01-01
Studies of the distribution of and textural relationships among pyrite and marcasite in host rocks for a number of roll-type sedimentary U deposits have enabled identification of several generations of FeS2 minerals. A critical factor influencing mineral formation is the complex relationship of pH and the S species that are precursors of FeS2 minerals. The presence or absence of intrinsic organic matter for bacterial sulphate reduction also plays a key role. In deposits lacking such organic matter, the pre-ore is often euhedral pyrite and the ore-stage is marcasite. In contrast, in deposits containing organic matter the pre-ore is pyrite occurring as framboids or as replacements of plant material, and the ore-stage is also pyrite. These contrasting FeS2 assemblages and their respective modes of origin are consistent with previously proposed biogenic and nonbiogenic theories of the genesis of roll-type U deposits. -J.E.S.
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
1958-10-31
The progress and trends of research are presented along with a description of operational, service, end administrative activities. Some scientific and technical details are given on research programs in the physical sciences, life sciences, and engineering, however, more complete technical information is available in quarterly progress reports, BNL technical reports, and scientific and technical periodicals. A bibliography of these publications is appended. (For preceding period see BNL-426.) (D.E.B.)
NASA Astrophysics Data System (ADS)
El Makkaoui, Mohammed
Iron pyrite (cubic FeS2) is a non-toxic, earth abundant semiconductor possessing a set of excellent optical/electronic properties for serving as an absorber layer in PV devices. Additionally, pyrite is a very efficient hydroxyl radical generator via Fenton chemistry and has shown promise in oxidative protein and DNA foot-printing application. The main focus of this thesis is on fabricating phase and elementally pure iron pyrite thin films using a solution-based approach that employs hydrazine as a solvent. A precursor ink is formed at room temperature by mixing elemental iron and sulfur in anhydrous hydrazine and then deposited on Mo-coated glass substrates, via spin coating, to yield amorphous iron sulfide films that are then annealed in H2S (340°C) and sulfur gas (≤ 500 °C) to form uniform, polycrystalline and phase pure pyrite films with densely packed grains. This approach is likely to yield the most elementally pure pyrite thin films made to date, through a very simple and scalable process. The ink has shown to be very sensitive to environmental conditions and has a very short shelf life (˜1 day). Additionally, the film microstructure is greatly influenced by the S:Fe concentration ratio that when tuned to 3:1, yielded uniform, robust and optically flat iron sulfide thin films with an optimal thickness (˜320 nm) for PV application. The results however were not reproducible, mainly due to failure in applying multiple layers without compromising film morphology. Thinner (< 100 nm) iron sulfide films, on the other hand, are reproducibly produced, but are too thin to be employed in PV devices. Direct annealing in sulfur gas at 475°C for 4 hours, bypassing the > 12 hour H2S annealing step, yielded phase pure pyrite films, with good morphology, at lower processing time and annealing temperatures (< 500°C). The latter part of this thesis regards the use of pyrite nano-crystals in conjunction with high surface area polymer laminates for protein foot-printing application in collaboration with the Brenowitz lab at the Albert Einstein College of Medicine and the Khine lab at the University of California, Irvine. A thin film of pyrite nano-crystals is spray deposited (Video in supplementary ) onto a shape memory polymer that is then thermally treated with a heat gun, causing the sheet to retract and stiffen as the nanocrystalline layer crumples and integrates into the polyolefin, forming a mechanically robust and highly reactive laminate of pyrite nano-crystals. Micro-wells are thermoformed into the laminate under negative pressure. ˙OH dose-oxidation response relationship were established via varying the H2O 2 concentration and reaction time. The flexibility, cost effectiveness and scalability of this platform enables integration into macro-structural analysis systems. Pyrite shrink laminates and hydrazine ink films were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), and Raman Spectroscopy. Drop deposition oxidation experiments and MALDI-TOF "Matrix Assisted Laser Desorption/Ionization-Time of Flight" Mass Spectroscopy of protein aliquots reacted on PSWL were conducted in the Brenowitz lab at the department of biochemistry at the Albert Einstein College of Medicine in New York.
Biswas, Ashis; Hendry, M Jim; Essilfie-Dughan, Joseph
2017-02-01
This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO 4 2- in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91μg/L) and rock-drain effluent (median: 0.31μg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley. Copyright © 2016 Elsevier B.V. All rights reserved.
Assessing the impact of preload on pyrite-rich sediment and groundwater quality.
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.
NASA Astrophysics Data System (ADS)
Varol, Baki; Koşun, Erdal; Ünal Pinar, Neslihan; Ayranci, Korhan
2011-03-01
This paper is the first study of pyritized mudstones (PM) in the Permian-Triassic (P-T) boundary section of the Çürük Dağ (Taurus, Antalya Nappes, Turkey). The mudstones were generally formed as lensoidal-shaped layers or infill materials within nodular platform limestones (hardground). Normal marine fauna is diminished in the pyritized limestones, whereas tube-like microorganisms are apparently increased with the association of pyrite crystals consisting of both framboidal and cubic crystals. The total rock volumes are up to 50-60% clay minerals and are mainly made up of in situ kaolinite and subordinate mixed layer clays (illite-vermiculite). Kaolinite preferentially developed on feldspar crystals, sometimes covering ostracoda bivalves together with gypsum micronodules composed of fan-shaped gypsum crystals. The origin of the kaolinite is, in situ, directly related to feldspar dissolution via heterotrophic bacteria. Thus, kaolinite is found along with bacterial structures. Other mineralogical compositions include established quartz (mostly β-quartz), gypsum crystals (100-200 μm) glauconite and magnetite. Magnetite grains comprise a minor amount (1-2%) and show some bacterial-induced crystal orientations. Glauconite is formed as an accessory mineral that occurs as infill material in biogenic grains. On the other hand, some microspheres represented by a silica-dominated composition are only observed in scanning electron microscopes (SEM) studies under high magnification. Isotope values (d34S) obtained from the pyritized mudstones show an isotopic heterogeneity that suggests that the pyritized mudstone consists of at least two components, with different sulphur-concentrations and d34S values.
NASA Astrophysics Data System (ADS)
Passos, Tassia R. G.; Artur, Adriana G.; Nóbrega, Gabriel N.; Otero, Xosé L.; Ferreira, Tiago O.
2016-06-01
The performance of the Walkley-Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (CWB) was compared to that assessed by means of a standard elemental analyzer (CEA) for surficial samples (<30 cm depth) from the three wetland settings. The pyrite fraction was quantified in various steps of the chemical oxidation method, evaluating the effects of pyrite oxidation. Regardless of the method used, and consistent with site-specific physicochemical conditions, higher pyrite and SOC contents were recorded in the mangroves, whereas lower values were found in the other settings. CWB values were higher than CEA values. Significant differences in SCS calculations based on CWB and CEA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the CWB and CEA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.
20 CFR 411.180 - What is timely progress toward self-supporting employment?
Code of Federal Regulations, 2010 CFR
2010-04-01
... certificate or vocational or technical training that will enhance your ability to return to work. In addition...-secondary education requirement or vocational or technical training requirement in the applicable progress... this 12-month period; or (iv) You must have been enrolled in a vocational or technical training program...
Brown, Craig J.; Rakovan, John; Schoonen, Martin A.A.
2000-01-01
Abundance and distribution of iron-bearing and other heavy minerals in sediments of Long Island, N.Y., were examined to identify sources and sinks of dissolved iron and other ground-water constituents along a deep flow path from the ground-water divide to the southern shore along the Nassau-Suffolk County border. The occurrence and reactivity of many iron-bearing minerals in the aquifer system are affected by terminal electron-accepting processes, which are a function of depth below land surface, distance from the ground-water divide, and organic-matter content of the sediment. The lateral distribution of heavy minerals within lithologic sediments is not uniform throughout Long Island, or even along the 30-kilometer study section at the Nassau-Suffolk County border. Mineralogy and mineral abundance in Pleistocene units differ from those in Cretaceous sediments, and some of the trends vary with depth as well as from north to south. Major heavy minerals in the Cretaceous sediments at the study sites include pyrite, marcasite, muscovite, leucoxene, ilmenite, rutile, staurolite, chloritoid, and aluminosilicates (Al2SiO5); those in the overlying Pleistocene deposits at one site include iron oxides, leucoxene, zircon, garnet, ilmenite, aluminosilicates, and hornblende. Pyrite, marcasite, garnet, hornblende, and tourmaline were found locally in the Cretaceous sediments. Pyrite and marcasite were detected less frequently in borehole samples from near the ground-water divide, where the ground water is generally oxic, than in those from near the southern shore of Long Island, but were found in sulfate- reducing zones throughout the Magothy aquifer. Glauconite was present in Cretaceous and Pleistocene deposits, but only in the marine or transitional units. The most abundant and potentially reactive of the iron-bearing minerals found were iron (hydr)oxides, leucoxene, glauconite, chlorite, pyrite, and marcasite. The presence and morphology of pyrite and marcasite can be indicative of the microbial and geochemical environments. Pyrite generally was found in association with lignite or as interstitial cement. Marcasite was found as interstitial cement and is associated with the oxidation of iron-sulfide minerals upgradient. Pyrite crystals were octahedral, cubic, cubo-octahedral, and framboidal, and many samples showed more than one generation of crystal growth. Marcasite cement, which consisted of platey crystals in most samples, probably forms only under nonmarine conditions.
Constraining Δ33S signatures of Archean seawater sulfate with carbonate-associated sulfate
NASA Astrophysics Data System (ADS)
Peng, Y.; Bao, H.; Bekker, A.; Hofmann, A.
2017-12-01
Non-mass dependent sulfur isotope deviation of S-bearing phases in Archean sedimentary strata, and expressed as Δ33S, has a consistent pattern, i.e., sulfide (pyrite) predominantly bear positive Δ33S values, while Paleoarchean sulfate (barite) has negative Δ33S values. This pattern was later corroborated by observations of negative Δ33S values in Archean volcanogenic massive sulfide deposits and negative Δ33S values in early diagenetic nodular pyrite with a wide range of δ34S values, which is thought to be due to microbial sulfate reduction. These signatures have provided a set of initial conditions for a mechanistic interpretation at physical chemistry level. Unlike the younger geological times when large bodies of seawater evaporite deposits are common, to expand seawater sulfate records, carbonate-associated sulfate (CAS) was utilized as a proxy for ancient seawater sulfate. CAS extracted from the Archean carbonates carries positive Δ33S values. However, CAS could be derived from pyrite oxidation following exposure to modern oxidizing conditions and/or during laboratory extraction procedures. It is, therefore, important for us understanding context of the overall early earth atmospheric condition to empirically confirm whether Archean seawater sulfate was generally characterized by negative Δ33S signatures. Combined δ18O, Δ17O, δ34S, and Δ33S analyses of sequentially extracted water-leachable sulfate (WLS) and acid-leachable sulfate (ALS = CAS) and δ34S and Δ33S analyses of pyrite can help to identify the source of extracted sulfate. We studied drill-core samples of Archean carbonates from the 2.55 Ga Malmani and Campell Rand supgroups, South Africa. Our preliminary results show that 1) neither WLS nor ALS were extracted from samples with extremely low pyrite contents (less than 0.05 wt.%); 2) extractable WLS and ALS is present in samples with relatively high pyrite contents (more than 1 wt.%), and that δ34S and Δ33S values of WLS, ALS, and pyrite are similar; 3) δ18O and Δ17O values of WLS and ALS are negative and close to 0 ‰ V-SMOW, respectively. Our study indicates that ALS (=CAS) extractable from Archean carbonates is mostly derived from pyrite oxidation. Therefore, up to date, whether Archean seawater sulfate carried positive Δ33S values remains conjectural.
Investigating the formation of acid mine drainage of Toledo pyrite concentrate using column cells
NASA Astrophysics Data System (ADS)
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.
Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik
2018-01-01
A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.
Lara, René H; García-Meza, J Viridiana; Cruz, Roel; Valdez-Pérez, Donato; González, Ignacio
2012-08-01
Massive pyrite (FeS₂) electrodes were potentiostatically modified by means of variable oxidation pulse to induce formation of diverse surface sulfur species (S(n)²⁻, S⁰). The evolution of reactivity of the resulting surfaces considers transition from passive (e.g., Fe(1-x )S₂) to active sulfur species (e.g., Fe(1-x )S(2-y ), S⁰). Selected modified pyrite surfaces were incubated with cells of sulfur-oxidizing Acidithiobacillus thiooxidans for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the attached cells density and their exopolysaccharides were analyzed by confocal laser scanning microscopy (CLMS) and atomic force microscopy (AFM) on bio-oxidized surfaces; additionally, S(n)²⁻/S⁰ speciation was carried out on bio-oxidized and abiotic pyrite surfaces using Raman spectroscopy. Our results indicate an important correlation between the evolution of S(n)²⁻/S⁰ surface species ratio and biofilm formation. Hence, pyrite surfaces with mainly passive-sulfur species were less colonized by A. thiooxidans as compared to surfaces with active sulfur species. These results provide knowledge that may contribute to establishing interfacial conditions that enhance or delay metal sulfide (MS) dissolution, as a function of the biofilm formed by sulfur-oxidizing bacteria.
Romar-Gasalla, Aurora; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Fernández-Sanjurjo, María J; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino
2018-05-13
Batch experiments were used to test P sorbent potential of soil samples, pyritic and granitic materials, mussel shell, mussel shell ash, sawdust, and slate waste fines for different pH and incubation times. Maximum P sorption varied in a wide range of pH: < 4 for pyritic material, 4-6 for forest soil, > 5 for slate fines, > 6 for shell ash, and pH 6-8 for mussel shell. P sorption was rapid (< 24 h) for forest soil, shell ash, pyritic material, and fine shell. On the opposite side, it was clearly slower for vineyard soil, granitic material, slate fines, pine sawdust, and coarse shell, with increased P sorption even 1 month later. For any incubation time, P sorption was > 90% in shell ash, whereas forest soil, pyritic material, and fine shell showed sorption rates approaching 100% within 24 h of incubation. These results could be useful to manage and/or recycle the sorbents tested when focusing on P immobilization or removal, in circumstances where pH changes and where contact time may vary from hours to days, thus aiding to diminish P pollution and subsequent eutrophication risks, promoting conservation and sustainability.
Lead distribution in Permo-Carboniferous coal from the North China Plate, China.
Kunli, Luo; Jidong, Lu; Lianwu, Chen
2005-02-01
The content and distribution of the lead in coal, gangue and the sulfur ball and the pyritic gangue of the Permo-Carboniferous in the North China Plate have been systematically studied (nearly 300 samples) in this paper. The Permo-Carboniferous coals in the North China Plate account for nearly 44.45% of total Chinese coal resources, and most of the steam coals in China come from the Permo-Carboniferous coals in the North China Plate. The result shows that lead content in the coal varied from 1.45 to 63.60 mg kg(-1), averaging 23.95 mg kg(-1); the lead content of the sulfur ball and the pyritic gangue in the coal seam ranges from 70.26-1060 mg kg(-1), with an average of 271.28 mg kg(-1); the lead content of the gangue is from 29.5 to 77.81 mg kg(-1), averaging at 40.77 mg kg(-1). The lead in the coal seam is mainly concentrated in the pyrite, such as sulfur ball, pyritic gangue or pyrite, and is the least concentrated in the organic of coal. The content of the lead has a direct ratio with the ash and the pyretic sulfur. Coal washing can reduce the content of the pyretic sulfur and the lead.
A mechanism for the production of hydroxyl radical at surface defect sites on pyrite
NASA Astrophysics Data System (ADS)
Borda, Michael J.; Elsetinow, Alicia R.; Strongin, Daniel R.; Schoonen, Martin A.
2003-03-01
A previous contribution from our laboratory reported the formation of hydrogen peroxide (H 2O 2) upon addition of pyrite (FeS 2) to O 2-free water. It was hypothesized that a reaction between adsorbed H 2O and Fe(III), at a sulfur-deficient defect site, on the pyrite surface generates an adsorbed hydroxyl radical (OH •). ≡Fe(III) + H 2O (ads) → ≡Fe(II) + OH •(ads) + H + The combination of two OH • then produces H 2O 2. In the present study, we show spectroscopic evidence consistent with the conversion of Fe(III) to Fe(II) at defect sites, the origin of H 2O 2 from H 2O, and the existence of OH • in solution. To demonstrate the iron conversion at the surface, X-ray photoelectron spectroscopy (XPS) was employed. Using a novel mass spectrometry method, the production of H 2O 2 was evaluated. The aqueous concentration of OH • was measured using a standard radical scavenger method. The formation of OH • via the interaction of H 2O with the pyrite surface is consistent with several observations in earlier studies and clarifies a fundamental step in the oxidation mechanism of pyrite.
S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides
Ono, Shuhei; Shanks, Wayne C.; Rouxel, O.J.; Rumble, D.
2007-01-01
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different ??33S (?????33S-0.515 ??34S) values of up to 0.04??? even if ??34S values are identical. Detection of such small ??33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006??? (2??). Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10??N, 13??N, and 21??S and Mid-Atlantic Ridge (MAR) 37??N yield ??33S values ranging from -0.002 to 0.033 and ??34S from -0.5??? to 5.3???. The combined ??34S and ??33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13??N and marcasite from MAR 37??N are in isotope disequilibrium not only in ??34S but also in ??33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low ??33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles. ?? 2006 Elsevier Inc. All rights reserved.
Composition and risk assessment of roasted pyrite ash from fertiliser production.
Gabarrón, M; Babur, O; Soriano-Disla, J M; Faz, A; Acosta, J A
2018-06-18
Pyrite ash is a residue from the roasting of pyrite ores to obtain sulphuric acid used in the fertiliser industry and its production is widely extended worldwide. The mismanagement of this waste may result in environmental and health damages due to its physico-chemical characteristics. The main objective of this study was to examine the physico-chemical and mineralogical composition of roasted pyrite ash from an abandoned fertiliser company, and to evaluate the environmental risk caused by the wind and water dispersion of metals posed by this waste. In order to achieve these objectives, a sequential extraction procedure and a physical fractionation into six size fractions: >100, 100-50, 50-20, 20-10, 10-2.5 and < 2.5 μm were applied. Results showed that pyrite ash is composed mainly of iron-oxides such as hematite (46%) and secondary minerals as anglesite and shows high concentrations of Pb (7464 mg kg -1 ), Zn (2663 mg kg -1 ) and Cu (585 mg kg -1 ). The highest Risk Assessment Code (RAC) values were found for Cd, Pb and Zn, bound to the more labile fractions. Conversely, Pb showed the lowest water solubility due to the covering effect provided by a coating of anglesite in the pyrite ash surface. Most of the metals were associated to both the coarsest (>100 μm) and the finest (2.5-10 μm) fractions, although none represented an environmental risk according to the ecological risk index results. However, 30% of the metals were bound to the respirable fraction (≤100 μm) posing a potential risk for human health and a high potential dispersion by wind to the surrounding areas. Copyright © 2018 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schlatterer, Joerg C., E-mail: joerg.schlatterer@einstein.yu.edu; Wieder, Matthew S.; Jones, Christopher D.
2012-08-24
Highlights: Black-Right-Pointing-Pointer RNA structure is mapped by pyrite mediated {sup {center_dot}}OH footprinting. Black-Right-Pointing-Pointer Repetitive experiments can be done in a powdered pyrite filled cartridge. Black-Right-Pointing-Pointer High {sup {center_dot}}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 ({sup {center_dot}}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{sub 2}) can produce sufficient {sup {center_dot}}OH tomore » 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 {sup {center_dot}}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 {sup {center_dot}}OH footprinting is a readily accessible approach to gleaning information about the architecture of small RNA molecules.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Iverson, C.H.; Coury, G.E.
1979-01-01
Progress to date in the development of a study of the application of the technologies of mechanical vapor recompression and falling film evaporators as applied to the beet sugar industry is reported. Progress is reported in the following areas: technical literature search and plant visitations of existing applications of VR/FFE.
Stainthorpe, A C
1989-02-05
The biological molecule responsible for the suppression of pyritic sulfur in fine coal simulated froth flotation treated with bacteria was identified. Protein was found to be the most effective agent in pyrite suppression of the three cell components (protein, lipid, and carbohydrate) assayed. Coal recovery and ash removal of the flotation process were only slightly reduced by this treatment. Other protein-containing materials were evaluated for their ability to suppress pyrite flotation. Whey was found to be the most cost-effective flotation additive of those assayed. The sulfur content of the whey-treated float was reduced by 84.0% in a synthetically prepared fractionated coal (10.7% sulfur), by a raw whey dosage of 20 microL/g coal. The inorganic sulfur component of a natural high sulfur coal fraction (10.9%) was completely depressed by this whey addition. The effect of particle size and pulp density upon the process were investigated.
Selective Sulfidation of Lead Smelter Slag with Pyrite and Flotation Behavior of Synthetic ZnS
NASA Astrophysics Data System (ADS)
Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Zhang, Tianfu; Qin, Wenqing
2016-08-01
The selective sulfidation of lead smelter slag with pyrite in the presence of carbon and Na salts, and the flotation behavior of synthetic ZnS were studied. The effects of temperature, time, pyrite dosage, Na salts, and carbon additions were investigated based on thermodynamic calculation, and correspondingly, the growth mechanism of ZnS particles was studied at high temperatures. The results indicated that the zinc in lead smelter slag was selectively converted into zinc sulfides by sulfidation roasting. The sulfidation degree of zinc was increased until the temperature, time, pyrite, and carbon dosages reached their optimum values, under which it was more than 95 pct. The growth of ZnS particles largely depended upon roasting temperature, and the ZnS grains were significantly increased above 1373 K (1100 °C) due to the formation of a liquid phase. After the roasting, the zinc sulfides generated had a good floatability, and 88.34 pct of zinc was recovered by conventional flotation.
NASA Astrophysics Data System (ADS)
Wu, Xudong; Wang, Yong; Bian, Liu; Shen, Ji
2016-09-01
Post-depositional reductive diagenesis usually results in partial or entire cleansing of the pristine palaeomagnetic signal, therefore, its intensity is important to be assessed for sediments that are in the purpose of retrieving palaeomagnetic information. Grain size, rock magnetic and geochemical studies on the entire core, along with scanning electron microscope observations and X-ray diffraction analyses for representative samples were carried out on a Holocene sediment core retrieved from the deep water part of Huguangyan maar lake (HGY), southeast China. The pristine magnetic mineral assemblage of the studied core is domianted by superparamagnetic (SP) and stable single domain titanomagnetite, and high coercivity minerals are not detectable. Based on down-core variations of the average grain size (MZ), total organic carbon (TOC), detrital elements (Al, Ti, Fe and Mn) and the concentration and mineralogy of magnetic minerals, the studied core could be divided into three subsections. The uppermost subsection is the least affected by diagenesis, with detrital titanomagnetite as the dominant magnetic mineral. This is owing to low TOC contents, but high detrital input generated by weak Asian summer monsoon intensity during the late Holocene. The intermediate subsection shows down-core progressively enhanced dissolution of detrital titanomagnetite, and concomitant formation of authigenic pyrite and siderite, which indicates down-core progressively enhanced diagenesis generated by down-core progressive increasing TOC content, but decreasing detrital input as the result of down-core progressively strengthened Asian summer monsoon intensity. The pristine magnetic mineral assemblage has been profoundly modified in the lowermost subsection. At certain positions of the lowermost subsection, detrital titanomagnetite has been even completely dissolved via diagenesis, giving place to authigenic pyrite and siderite. High TOC content, but low detrital input generated from strong Asian summer monsoon intensity during the early Holocene are accountable for intensive diagenesis in the lowermost subsection. Complete erasing of detrital magnetic input signal at certain positions of the lowermost subsection, and considerable formation of authigenic siderite indicate that palaeomagnetic records of the studied core have been significantly compromised. The studied core has relatively higher TOC content, lower detrital matter content, calmer sedimentary environments, and less DO available at its water-sediment interface than the cores retrieved at relatively shallower water depths, which all contribute to its relatively stronger diagenesis. Progressive thickening of the upper two subsections with increasing water depth is owing to progressive increase in sedimentation rate with increasing water depth, which is the key factor in determining the thickness of each diagenetic subsection of cores from HGY. It would be better that lake sediments for palaeomagnetic investigations collected at a water depth shallower than the depth of its thermocline.
Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt
NASA Astrophysics Data System (ADS)
Zoheir, Basem; Emam, Ashraf; Pitcairn, Iain K.; Boskabadi, Arman; Lehaye, Yann; Cooper, Matthew J.
2018-04-01
Trace element composition of sulfides and O, C, Sr and S isotopic data are assessed to constrain the evolution and potential fluid and metal sources of the Um Garayat gold deposit. Ore microscopy and BSE investigations of quartz veins show blocky arsenopyrite and pyrite replaced in part by pyrrhotite, chalcopyrite, sphalerite, galena, and gersdorffite. Free-milling gold occurs commonly in close association with the late sulfides, and along fractures in pyrite. On the other hand, recrystallized pyrite is disseminated in host metavolcaniclastic/metasedimentary rocks that commonly contain carbonaceous material. In situ LA-ICP-MS analysis of sulfides shows the recrystallized pyrite enriched in most trace elements, while blocky pyrite contains only some traces of arsenic. Detected concentrations of gold (up to 17 ppm) were only reported in arsenopyrite disseminated in quartz veins. The δ34S values of blocky pyrite and pyrrhotite in quartz veins define a narrow range (1.6 to 3.7‰), suggesting a homogenous sulfur source which is consistent with the dominantly mafic host rocks. The recrystallized pyrite has a distinctive sulfur isotope composition (δ34S - 9.3 to - 10.6‰), which is rather comparable to diagenetic sulfides. Hydrothermal carbonate in quartz veins and wallrock have nearly constant values of δ18O (10.5 to 11.9‰) and δ13C (- 4.2 to - 5.5‰). Based on constraints from mineral assemblages and chlorite thermometry, data of six samples indicate that carbonate precipitation occurred at 280 °C from a homogenous hydrothermal fluid with δ18OH2O 4.4 ± 0.7‰ and δ13C = 3.7 ± 0.8‰. Strontium isotope values of two samples (87Sr/86Sr = 0.7024 and 0.7025) are similar to the initial 87Sr/86Sr ratios of island arc metabasalts ( 710 Ma) in the South Eastern Desert. The generally homogenous sulfur, C, O, Sr isotope data are suggestive of metamorphogenic fluids, likely produced from dominantly mafic volcanic rocks at the greenschist-amphibolite facies transition.
25 CFR 30.109 - Will the Secretary provide assistance in developing an alternative AYP definition?
Code of Federal Regulations, 2011 CFR
2011-04-01
... EDUCATION ADEQUATE YEARLY PROGRESS Defining Adequate Yearly Progress Technical Assistance § 30.109 Will the... Bureau, shall provide technical assistance either directly or through contract to the tribal governing...
25 CFR 30.109 - Will the Secretary provide assistance in developing an alternative AYP definition?
Code of Federal Regulations, 2010 CFR
2010-04-01
... EDUCATION ADEQUATE YEARLY PROGRESS Defining Adequate Yearly Progress Technical Assistance § 30.109 Will the... Bureau, shall provide technical assistance either directly or through contract to the tribal governing...
Process for removal of hazardous air pollutants from coal
Akers, David J.; Ekechukwu, Kenneth N.; Aluko, Mobolaji E.; Lebowitz, Howard E.
2000-01-01
An improved process for removing mercury and other trace elements from coal containing pyrite by forming a slurry of finely divided coal in a liquid solvent capable of forming ions or radicals having a tendency to react with constituents of pyrite or to attack the bond between pyrite and coal and/or to react with mercury to form mercury vapors, and heating the slurry in a closed container to a temperature of at least about 50.degree. C. to produce vapors of the solvent and withdrawing vapors including solvent and mercury-containing vapors from the closed container, then separating mercury from the vapors withdrawn.
Formation and resulfidization of a South Texas roll-type uranium deposit
Goldhaber, Martin B.; Reynolds, Richard L.; Rye, Robert O.
1979-01-01
Core samples from a roll type uranium deposit in Live Oak County, south Texas have been studied and results are reported for Se, Mo, FeS2 and organic-carbon distribution, sulfide mineral petrology, and sulfur isotopic composition of iron-disulfide phases. In addition, sulfur isotopic compositions of dissolved sulfate and sulfide from the modern ground water within the ore bearing sand have been studied. The suite of elements in the ore sand and their geometric relationships throughout the deposit are those expected for typical roll-type deposits with well-developed oxidation-reduction interfaces. However, iron-disulfide minerals are abundant in the altered tongue, demonstrating that this interval has been sulfidized after mineralization (resulfidized or rereduced). Iron disulfide minerals in the rereduced interval differ mineralogically and isotopically from those throughout the remainder of the deposit. The resulfidized sand contains dominantly pyrite that is enriched in 34S, whereas the sand beyond the altered tongue contains abundant marcasite that is enriched in the light isotope, 32S. Textural relationships between pyrite and marcasite help to establish relative timing of iron disulfide formation. In reduced rock outside the altered tongue, three distinct generations of iron disulfide are present. The oldest of these generations consists largely of pyrite with lesser amounts of marcasite. A major episode of marcasite formation contemporaneous with ore genesis postdates the oldest pyrite generation but predates a younger pyrite generation. Resulfidization probably led to the final pyrite stage recognized beyond the altered tongue. Stable isotope data establish that the source of sulfur for the resulfidization was fault-leaked H2S probably derived from the Edwards Limestone of Cretaceous age which underlies the deposit. The deposit formed in at least two stages: (1) a pre-ore process of host rock sulfidization which produced disseminated pyrite as the dominant iron disulfide phase; and (2) an ore-stage process which led to the development of the uranium roll with emplacement of the characteristic suite of minor and accessory elements and which produced abundant isotopically light marcasite. The host rock was modified by a post-ore stage of resulfidization which precipitated isotopically heavy pyrite. Sulfur isotopic compositions of sulfide and sulfate present in modern ground water within the host sand differ greatly from sulfur isotopic composition of iron disulfides formed during the resulfidization episode. Iron disulfide minerals formed from the sulfur species of modern ground water have not been unequivocally identified.
Okita, P.M.; Shanks, Wayne C.
1992-01-01
Carbonate and sulfide minerals from the Molango, Mexico, and TaoJiang, China, Mn deposits display similar and distinctive ??34S and ??13C patterns in intervals of manganese carbonate mineralization. ??13C-values for Mn-bearing carbonate range from -17.8 to +0.5??? (PDB), with the most negative values occurring in high-grade ore zones that are composed predominantly of rhodochrosite. In contrast, calcite from below, within and above Mn-carbonate zones at Molango has ??13C???0??? (PDB). Markedly negative ??13C data indicate that a large proportion of the carbon in Mn-carbonates was derived from organic matter oxidation. Diagenetic reactions using MnO2 and SO2-4 to oxidize sedimentary organic matter were the principle causes of such 12C enrichment. Pyrite content and sulfide ?? 34S-values also show distinctive variations. In unmineralized rocks, very negative ??34S-values (avg. < -21??? CDT) and abundant pyrite content suggest that pyrite formed from diagenetic, bacteriogenic sulfate reduction. In contrast, Mn-bearing horizons typically contain only trace amounts of pyrite (e.g., <0.5 wt% S with ??34S-values 34S-enriched, in some cases to nearly the value for contemporaneous seawater. 34S-enriched pyrite from the Mn-carbonate intervals indicates sulfide precipitation in an environment that underwent extensive SO2-4 reduction, and was largely a closed system with regard to exchange of sulfate and dissolved sulfide with normal seawater. The occasional occurrence of 34S-depleted pyrite within Mn-carbonate zones dominated by 34S-enriched pyrite is evidence that closed-system conditions were intermittent and limited to local pore waters and did not involve entire sedimentary basins. Mn-carbonate precipitation may have occluded porosity in the surficial sediments, thus establishing an effective barrier to SO2-4 exchange with overlying seawater. Similar isotopic and mineralogic characteristics from both the Molango and TaoJiang deposits, widely separated in geologic time and space, suggest they were formed similarly by MnO2 precipitation at the margins of dysaerobic to anoxic marine basins. Mn-carbonate formed predominantly by early-diagenetic reduction of Mn-oxides via oxidation of organic matter in near-surface sediments. In addition to MnCO3 precipitation, organic matter oxidation reactions resulted in oxidation of FeS to Fe-oxides such as magnetite, maghemite and hematite. The latter process explains anomalously low pyrite content and abundant Fe-oxide minerals in ore zones dominated by rhodochrosite. ?? 1992.
Kolker, Allan; Senior, Connie L.; van Alphen, Chris; Koenig, Alan E.; Geboy, Nicholas J.
2017-01-01
Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm3, and the sink fraction for 2.0 g/cm3. Bulk analysis of the separates shows strong (R2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.
Bacterial and chemical oxidation of pyritic mine tailings at low temperatures
NASA Astrophysics Data System (ADS)
Elberling, Bo; Schippers, Axel; Sand, Wolfgang
2000-02-01
Microbial and chemical sulfide oxidation activity and oxygen consumption was investigated in the active layer of pyritic mine tailings at Nanisivik Mine, located in a permafrost area on Baffin Island in northern Canada. Samples of tailings were collected up to a depth of 60 cm in mid-August 1998 at 4 sites, for which the metabolic activity of sulfur- and iron-oxidizing leaching bacteria besides the chemical pyrite oxidation activity were measured on 39 tailings samples and 7 samples from a natural pyritic site by calorimetry. The tailings of varying age and water content were deposited under alkaline conditions. In situ oxygen uptake rates were measured at the tailings surface every third day, prior to sampling. In addition, cell counts of iron(II), sulfur, and thiosulfate oxidizing, lithotrophic bacteria and chemoorganotrophic microorganisms were determined quantitatively by the most-probable-number technique or by agar-plating. Results show consistent pyrite oxidation rates based on in situ oxygen uptake rates, and laboratory heat output measurements. Litho- and organotrophic bacteria were found in the tailings. Calorimetric measurements revealed that the present bacterial activity is responsible for approximately one third of the ongoing oxidation. Although leaching bacteria have previously been found in the Arctic, this study is the first to prove the significance of bacterial activity in the overall pollution resulting from tailings deposited in the Arctic.
Detachment of particulate iron sulfide during shale-water interaction
NASA Astrophysics Data System (ADS)
Emmanuel, S.; Kreisserman, Y.
2017-12-01
Hydraulic fracturing, a commonly used technique to extract oil and gas from shales, is controversial in part because of the threat it poses to water resources. The technique involves the injection into the subsurface of large amounts of fluid, which can become contaminated by fluid-rock interaction. The dissolution of pyrite is thought to be a primary pathway for the contamination of fracturing fluids with toxic elements, such as arsenic and lead. In this study, we use direct observations with atomic force microscopy to show that the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment of embedded pyrite grains. To simulate the way fluid interacts with a fractured shale surface, we also reacted rock samples in a flow-through cell, and used environmental scanning electron microscopy to compare the surfaces before and after interaction with water. Crucially, our results show that the flux of particulate iron sulfide into the fluid may be orders of magnitude higher than the flux of pyrite from chemical dissolution. This result suggests that mechanical detachment of pyrite grains could be the dominant mode by which arsenic and other inorganic elements are mobilized in the subsurface. Thus, during hydraulic fracturing operations and in groundwater systems containing pyrite, the transport of many toxic species may be controlled by the transport of colloidal iron sulfide particles.
Electrical Resistivity of natural Marcasite at High-pressures
NASA Astrophysics Data System (ADS)
Parthasarathy, Gopalakrishnarao
2013-06-01
Marcasite is considered to be a common iron sulfide in reducing Martian sediments and may enclose microbial remains during growth and hence study of marcasite may have significance in the search for fossil life on Mars. The high-pressure phase stability investigations of marcasite are useful in understanding the sulfide mineralogy of Martian surface, affected by meteorite impacts. The sulfides were characterized by electron microprobe micro analyses (EPMA), powder X-ray diffraction, DTA, and FTIR spectroscopic measurements. The samples were powdered using a porcelain mortar and pestle. The chemical composition of the sample was determined by an electron probe micro-analyzer (EPMA). High-pressure electrical resistivity measurements were carried out on natural marcasite, and marcasite rich samples (Marcasite 95 mol % pyrite 5 mol %) up to 7 GPa. Marcasite sample shows a discontinuous decrease in the electrical resistivity at 5. 2 (+/- 0.5) GPa indicating a first order phase transition. The Differential thermal analyses and the Fourier transform infrared spectroscopic measurements on the pressure quenched sample shows the characteristics of pyrite, indicating the pressure induced marcasite-to -pyrite transition of the natural marcasite at 5. 2 (+/- 0.5) GPa. The observation of marcasite to pyrite phase transition may be useful in estimating the pressure experienced by shock events on the Martian surface as well as the meteorites where marcasite- pyrite phases coexist. Financial support from CSIR-SHORE-PSC0205.
Sulfidation behavior and mechanism of zinc silicate roasted with pyrite
NASA Astrophysics Data System (ADS)
Ke, Yong; Peng, Ning; Xue, Ke; Min, Xiaobo; Chai, Liyuan; Pan, Qinglin; Liang, Yanjie; Xiao, Ruiyang; Wang, Yunyan; Tang, Chongjian; Liu, Hui
2018-03-01
Sulfidation roasting followed by flotation is widely known as a possible generic technology for enriching valuable metals in low-grade Zn-Pb oxide ores. Zn2SiO4 is the primary Zn phase in willemite. Zn4Si2O7(OH)2(H2O), the main Zn phase in hemimorphite, transforms into Zn2SiO4 at temperatures above 600 °C. To enrich the Zn in willemite and hemimorphite, the Zn species should first be converted to ZnS. Therefore, a thorough understanding of the sulfidation reaction of Zn2SiO4 during roasting with pyrite is of vital important. In this study, the sulfidation behavior and reaction mechanisms of a Zn2SiO4-pyrite roasting system were determined using HSC 5.0 software, TG-FTIR spectroscopy, XRD, XPS and SEM-EDS. The results indicate that the sulfidation process can be divided into three steps: the decomposition of pyrite and formation of a sulfur-rich environment, the sulfur-induced migration of O2- and transformation of sulfur vapor, and the sulfidation reaction via oxygen-sulfur exchange. During the sulfidation roasting process, pyrite was converted to loose and porous Fe3O4, whereas Zn2SiO4 was transformed into ZnS and SiO2 in situ. These findings provide theoretical support for controlling the sulfidation roasting process of willemite and hemimorphite.
Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants
Losa-Adams, Elisabeth; F.-Dávila, Alfonso; Gago-Duport, Luis
2014-01-01
Summary 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. PMID:24991522
Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants.
Gil-Lozano, Carolina; Losa-Adams, Elisabeth; F-Dávila, Alfonso; Gago-Duport, Luis
2014-01-01
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 Fe(3+) into Fe(2+) 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.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ulm, Franz-Josef
2000-03-31
OAK-B135 Monitoring the Durability Performance of Concrete in Nuclear Waste Containment. Technical Progress Report No. 3(NOTE: Part II A item 1 indicates ''PAPER'', but a report is attached electronically)
NASA Astrophysics Data System (ADS)
Osaliya, R.; Kansiime, F.; Oryem-Origa, H.; Kateyo, E.
During the operation of the Kilembe Mines (copper mining) a cobaltiferous stockpile was constructed, which began to erode after the closure of the mines in the early 1970s. The erosion of the pyrite stockpile resulted in a large acid trail all the way to Lake George (a Ramsar site). The acid trail contaminated a large area of Queen Elizabeth National Park (QENP) resulting in the death of most of the shallow-rooted vegetation. Processes and conditions created by storm water and effluent from a constructed wetland were assessed for vegetation regeneration in the degraded QENP pyrite trail. Cynodon dactylon, Imperata cylindrica and Hyparrhenia filipendula dominated the regeneration zone (RZ) where storm water and effluent from a constructed wetland was flowing; and the adjacent unpolluted area (UP) with importance value indices of 186.4 and 83.3 respectively. Typha latifolia and C. dactylon formed two distinct vegetation sub-zones within the RZ with the former inhabiting areas with a higher water table. Soil pH was significantly higher in the RZ, followed by UP and bare pyrite trail (BPT) at both 0-15 cm and 16-30 cm depths. Soil electrical conductivity was not significantly different in the RZ and BPT but significantly higher than that in UP for both depths. For 0-15 cm depth, RZ had significantly higher concentrations of copper than BPT and UP which had similar concentrations. Still at this depth (0-15 cm), the unpolluted area had significantly higher concentrations of total phosphorus and total nitrogen than the regeneration zone and the bare pyrite trail which had similar concentrations. The RZ dominated by Typha had significantly higher concentrations of TP and TN compared to the RZ dominated by Cynodon. The concentrations of NH 4-N were significantly lower in Typha regeneration zone than in CRZ at 0-15 cm depth but similar at 16-30 cm depth. At 16-30 cm depth, concentrations of copper were significantly higher in the regeneration zone followed by the bare pyrite trail and the unpolluted zone. The concentration of lead in the regeneration zone and bare pyrite trail were similar but significantly higher in the unpolluted zone. Concentrations of TP and TN were significantly higher in unpolluted zone, followed by regeneration zone and bare pyrite trail. Storm water and effluent from a constructed wetland enhanced the revegetation process by modifying soil pH, making plant growth nutrients available and by providing a steady supply of moisture necessary for plant growth. T. latifolia and C. dactylon which seem to have tolerance of high concentrations of metals were the dominant species in the regeneration zone. If storm water and effluent supply continues, the aforementioned vegetation will colonize the pyrite trail and will eventually protect QENP and Lake George from metal contamination.
Crosscutting Technology Development at the Center for Advanced Separation Technologies
DOE Office of Scientific and Technical Information (OSTI.GOV)
Christopher E. Hull
2006-09-30
This Technical Progress Report describes progress made on the twenty nine subprojects awarded in the second year of Cooperative Agreement DE-FC26-02NT41607: Crosscutting Technology Development at the Center for Advanced Separation Technologies. This work is summarized in the body of the main report: the individual sub-project Technical Progress Reports are attached as Appendices.
CROSSCUTTING TECHNOLOGY DEVELOPMENT AT THE CENTER FOR ADVANCED SEPARATION TECHNOLOGIES
DOE Office of Scientific and Technical Information (OSTI.GOV)
Christopher E. Hull
2006-05-15
This Technical Progress Report describes progress made on the twenty nine subprojects awarded in the second year of Cooperative Agreement DE-FC26-02NT41607: Crosscutting Technology Development at the Center for Advanced Separation Technologies. This work is summarized in the body of the main report: the individual sub-project Technical Progress Reports are attached as Appendices.
NASA Astrophysics Data System (ADS)
Saha, Debasree; Chatterjee, Debashis; Chakravarty, Sanchita; Mazumder, Madhurina
2018-04-01
Coal samples of Samaleswari open cast coal block (S-OCB) are high ash (Aad, mean value 35.43%) and low sulphur content (St, on dry basis, mean value 0.91% < 1%) in quality. The stratigraphic variation of volatile matter and fixed carbon (dry ash-free) reflect a progress of coal metamorphism with depth that accordance to the coal rank variation from lignite to high volatile bituminous in the studied borehole. The younger coal seams have greater detrital minerals (quartz, illite, rutile) influence whereas older coal seams have greater authigenic mineral (kaolinite, dolomite, siderite, apatite) contribution that are possibly due to subsidence and sediment transportation. In S-OCB coal trace elements affinities in-between mineral and organic fraction are identified with statistical hierarchical cluster analysis. The work is further supported by the use of chemical fractionation experiment that reveals the multi mode of occurrence of several environmentally concern and interested trace elements (Sb, As, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, Zn). Among the analysed trace elements Co, Mn and Zn have major silicate association along with significant carbonate/oxide/monosulfide association. Whereas As, Cd, Cu, Pb and Ni have dominant pyritic association with notable silicate and carbonate/oxide/monosulfide association. The rest three elements (Sb, Be, Cr) have principally organic association with minor silicate and carbonate/oxide/monosulfide association. The stratigraphic variation of organo-mineral matrix content and detrital-authigenic mineral ratio are primarily related to coal rank. Geochemical character of coal also reflects a light towards proper utilisation of S-OCB coal from technical and environmental view point.
ERIC Educational Resources Information Center
Park, Bitnara Jasmine; Alonzo, Julie; Tindal, Gerald
2011-01-01
This technical report describes the process of development and piloting of reading comprehension measures that are appropriate for seventh-grade students as part of an online progress screening and monitoring assessment system, http://easycbm.com. Each measure consists of an original fictional story of approximately 1,600 to 1,900 words with 20…
NASA Astrophysics Data System (ADS)
Magnall, J. M.; Gleeson, S. A.; Stern, R. A.; Newton, R. J.; Poulton, S. W.; Paradis, S.
2016-05-01
Highly positive δ34S values in sulphide minerals are a common feature of shale hosted massive sulphide deposits (SHMS). Often this is attributed to near quantitative consumption of seawater sulphate, and for Paleozoic strata of the Selwyn Basin (Canada), this is thought to occur during bacterial sulphate reduction (BSR) in a restricted, euxinic water column. In this study, we focus on drill-core samples of sulphide and barite mineralisation from two Late Devonian SHMS deposits (Tom and Jason, Macmillan Pass, Selwyn Basin), to evaluate this euxinic basin model. The paragenetic relationship between barite, pyrite and hydrothermal base metal sulphides has been determined using transmitted and reflected light microscopy, and backscatter electron imaging. This petrographic framework provides the context for in-situ isotopic microanalysis (secondary ion mass spectrometry; SIMS) of barite and pyrite. These data are supplemented by analyses of δ34S values for bulk rock pyrite (n = 37) from drill-core samples of un-mineralised (barren), siliceous mudstone, to provide a means by which to evaluate the mass balance of sulphur in the host rock. Three generations of barite have been identified, all of which pre-date hydrothermal input. Isotopically, the three generations of barite have overlapping distributions of δ34S and δ18O values (+22.5‰ to +33.0‰ and +16.4‰ to +18.3‰, respectively) and are consistent with an origin from modified Late Devonian seawater. Radiolarian tests, enriched in barium, are abundant within the siliceous mudstones, providing evidence that primary barium enrichment was associated with biologic activity. We therefore propose that barite formed following remobilisation of productivity-derived barium within the sediment, and precipitated within diagenetic pore fluids close to the sediment water interface. Two generations of pyrite are texturally associated with barite: framboidal pyrite (py-I), which has negative δ34S values (-23‰ to -28‰; n = 9), and euhedral pyrite (py-II), which has markedly more positive δ34S values (+8‰ to +26‰; n = 86). We argue that stratiform pyrite and barite developed along diagenetic redox fronts, where the isotopic relationships (δ34Spyrite ≈ δ34Sbarite) are explained by anaerobic oxidation of methane coupled to sulphate reduction (AOM-SR). Furthermore, the relatively narrow distribution of δ34Sbarite values is consistent with an open system model of sulphate reduction, in which reduced sulphur generation occurred with a reduced isotopic fractionation (ε34S = <15‰) linked to higher rates of sulphate reduction and AOM-SR. Importantly, hydrothermal sulphides (pyrite, sphalerite and galena) all post-date this diagenetic barite-pyrite assemblage, and textural and mineralogical evidence indicates barite replacement to be an important process during hydrothermal mineralisation. Neither the textures nor the documented isotopic relationships can be produced by processes operating in a euxinic water column, which represents a major departure from the conventional model for SHMS formation at Macmillan Pass. We suggest that positive δ34S values in sulphides, a common feature of SHMS systems both in the Selwyn Basin and throughout the geologic record, could be linked to AOM-SR. At Macmillan Pass, positive δ34Spyrite values developed during open system diagenesis, which was critical for rapid sulphur cycling and the development of an effective metal trap.
Stein, H.J.; Sundblad, K.; Markey, R.J.; Morgan, J.W.; Motuza, G.
1998-01-01
Seven 187Re-187Os ages were determined for molybdenite and pyrite samples from two well-dated Precambrian intrusions in Fennoscandia to examine the sustainability of the Re-Os chronometer in a metamorphic and metasomatic setting. Using a new 187Re decay constant (1.666 x 10-11y-1) with a much improved uncertainty (±0.31%), we determined replicate Re-Os ages for molybdenite and pyrite from the Kuittila and Kivisuo prospects in easternmost Finland and for molybdenite from the Kabeliai prospect in southernmost Lithuania. These two localities contain some of the oldest and youngest plutonic activity in Fennoscandia and are associated with newly discovered economic Au mineralization (Ilomantsi, Finland) and a Cu-Mo prospect (Kabeliai, Lithuania). Two Re-Os ages for veinhosted Kabeliai molybdenite average 1486 ± 5 Ma, in excellent agreement with a 1505 ± 11 Ma U-Pb zircon age for the hosting Kabeliai granite pluton. The slightly younger age suggests the introduction of Cu-Mo mineralization by a later phase of the Kabeliai magmatic system. Mean Re-Os ages of 2778 ± 8 Ma and 2781 ± 8 Ma for Kuittila and Kivisuo molybdenites, respectively, are in reasonable agreement with a 2753 ± 5 Ma weighted mean U-Pb zircon age for hosting Kuittila tonalite. These Re-Os ages agree well with less precise ages of 2789 ± 290 Ma for a Rb-Sr whole-rock isochron and 2771 ± 75 Ma for the average of six Sm-Nd T(DM) model ages for Kuittila tonalite. Three Re-Os analyses of a single pyrite mineral separate, from the same sample of Kuittila pluton that yielded a molybdenite separate, provide individual model ages of 2710 ± 27, 2777 ± 28, and 2830 ± 28 Ma (Re = 17.4, 12.1, and 8.4 ppb, respectively), with a mean value of 2770 ± 120 Ma in agreement with the Kuittila molybdenite age. The Re and 187Os abundances in these three pyrite splits are highly correlated (r = 0.9994), and provide a 187Re-187Os isochron age of 2607 ± 47 Ma with an intercept of 21 ppt 187Os (MSWD = 1.1). It appears that the Re-Os isotopic system in pyrite has been reset on the millimeter scale and that the 21 ppt 187Os intercept reflects the in situ decay of 187Re during the ~160 to 170 m.y. interval from ~2778 Ma (time of molybdenite ± pyrite deposition) to ~2607 Ma (time of pyrite resetting). When the Re-Os data for molybdenites from the nearby Kivisuo prospect are plotted together with the Kuittila molybdenite and pyrite data, a well-constrained five-point isochron with an age of 2780 ± 8 Ma and a 187Os intercept (-2.4 ± 3.8 ppt) of essentially zero results (MSWD = 1.5). We suggest that the pyrite isochron age records a regional metamorphic and/or hydrothermal event, possibly the time of Au mineralization. A proposed Re-Os age of ~2607 Ma for Au mineralization is in good agreement with radiometric ages by other methods that address the timing of Archean Au mineralization in deposits worldwide (so-called 'late Au model'). Molybdenite, in contrast, provides a robust Re-Os chronometer, retaining its original formation age of ~2780 Ma, despite subsequent metamorphic disturbances in Archean and Proterozoic time.
The origin of jarosite associated with a gossan on Archean gneiss in Southwest Greenland
NASA Astrophysics Data System (ADS)
Peng, Y.; Pratt, L. M.; Young, S. A.; Cadieux, S. B.; White, J. R.
2013-12-01
The mineral Jarosite [KFe3(SO4)2(OH)6] since its discovery, by Opportunity rover at Meridiani Planum on Mars, has been the subject of intense geochemical and environmental study over the last 5-10 years. Jarosite requires highly acidic, K-enriched, and oxidizing aqueous conditions for formation. Stable isotopes of O, H, and S of jarosite have the ability to record the temperatures of formation, environments of deposition, fluids, and fluid/atmospheric interactions. Therefore, the origin of jarosite is important for understanding present and past environmental conditions on Mars. Unfortunately, the origin of jarosite on Mars remains unclear. Jarosite is commonly found on Earth in the weathering zones of pyrite-bearing ore deposits, near-surface playa sediments in acid-saline lakes, or epithermal environments and hot springs. Here, we report the occurrence of jarosite in association with a gossan overlying weathered Archean gneiss and Paleoproterozoic mafic dikes at the ice-free margin of southwestern Greenland. In our 2012 field campaign, we excavated soil pits to a depth of 40 cm with a high vertical sampling resolution. No visible pyrite was found in the nearby outcroppings of gneiss in the field. XRD data show that all samples were composed of anorthite, quartz, albite, jarosite, muscovite, and microcline. Jarosite was the only sulfur-bearing mineral identified by XRD, with abundance of jarosite increasing with depth (up to 8.4 wt. %) in the soil pits. Water soluble and acid soluble sulfate were sequentially extracted using 10% NaCl and 2N HCl solutions, respectively. Pyrite was then subsequently extracted from insoluble residues by a chromium reduction method. The average abundance of water soluble sulfate, acid soluble sulfate, and pyrite were 100 ppm, 7 wt. %, and 10 ppm, respectively. The δ34S values of water soluble sulfate, acid soluble sulfate, and pyrite range from -0.7‰ to 3.1‰ (average= 1.5‰), -1.2 to 1.5‰ (average= 0.7‰), and 0.3‰ to 6.7‰ (average= 2.6‰) respectively. δ34S values of all water soluble sulfate and pyrite, were higher than acid soluble sulfate. δ34S values of pyrite were higher than all water soluble sulfate except the surficial sample (0-10 cm depth). The δ34S values of water soluble sulfate and acid soluble sulfate did not change with depth while δ34S values of pyrite increased with depth from 2.4‰ to 6.7 ‰ (peak at 10-15 cm) and dropped to 2.0‰. Preliminary data indicate that the acid soluble sulfate was dominated by jarosite while the water soluble sulfate fraction may have been a mixture of leached jarosite and other sulfate sources, such as atmospheric sulfate. Jarosite formation may result from the oxidative weathering of pyrite inferred to originate from localized, stratiform, hydrothermal mineralization. To constrain the origin of jarosite, a new profile containing soil, permafrost, and bedrock was collected at the same location during the summer 2013 field campaign by drilling ~ 1.0 meter into the permafrost zone. We will employ multiple sulfur isotope and triple oxygen isotope of sulfate and pyrite, which can define the source of sulfur and oxygen. A greater understanding of the formation of jarosite on this ice-free margin of Greenland will provide an insightful potential analogue for jarosite formation and on Mars.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hammer, D.A.; Kusse, B.R.; Sudan, R.N.
1983-07-01
The progress on this contract is described in three parts. The first deals with the technical operation of the LION accelerator. The second and third parts are concerned with the experimental results.
2011-02-01
cuprite [Cu2O], hematite [Fe2O3], ilmenite [FeTiO3], magnesite [MgCO3], malachite [Cu2(CO3)(OH)2], pyrite [FeS2], pyrolusite [MnO2], siderite [FeCO3...0.3 m2/g], malachite [3.65 ± 0.03 m2/g], pyrite [2.12 ± 0.01 m2/g], pyrolusite [1.39 ± 0.04 m2/g], siderite [6.8 ± 0.4 m2/g], willemite [1.8 ± 0.02 m2...0.4 0.6 0.8 1 0 10 20 30 40 50 60 Anatase Bauxite Calcite Cobaltite Control Cuprite Hematite Ilmenite Magnesite Malachite Pyrite Pyrolusite Siderite
NASA Astrophysics Data System (ADS)
Altin Massinai, Muhammad; Lantu; Latuconsina, Hidayat; Fawzy Ismullah M, Muhammad
2018-03-01
Sulphide minerals are any member of a group of compounds of sulphur with one or more metals. Some of these sulphide minerals are economically important. This study used induced polarization method to identify distribution and mineralized zone of sulphide mineral (Pyrite), in Libureng, Bone Regency, South Sulawesi. The data processing yielded resistivity value, percent frequency effect (PPE) value, and metal factor (MF) value which were then used to produce 2-D and 3-D section model. Based on the data interpretation, an anomaly linked to pyrite deposits was seen in four trajectories with resistivity value < = 50, PFE = > 3%, and MF > = 150, deposited in hydrothermal alteration zone, sericite zone.
ERIC Educational Resources Information Center
Alonzo, Julie; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in kindergarten. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2008 and administered to approximately 2800 students from…
Federal Register 2010, 2011, 2012, 2013, 2014
2010-10-19
... Purpose. 148.205 Ammonium nitrate and ammonium nitrate fertilizers. 148.220 Ammonium nitrate-phosphate fertilizers. 148.225 Calcined pyrites (pyritic ash, fly ash). 148.227 Calcium nitrate fertilizers. 148.230... tankage fertilizer. 148.325 Wood chips; wood pellets; wood pulp pellets. 148.330 Zinc ashes; zinc dross...
Near-infrared Raman imaging microscopy (NIRIM) was used to produce chemical images of the distribution of elemental sulfur on oxidized pyrite and arsenopyrite surfaces. Analysis using Savitsky¯Golay filtering permits an unambiguous identificati...
Thermal activated ("thermal") battery technology. Part IIIa: FeS 2 cathode material
NASA Astrophysics Data System (ADS)
Masset, Patrick J.; Guidotti, Ronald A.
This article presents an overview of the pyrite FeS 2 used as cathode material in thermally activated ("thermal") batteries. A large emphasis was placed on the physicochemical properties and electrochemical performance of the pyrite FeS 2, including the discharge mechanisms, self-discharge phenomena, and recent developments.
AMD in the Iberian Pyrite Belt is a problem of global scale. Successful implementation of passive treatment systems could remediate at least part of this problem at reasonable costs. However, initial trials with ALD and RAPS based on gravel size limestone failed due to rapid loss...
Heterocoagulation of chalcopyrite and pyrite minerals in flotation separation.
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.
Surface chemical reactions induced on pyrite by ion bombardment
NASA Astrophysics Data System (ADS)
Ruano, Gustavo; Pomiro, Fernando; Ferrón, Julio
2018-01-01
Through X-ray photoemission spectroscopy (XPS), we studied the chemical changes induced in a natural crystal of pyrite (FeS2) upon exposure to 4.5 keV He+ beam. We found an important reducing effect induced by ion bombardment leading to the production of iron embedded in the pyrite matrix. Through a combination of the usual Doniach-Sunjic treatment and Factor Analysis of XPS yields, we were able of analyzing the full Fe 2p XPS signal. We could in this way distinguish Fe compounds with the same binding energy for the Fe 2p3/2 yield. Our results show that He+ bombardment disrupts the ionic environment producing S2-2 and S0, Fe2+ and Fe3+ ions, and the reduction to metallic iron. The remaining pyrite matrix does not passivate the embedded iron structures, which are readily oxidized under air exposure. The oxide formed resembled that of magnetite from the XPS point of view. Further He+ bombardment proved to be efficient to reduce the iron oxide back to iron again.
Bioleaching of multiple heavy metals from contaminated sediment by mesophile consortium.
Gan, Min; Zhou, Shuang; Li, Mingming; Zhu, Jianyu; Liu, Xinxing; Chai, Liyuan
2015-04-01
A defined mesophile consortium including Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, and Leptospirilum ferriphilum was applied in bioleaching sediments contaminated with multiple heavy metals. Flask experiments showed that sulfur favored the acidification in the early stage while pyrite led to a great acidification potential in the later stage. An equal sulfur/pyrite ratio got the best acidification effect. Substrate utilization started with sulfur in the early stage, and then the pH decline and the community shift give rise to the utilization of pyrite. Solubilization efficiency of Zn, Cu, Mn, and Cd reached 96.1, 93.3, 92.13, and 87.65%, respectively. Bioleaching efficiency of other elements (As, Hg, Pb) was not more than 30%. Heavy metal solubilization was highly negatively correlated with pH variation. Logistic models were well fitted with the solubilization efficiency, which can be used to predict the bioleaching process. The dominant species in the early stage of bioleaching were A. ferrooxidans and A. thiooxidans, and the abundance of L. ferriphilum increased together with pyrite utilization and pH decline.
Carbonaceous structures in the Tissint Martian Meteorite: evidence of a biogenetic origin
NASA Astrophysics Data System (ADS)
Wallis, Jamie; Wickramasinghe, N. C.; Wallis, Daryl H.; Miyake, Nori; Wallis, M. K.; Hoover, Richard B.
2015-09-01
We report for the first time in situ observations of 5-50μm spherical carbonaceous structures in the Tissint Martian meteorite comprising of pyrite (FeS2) cores and carbonaceous outer coatings. The structures are characterized as smooth immiscible spheres with curved boundaries occasionally following the contours of the pyrite inclusion. The structures bear striking resemblance to similar-sized immiscible carbonaceous spheres found in hydrothermal calcite vein deposits in the Mullaghwornia Quarry in central Ireland. Similar structures have been reported in Proterozoic and Ordovician sandstones from Canada as well as in a variety of astronomical sources including carbonaceous chondrites, chondritic IDPs and primitive chondritic meteorites. SEM and X-Ray elemental mapping confirmed the presence of organic carbon filling the crack and cleavage space in the pyroxene substrate, with further evidence of pyrite acting as an attractive substrate for the collection of organic matter. The detection of precipitated carbon collecting around pyrite grains is at variance with an igneous origin as proposed for the reduced organic component in Tissint, and is more consistent with a biogenetic origin.
Extraction of manganese from electrolytic manganese residue by bioleaching.
Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo
2011-01-01
Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. Copyright © 2010 Elsevier Ltd. All rights reserved.
Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain
NASA Astrophysics Data System (ADS)
Castelló, Ricardo; Recio, Clemente; Morillas, Pilar; Vizcayno, Carmen
2008-04-01
The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H2S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ34S values for sulfates were consistent with previously reported data; however, the measured δ18O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ34S values (≈-8‰) than gypsum-coating pyrite crystals (δ34S < -30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H2S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as δ_{text{SO}4^{2-}-{text{S}^{2-}}}≈ - {text{50}}permille.
Assessment Program Technical Progress Report, 1996-1997.
ERIC Educational Resources Information Center
McCown, Laurie; Fanning, Erin; Eickmeyer, Barbara
Coconino Community College (CCC) annually assesses its institutional effectiveness to demonstrate its commitment to improving programs and services to students. The 1996-97 Assessment Program Technical Progress Report records the assessment and institutional activities enacted during the academic year, detailing the assessment model, timelines,…
Mineralization of Basalts in the CO 2-H 2O-H 2S System
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.
2013-05-10
Basalt samples representing five different formations were immersed in water equilibrated with supercritical carbon dioxide containing 1% hydrogen sulfide (H2S) at reservoir conditions (100 bar, 90°C) for up to 3.5 years. Surface coatings in the form of pyrite and metal cation substituted carbonates were identified as reaction products associated with all five basalts. In some cases, high pressure tests contained excess H2S, which produced the most corroded basalts and largest amount of secondary products. In comparison, tests containing limited amounts of H2S appeared least reacted with significantly less concentrations of reaction products. In all cases, pyrite appeared to precede carbonation,more » and in some instances, was observed in the absence of carbonation such as in cracks, fractures, and within the porous glassy mesostasis. Armoring reactions from pyrite surface coatings observed in earlier shorter duration tests were found to be temporary with carbonate mineralization observed with all the basalts tested in these long duration experiments. Geochemical simulations conducted with the geochemical code EQ3/6 accurately predicted early pyrite precipitation followed by formation of carbonates. Reactivity with H2S was correlated with measured Fe(II)/Fe(III) ratios in the basalts with more facile pyrite formation occurring with basalts containing more Fe(III) phases. These experimental and modeling results confirm potential for long term sequestration of acid gas mixtures in continental flood basalt formations.« less
NASA Astrophysics Data System (ADS)
Carrillo-Rosúa, J.; Morales-Ruano, S.; Morata, D.; Boyce, A. J.; Belmar, M.; Fallick, A. E.; Fenoll Hach-Alí, P.
2008-03-01
The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47'S Lat., 70°43'W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06-0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21-0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ18O and δD for the hydrothermal fluids were between 3 and 10‰ and between -95 and -75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit.
Liu, Yuanyuan; Mou, Haiyan; Chen, Liqun; Mirza, Zakaria A; Liu, Li
2015-11-15
Permeable reactive barriers (PRBs) are efficient technologies for in situ remediation of contaminated groundwater, the effectiveness of which greatly depends on the reactive media filled. Natural pyrite is an iron sulfide material with a very low content of iron and sulfur, and a mining waste which is a potential material for Cr(VI) immobilization. In this study, we conducted a series of batch tests to research the effects of typical environmental factors on Cr(VI) removal and also simulated PRB filled with natural pyrite to investigate its effectiveness, in order to find a both environmentally and economically fine method for groundwater remediation. Batch tests showed that pH had the significant impact on Cr(VI) removal with an apparently higher efficiency under acidic conditions, and dissolved oxygen (DO) would inhibit Cr(VI) reduction; a relatively high initial Cr(VI) concentration would decrease the rate of Cr(VI) sorption; ionic strength and natural organic matter resulted in no significant effects on Cr(VI) removal. Column tests demonstrated that the simulated PRB with natural pyrite as the reactive media was considerably effective for removing Cr(VI) from groundwater, with a sorption capability of 0.6222 mg Cr per gram of natural pyrite at an initial Cr(VI) concentration of 10mg/L at pH 5.5 in an anoxic environment. Copyright © 2015 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Chugaev, A. V.; Znamensky, S. E.
2018-01-01
The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide-carbonate-quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite 206Pb/204Pb = 18.250-18.336, 207Pb/204Pb = 15.645-15.653, 208Pb/204Pb = 38.179-38.461; while for late pyrite 206Pb/204Pb = 18.102-18.378, 207Pb/204Pb = 15.635-15.646, 208Pb/204Pb = 38.149-38.320. The model parameters μ2 (238U/204Pb = 9.91 ± 2), ω2 (232Th/204Pb = 38.5 ± 4), and 232Th/238U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.
Panda, Sandeep; Akcil, Ata; Mishra, Srabani; Erust, Ceren
2017-03-05
Pyrite ash, a waste by-product formed during roasting of pyrite ores, is a good source of valuable metals. The waste is associated with several environmental issues due to its dumping in sea and/or land filling. Although several other management practices are available for its utilization, the waste still awaits and calls for an eco-friendly biotechnological application for metal recovery. In the present study, chemolithotrophic meso-acidophilic iron and sulphur oxidisers were evaluated for the first time towards simultaneous mutli-metal recovery from pyrite ash. XRD and XRF analysis indicated higher amount of Hematite (Fe 2 O 3 ) in the sample. ICP-OES analysis indicated concentrations of Cu>Zn>Co>As that were considered for bioleaching. Optimization studies indicated Cu - 95%, Co - 97%, Zn - 78% and As - 60% recovery within 8days at 10% pulp density, pH - 1.75, 10% (v/v) inoculum and 9g/L Fe 2+ . The productivity of the bioleaching system was found to be Cu - 1696ppm/d (12% dissolution/d), Co - 338ppm/d (12.2% dissolution/d), Zn k 576ppm/d (9.8% dissolution/d) and As - 75ppm/d (7.5% dissolution/d). Synergistic actions for Fe 2+ - S° oxidation by iron and sulphur oxidisers were identified as the key drivers for enhanced metal dissolution from pyrite ash sample. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Piña, R.; Gervilla, F.; Barnes, S.-J.; Oberthür, T.; Lunar, R.
2016-10-01
The Main Sulfide Zone (MSZ) of the Great Dyke of Zimbabwe hosts the world's second largest resource of platinum-group elements (PGE) after the Bushveld Complex in South Africa. The sulfide assemblage of the MSZ comprises pyrrhotite, pentlandite, chalcopyrite, and minor pyrite. Recently, several studies have observed in a number of Ni-Cu-PGE ore deposits that pyrite may host significant amounts of PGE, particularly Pt and Rh. In this study, we have determined PGE and other trace element contents in pyrite from the Hartley, Ngezi, Unki, and Mimosa mines of the Great Dyke by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on the textures and PGE contents, two types of pyrite can be differentiated. Py1 occurs as individual euhedral or subhedral grains or clusters of crystals mostly within chalcopyrite and pentlandite, in some cases in the form of symplectitic intergrowths, and is PGE rich (up to 99 ppm Pt and 61 ppm Rh; 1.7 to 47.1 ppm Ru, 0.1 to 7.8 ppm Os, and 1.2 to 20.2 ppm Ir). Py2 occurs as small individual euhedral or subhedral crystals within pyrrhotite, pentlandite, and less frequently within chalcopyrite and silicates and has low PGE contents (<0.11 ppm Pt, <0.34 ppm Rh, <2.5 ppm Ru, <0.37 ppm Ir, and <0.40 ppm Os). Py1 contains higher Os, Ir, Ru, Rh, and Pt contents than the associated pyrrhotite, pentlandite, and chalcopyrite, whereas Py2 has similar PGE contents as coexisting pyrrhotite and pentlandite. Based on the textural relationships, two different origins are attributed for each pyrite type. Py1 intergrowth with pentlandite and chalcopyrite is inferred to have formed by late, low temperature (<300 °C) decomposition of residual Ni-rich monosulfide solid solution, whereas Py2 is suggested to have formed by replacement of pyrrhotite and pentlandite caused by late magmatic/hydrothermal fluids.
NASA Astrophysics Data System (ADS)
Huang, C.; Chien, C.; Yang, T. F.; Lin, S.
2005-12-01
The Kaoping Slope off SW Taiwan represents the syn-collision accretionary prism characterized by active NW-trending folding - thrusting structures and high sedimentation rate favoring the formation of gas hydrate. For an assessment of gas hydrate potential in the Kaoping Slope off SW Taiwan, sedimentology, paleontology and geochemistry in box cores and piston cores were studied. BSRs are commonly found in seismic profiles in 400-600 m below seafloor of water depth 2500-1000 m. Active expulsions of methane were found along active thrust faults where sulfate/methane interface could be as shallow as 30 cm and the methane concentration of dissolved gases in bottom water and in pore-space of drilled core samples could be three-four order higher than the normal marine environments. Occurrences of authigenic carbonate and elongated pyrite tubes are correlated with shallow SMI depth and high methane content in bottom water and pore-space of sediment cores. Authigenic carbonates were found in seafloor surface and in 20-25 meters below seafloor. The authigenic carbonate nodules are characterized by irregular shape, whitish color, no visible microfossil, containing native sulfur, pyrites, gypsum, small open spaces, and very depleted carbon isotope (-54 ~ -43 per mil PDB). Tiny native sulfur and gypsum crystals were commonly found either on surface of foraminiferal tests and elongated pyrite tubes or in the authigenic carbonate nodules. Morphological measurements of elongated pyrite tubes show that they could represent pseudomorphs after three types of Pogonophora tube worm. Foraminifers are commonly filled by rhomboidal pyrites or cemented by pyrite crystals. Normal marine benthic foraminifers predominated by calcareous tests of slope fauna are associated with authigenic carbonate nodules in the study area, suggesting no major geochemistry effect on distribution of benthic foraminifers. Integrating sedimentology, paleontology and geochemistry characters, there could be high potential to have gas hydrate in the accretionary prism off SW Taiwan.
Wacey, D; Saunders, M; Kong, C; Kilburn, M R
2016-09-01
Ambient inclusion trails (AITs) are tubular microstructures thought to form when a microscopic mineral crystal is propelled through a fine-grained rock matrix. Here, we report a new occurrence of AITs from a fossilized microbial mat within the 1878-Ma Gunflint Formation, at Current River, Ontario. The AITs are 1-15 μm in diameter, have pyrite as the propelled crystal, are infilled with chlorite and have been propelled through a microquartz (chert) or chlorite matrix. AITs most commonly originate at the boundary between pyrite- and chlorite-rich laminae and chert-filled fenestrae, with pyrite crystals propelled into the fenestrae. A subset of AITs originate within the fenestrae, rooted either within the chert or within patches of chlorite. Sulphur isotope data ((34) S/(32) S) obtained in situ from AIT pyrite have a δ(34) S of -8.5 to +8.0 ‰, indicating a maximum of ~30 ‰ fractionation from Palaeoproterozoic seawater sulphate (δ(34) S ≈ +20 ‰). Organic carbon is common both at the outer margins of the fenestrae and in patches of chlorite where most AITs originate, and can be found in smaller quantities further along some AITs towards the terminal pyrite grain. We infer that pyrite crystals now found within the AITs formed via the action of heterotrophic sulphate-reducing bacteria during early diagenesis within the microbial mat, as pore waters were becoming depleted in seawater sulphate. Gases derived from this process such as CO2 and H2 S were partially trapped within the microbial mat, helping produce birds-eye fenestrae, while rapid microquartz precipitation closed porosity. We propose that propulsion of the pyrite crystals to form AITs was driven by two complementary mechanisms during burial and low-grade metamorphism: firstly, thermal decomposition of residual organic material providing CO2 , and potentially CH4 , as propulsive gases, plus organic acids to locally dissolve the microquartz matrix; and secondly, reactions involving clay minerals that potentially led to enhanced quartz solubility, plus increases in fluid and/or gas pressure during chlorite formation, with chlorite then infilling the AITs. This latter mechanism is novel and represents a possible way to generate AITs in environments lacking organic material. © 2016 John Wiley & Sons Ltd.
Sommerfield, C.K.; Aller, R.C.; Nittrouer, C.A.
2001-01-01
Depositional and diagenetic controls on the distributions of carbon, sulfur, and iron (C-S-Fe) in modern sediments and upper Pleistocene mudrocks of the Eel River Basin (ERB), northern California continental margin, were investigated using a combination of geochemical, radioisotopic, and sedimentological methods. A mass balance based on down-core profiles of porewater and solid-phase constituents and diagenetic modeling suggests that only 12-30% of the pyrite-S produced via SO4-2 reduction during burial is retained in modern shelf and upper slope deposits of the ERB. Bioturbational reoxidation of initially reduced S is inferred to be the major control on S preservation, on the basis of an observed inverse relationship between pyrite-S retention and biological mixing intensity, estimated from profiles of excess 234Th. Importantly, these findings argue that massive depositional episodes on the shelf following floods of the Eel River have a negligible long-term impact on bioturbating macrofauna and the potential to affect geochemical properties of the sediments. Down-core profiles of reactive Fe3+and Py-Fe(II) for the modern deposits suggest that highly reactive Fe phases are sulfidized well within ∼ 500-2000 years of burial, thereby limiting later pyritization, which could occur through sulfidation of less reactive phases. This result explains the low (≤ 0.4) degree of pyritization (DOP) values exhibited by both modern and ancient deposits of the ERB and lends support to the notion that pyritization in aerobic continental-margin sediments is largely associated with highly reactive detrital Fe oxides. Comparable mean C/S weight ratios for modern sediments (5.4 ± 3.3, 1σ) and mudrocks (6.9 ± 4.5) of the ERB suggest that the upper Pleistocene strata reflect a geochemical environment analogous to that of the modern margin. Specifically, the C-S-Fe signatures shared by the modern and ancient deposits are a consequence of similar detrital Fe mineralogies, initial organic-matter content (Corg ≤ 1%) and composition (C/N = 13 to 17, δ13Corg = -22 to -25‰), burial rate, and importantly, bioturbation intensity. The findings of this study have important implications for the use of C-S-Fe signatures as indicators of diagenetic processes in dynamic, continental-margin environments.
Invisible and microscopic gold in pyrite: Methods and new data for massive sulfide ores of the Urals
NASA Astrophysics Data System (ADS)
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 <10% (Galkinsk deposit) to 85% (Uchaly deposit). Major part of "invisible" gold occurs as micron- to nanoscale particles of Au minerals. The portion of gold structurally bound in pyrite lattice (from the bulk concentration of Au in pyrite) is estimated to be from few % (the Galkinsk deposit) to 20-25% (the Uchaly deposit). The presence of As and Sb in pyrite and sphalerite, as well as other trace elements (Te, Co, Mn, Cu, Hg, and Ag in both as well as Fe in sphalerite) stimulates the incorporation of Au in sulfide, but mostly in defect-associated, not isomorphic form. Micron particles of Ag sulfosalts (pyrargyrite, freibergite, stephanite, polybasite, pyrostilpnite, argentotetrahedrite, pearceite, proustite), Au-Ag alloys (from gold of high fineness to küstelite), Ag and Au-Ag tellurides (hessite, empressite, calaverite), and occasional Au-Ag sulfides (petrovskaite, uytenbogaardtite) were registered in the areas of Au enrichment of both deposits; selenotelluride (kurilite) particles were found on the Galkinsk deposit. Nanoscale (1-50 nm) native gold (spherical and disk-shaped particles, 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.
NASA Astrophysics Data System (ADS)
Dogramaci, Shawan; McLean, Laura; Skrzypek, Grzegorz
2017-02-01
Sulphur (S) is a commonly occurring element in most aquifers, primarily in oxidised (sulphates) and reduced (sulphides) forms. Sulphides often constitute a risk to groundwater quality due to acid rock drainage, especially in catchments that are subject to mining excavations or groundwater injection. However, in semi-arid regions detection of the acid rock drainage risk can be challenging and traditional methods based on observations of increasing SO4 concentrations or SO4/Cl ratios in surface and groundwater, are not necessarily applicable. In addition, decreasing pH, usually accompanying pyrite oxidation, can be masked by the high pH-neutralisation capacity of carbonate and silicate minerals. Analysis of 73 surface and groundwater samples from different water bodies and aquifers located in the Hamersley Basin, Western Australia found that most of the samples are characterised by neutral pH but there was also a large spatial variability in the dissolved sulphate (SO4) concentrations that ranged from 1 mg/L to 15,000 mg/L. Not surprisingly, groundwater in aquifers that contained pyrite had high sulphate concentrations (>1000 mg/L). This was associated with low δ34SSO4 values (+1.2‰ to +4.6‰) and was consistent with the values obtained from aquifer matrix pyritic rock samples (-1.9‰ to +4.4‰). It was also found that the SO4 concentrations and acidity levels were not only dependent on δ34SSO4 values and existence of pyrite but also on the presence of carbonate minerals in the aquifer matrix. The groundwater in aquifers containing both pyrite and carbonate minerals had a neutral pH and was also saturated with respect to gypsum and had high magnesium concentrations of up to 2200 mg/L suggesting de-dolomitisation as the process buffering the acidity generated by pyrite oxidation. Based on the findings from this study, a classification scheme has been developed for identification of the acid rock drainage contribution to groundwater that encompasses a myriad of geochemical processes that occur in aqueous systems. The classification uses five proxies (SO4, SO4/Cl, SI of calcite, δ34SSO4 and δ18OSO4) to improve assessment of the oxidation of sulphide potential contribution to overall sulphate ion concentrations regardless of acidity levels of the aqueous system.
Cravotta,, Charles A.
1991-01-01
Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.
Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev
2005-01-01
Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and ??34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite. Copyright ?? 2005 Elsevier Ltd.
ERIC Educational Resources Information Center
Alonzo, Julie; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grade 1. These measures, available as part of easyCBM [TM], an online progress monitoring assessment system, were developed in 2008 and administered to approximately 2800 students from schools…
ERIC Educational Resources Information Center
Alonzo, Julie; Lai, Cheng Fei; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
ERIC Educational Resources Information Center
Alonzo, Julie; Lai, Cheng Fei; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
ERIC Educational Resources Information Center
Lai, Cheng Fei; Alonzo, Julie; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
ERIC Educational Resources Information Center
Alonzo, Julie; Lai, Cheng Fei; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
ERIC Educational Resources Information Center
Lai, Cheng Fei; Alonzo, Julie; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
ERIC Educational Resources Information Center
Lai, Cheng Fei; Alonzo, Julie; Tindal, Gerald
2009-01-01
In this technical report, we describe the development and piloting of a series of mathematics progress monitoring measures intended for use with students in grades kindergarten through eighth grade. These measures, available as part of easyCBM[TM], an online progress monitoring assessment system, were developed in 2007 and 2008 and administered to…
Christopoulos, Georgios; Kandzari, David E; Yeh, Robert W; Jaffer, Farouc A; Karmpaliotis, Dimitri; Wyman, Michael R; Alaswad, Khaldoon; Lombardi, William; Grantham, J Aaron; Moses, Jeffrey; Christakopoulos, Georgios; Tarar, Muhammad Nauman J; Rangan, Bavana V; Lembo, Nicholas; Garcia, Santiago; Cipher, Daisha; Thompson, Craig A; Banerjee, Subhash; Brilakis, Emmanouil S
2016-01-11
This study sought to develop a novel parsimonious score for predicting technical success of chronic total occlusion (CTO) percutaneous coronary intervention (PCI) performed using the hybrid approach. Predicting technical success of CTO PCI can facilitate clinical decision making and procedural planning. We analyzed clinical and angiographic parameters from 781 CTO PCIs included in PROGRESS CTO (Prospective Global Registry for the Study of Chronic Total Occlusion Intervention) using a derivation and validation cohort (2:1 sampling ratio). Variables with strong association with technical success in multivariable analysis were assigned 1 point, and a 4-point score was developed from summing all points. The PROGRESS CTO score was subsequently compared with the J-CTO (Multicenter Chronic Total Occlusion Registry in Japan) score in the validation cohort. Technical success was 92.9%. On multivariable analysis, factors associated with technical success included proximal cap ambiguity (beta coefficient [b] = 0.88), moderate/severe tortuosity (b = 1.18), circumflex artery CTO (b = 0.99), and absence of "interventional" collaterals (b = 0.88). The resulting score demonstrated good calibration and discriminatory capacity in the derivation (Hosmer-Lemeshow chi-square = 2.633; p = 0.268, and receiver-operator characteristic [ROC] area = 0.778) and validation (Hosmer-Lemeshow chi-square = 5.333; p = 0.070, and ROC area = 0.720) subset. In the validation cohort, the PROGRESS CTO and J-CTO scores performed similarly in predicting technical success (ROC area 0.720 vs. 0.746, area under the curve difference = 0.026, 95% confidence interval = -0.093 to 0.144). The PROGRESS CTO score is a novel useful tool for estimating technical success in CTO PCI performed using the hybrid approach. Copyright © 2016 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.
John, D.A.; Sisson, T.W.; Breit, G.N.; Rye, R.O.; Vallance, J.W.
2008-01-01
Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8??km3 Osceola Mudflow (5600??y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz-alunite, quartz-topaz, quartz-pyrophyllite, quartz-dickite/kaolinite, and quartz-illite (all with pyrite). Clasts of smectite-pyrite and steam-heated opal-alunite-kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite-pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite-pyrite assemblages, whereas the proximal Electron Mudflow and a < 100??y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite-pyrite alteration within 1??km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H2S in the unsaturated zone above the water table. Weakly developed smectite-pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal-mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (??? 8??km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1-1.5??km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower
Patra, Partha; Natarajan, K A
2006-06-15
Selective separation of pyrite and galena from mixture of the two minerals was achieved through interaction with cells and metabolic products from a culture of Paenibacillus polymyxa. Adsorption of cells and metabolic products onto minerals and electrokinetic studies of minerals after interaction with cells and metabolic products were carried out to examine the resulting surface modification on the mineral surfaces. Flocculation and flotation techniques were successfully applied in the selective separation of minerals after bacterial interaction. The effect of varying conditions for production of extracellular polysaccharides and protein provided an insight into the possible mechanism involved in microbially induced flocculation and flotation of pyrite and galena.
DOT National Transportation Integrated Search
2000-01-01
The following progress report is intended to highlight the significant activities of the Florida Transit Training Program and Florida Technical Assistant Program. The following progress report is intended to highlight the significant activities of th...
DOT National Transportation Integrated Search
2001-01-01
The following progress report is intended to highlight the significant activities of the Florida Transit Training Program and Florida Technical Assistant Program for the 2001 year. Activities of the Florida Statewide Transit Training Program are pres...
NASA Astrophysics Data System (ADS)
Sillitoe, Richard H.
2018-06-01
Radiometric ages for supergene alunite and jarosite effectively date the oxidation of former concentrations of pyrite and any associated sulfide minerals. These K-bearing sulfate minerals, formed under low-pH conditions, are uncommon supergene products in low-sulfidation epithermal deposits because of the general paucity of pyrite for acid generation. For this reason, the age of supergene oxidation—locally to depths of 200 m or more—in the epithermal Au-Ag deposits of the Deseado massif, located in the extra-Andean foreland of Patagonia, southern Argentina, has remained unknown. Although, theoretically, the oxidation could have taken place anytime between the Late Jurassic, when the Au-Ag mineralization formed, and Pleistocene, K-Ar ages for alunite and jarosite from two widely separated and unusually pyritic, Ag-bearing hydrothermal breccias (Lejano and Libanesa) show it to have been mid-Miocene, 13.8 ± 1.8 Ma. This is the time when the Deseado massif underwent appreciable regional-scale tectonic uplift and valley incision, following 140 myr during which the region was topographically subdued and the site of either fluvio-lacustrine or shallow-marine sedimentation. The uplift, combined with increasing aridity due to the orographic rain shadow caused by growth of the Patagonian Andes to the west and enhanced by global cooling, would have depressed regional groundwater tables, thereby promoting the supergene sulfide oxidation. The mid-Miocene uplift appears to have been triggered by development of a slab tear and slab window beneath the Deseado massif during early stages of subduction of the Chile oceanic-ridge spreading center at the Pacific margin. Supergene sulfide oxidation in both the Deseado massif and Atacama Desert of northern Chile was the result of Cenozoic uplift during progressive aridification, although the causes of these phenomena were radically different. However, when the supergene oxidation was taking place in the Deseado massif, up to 30 myr of supergene activity in the Atacama Desert were coming to an end because of the onset of hyperaridity.
76 FR 64083 - Reliability Technical Conference; Notice of Technical Conference
Federal Register 2010, 2011, 2012, 2013, 2014
2011-10-17
... Technical Conference; Notice of Technical Conference Take notice that the Federal Energy Regulatory Commission will hold a Technical Conference on Tuesday, November 29, 2011, from 1 p.m. to 5 p.m. and... System. The conference will explore the progress made on the priorities for addressing risks to...
48 CFR 2052.211-70 - Preparation of technical reports.
Code of Federal Regulations, 2014 CFR
2014-10-01
....211-70 Preparation of technical reports. As prescribed at 2011.104-70(a), the contracting officer... Reports (JAN 1993) All technical reports required by Section C and all Technical Progress Reports required... 48 Federal Acquisition Regulations System 6 2014-10-01 2014-10-01 false Preparation of technical...
48 CFR 2052.211-70 - Preparation of technical reports.
Code of Federal Regulations, 2012 CFR
2012-10-01
....211-70 Preparation of technical reports. As prescribed at 2011.104-70(a), the contracting officer... Reports (JAN 1993) All technical reports required by Section C and all Technical Progress Reports required... 48 Federal Acquisition Regulations System 6 2012-10-01 2012-10-01 false Preparation of technical...
48 CFR 2052.211-70 - Preparation of technical reports.
Code of Federal Regulations, 2010 CFR
2010-10-01
....211-70 Preparation of technical reports. As prescribed at 2011.104-70(a), the contracting officer... Reports (JAN 1993) All technical reports required by Section C and all Technical Progress Reports required... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true Preparation of technical...
48 CFR 2052.211-70 - Preparation of technical reports.
Code of Federal Regulations, 2013 CFR
2013-10-01
....211-70 Preparation of technical reports. As prescribed at 2011.104-70(a), the contracting officer... Reports (JAN 1993) All technical reports required by Section C and all Technical Progress Reports required... 48 Federal Acquisition Regulations System 6 2013-10-01 2013-10-01 false Preparation of technical...
48 CFR 2052.211-70 - Preparation of technical reports.
Code of Federal Regulations, 2011 CFR
2011-10-01
....211-70 Preparation of technical reports. As prescribed at 2011.104-70(a), the contracting officer... Reports (JAN 1993) All technical reports required by Section C and all Technical Progress Reports required... 48 Federal Acquisition Regulations System 6 2011-10-01 2011-10-01 false Preparation of technical...
NASA Astrophysics Data System (ADS)
Guevremont, J. M.; Strongin, D. R.; Schoonen, M. A. A.
1997-11-01
Studies are presented that investigate the adsorption and binding of CH 3OH and H 2O on the atomically clean (100) crystallographic plane of pyrite, FeS 2. Temperature programmed desorption suggests that both reactants adsorb molecularly at 90 K and desorb thermally between 170 and 400 K depending on the surface coverage. Photoemission of adsorbed xenon (PAX) suggests that the surface of pyrite is heterogeneous and contains a significant fraction of defect sites that are believed to be, at least in part, anion vacancy or sulfur-deficient sites. An upper limit of 0.2 is proposed for the fraction of surface sites that are defects on FeS 2(100). PAX indicates that these defect sites at low adsorbate coverage serve as the exclusive binding sites for H 2O and CH 3OH adsorbate. We speculate, on the basis of our ability to interpret PAX data for pyrite, that PAX may be of use for understanding the effect of short range order on adsorbate binding on other complex mineral surfaces. On the basis of high resolution electron energy loss spectroscopy, it is found that some dissociation of the adsorbate occurs on the pyrite. Vibrational data obtained with this technique suggests that FeO species result from the adsorbate decomposition. After saturation of the defect sites, further molecular adsorption is accommodated on the less reactive surface that we postulate is largely disulfide, the characteristic structural group of pyrite.
Arsenic release during managed aquifer recharge (MAR)
NASA Astrophysics Data System (ADS)
Pichler, T.; Lazareva, O.; Druschel, G.
2013-12-01
The mobilization and addition of geogenic trace metals to groundwater is typically caused by anthropogenic perturbations of the physicochemical conditions in the aquifer. This can add dangerously high levels of toxins to groundwater, thus compromising its use as a source of drinking water. In several regions world-wide, aquifer storage and recovery (ASR), a form of managed aquifer recharge (MAR), faces the problem of arsenic release due to the injection of oxygenated storage water. To better understand this process we coupled geochemical reactive transport modeling to bench-scale leaching experiments to investigate and verify the mobilization of geogenic arsenic (As) under a range of redox conditions from an arsenic-rich pyrite bearing limestone aquifer in Central Florida. Modeling and experimental observations showed similar results and confirmed the following: (1) native groundwater and aquifer matrix, including pyrite, were in chemical equilibrium, thus preventing the release of As due to pyrite dissolution under ambient conditions; (2) mixing of oxygen-rich surface water with oxygen-depleted native groundwater changed the redox conditions and promoted the dissolution of pyrite, and (3) the behavior of As along a flow path was controlled by a complex series of interconnected reactions. This included the oxidative dissolution of pyrite and simultaneous sorption of As onto neo-formed hydrous ferric oxides (HFO), followed by the reductive dissolution of HFO and secondary release of adsorbed As under reducing conditions. Arsenic contamination of drinking water in these systems is thus controlled by the re-equilibration of the system to more reducing conditions rather than a purely oxidative process.
Geology of the Eymir iron mine, Edremit, Turkey
Jacobson, Herbert Samuel; Turet, Erdogan
1972-01-01
The Eymir mine near Edremit on Turkey's Aegean coast (long 27?30'E.,1at 39?36'N.) was investigated as part of the Maden Tetkik ve Arama Enstitutsu (MTA)-U. S. Geological Survey (USGS) mineral exploration and training project, for the purpose of increasing the known mineral reserves. Geologic mapping of the mine area indicates that hematite is restricted to argillized, silicified, and pyritized dacite and possibly andesite. Hematite is present as massive replacements, impregnations, disseminations, and fracture fillings. Most of the upper part of the iron deposit consists of a breccia composed mostly of silicifiled dacite fragments in a hematite matrix. The iron deposit was apparently formed in three steps: 1. Argillation, silicification, and pyritization of the andesitic lava and dacite units as a result of a regional intrusion. 2. Intrusion of the Dere Oren dacite stock, with associated faulting, fracturing, and breccia formation at the surface. 3. Deposition of hematite by oxidation of pyrite, and transfer of iron via fractures and faults by hydrothermal or meteoric fluids. The Eymir iron deposit is a blanketlike deposit on the crest of the Sivritepe-Eymir ridge. It is 1300 meters long, 80 to 450 meters wide, and has an average thickness of 18.6 meters. Drill holes in the deposit show the iron content to range from 32.0 to 57.6 percent, and to average 46.5 percent. Most of the gangue is silica, and an arsenic impurity averaging 0.39 percent is present. Most of the deposit cannot be utilized as iron ore because of low iron content, high silica content, and high arsenic content. Ore-dressing tests have shown that it is feasible to concentrate the low-grade material, producing a concentrate having increased iron content and reduced silica content. Tests have shown also that the arsenic content of the ore can be reduced substantially by sintering. Further tests and economic feasibility studies are necessary to determine whether an economic marketable iron ore can be produced. If such studies indicate the technical and economic feasibility of utilizing all the Eymir iron deposit, detailed additional studies are recommended including: 1. A detailed drilling and sampling program to include 60 drill holes averaging 40 meters in depth and detailed sampling of mine dumps. 2. Pilot-plant testing of concentration and sintering procedures. 3. A detailed pre-investment economic feasibility study.
Wilke, Franziska D H; Schettler, Georg; Vieth-Hillebrand, Andrea; Kühn, Michael; Rothe, Heike
2018-05-18
The production of gas from unconventional resources became an important position in the world energy economics. In 2012, the European Commission's Joint Research Centre estimate 16 trillion cubic meters (Tcm) of technically recoverable shale gas in Europe. Taking into account that the exploitation of unconventional gas can be accompanied by serious health risks due to the release of toxic chemical components and natural occurring radionuclides into the return flow water and their near-surface accumulation in secondary precipitates, we investigated the release of U, Th and Ra from black shales by interaction with drilling fluids containing additives that are commonly employed for shale gas exploitation. We performed leaching tests at elevated temperatures and pressures with an Alum black shale from Bornholm, Denmark and a Posidonia black shale from Lower Saxony, Germany. The Alum shale is a carbonate free black shale with pyrite and barite, containing 74.4 μg/g U. The Posidonia shales is a calcareous shale with pyrite but without detectable amounts of barite containing 3.6 μg/g U. Pyrite oxidized during the tests forming sulfuric acid which lowered the pH on values between 2 and 3 of the extraction fluid from the Alum shale favoring a release of U from the Alum shale to the fluid during the short-term and in the beginning of the long-term experiments. The activity concentration of 238 U is as high as 23.9 mBq/ml in the fluid for those experiments. The release of U and Th into the fluid is almost independent of pressure. The amount of uranium in the European shales is similar to that of the Marcellus Shale in the United States but the daughter product of 238 U, the 226 Ra activity concentrations in the experimentally derived leachates from the European shales are quite low in comparison to that found in industrially derived flowback fluids from the Marcellus shale. This difference could mainly be due to missing Cl in the reaction fluid used in our experiments and a lower fluid to solid ratio in the industrial plays than in the experiments due to subsequent fracking and minute cracks from which Ra can easily be released. Copyright © 2018 Elsevier Ltd. All rights reserved.
Microbially induced flotation and flocculation of pyrite and sphalerite.
Patra, Partha; Natarajan, K A
2004-07-15
Cells of Paenibacillus polymyxa and their metabolite products were successfully utilized to achieve selective separation of sphalerite from pyrite, through microbially induced flocculation and flotation. Adsorption studies and electrokinetic investigations were carried out to understand the changes in the surface chemistry of bacterial cells and the minerals after mutual interaction. Possible mechanisms in microbially induced flotation and flocculation are outlined.
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.
NASA Astrophysics Data System (ADS)
Wen, Xiangli; Liang, Yuxuan; Bai, Pengpeng; Luo, Bingwei; Fang, Teng; Yue, Luo; An, Teng; Song, Weiyu; Zheng, Shuqi
2017-11-01
The thermodynamic properties of Fe-S compounds with different crystal structure are very different. In this study, the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2) were investigated by first-principles calculations. Examination of the electronic density of states shows that mackinawite (FeS) is metallic and that pyrite (FeS2) is a semiconductor with a band gap of Eg = 1.02 eV. Using the stress-strain method, the elastic properties including the bulk modulus and shear modulus were derived from the elastic Cij data. Density functional perturbation theory (DFPT) calculations within the quasi-harmonic approximation (QHA) were used to calculate the thermodynamic properties, and the two Fe-S compounds are found to be dynamically stable. The isothermal bulk modulus, thermal expansion coefficient, heat capacities, Gibbs free energy and entropy of the Fe-S compounds are obtained by first-principles phonon calculations. Furthermore, the temperature of the mackinawite (FeS) ⟶ pyrite (FeS2) phase transition at 0 GPa was predicted. Based on the calculation results, the model for prediction of Fe-S compounds in the Fe-H2S-H2O system was improved.
Growth and Characterization of Pyrite Thin Films for Photovoltaic Applications
NASA Astrophysics Data System (ADS)
Wertheim, Alex
A series of pyrite thin films were synthesized using a novel sequential evaporation technique to study the effects of substrate temperature on deposition rate and micro-structure of the deposited material. Pyrite was deposited in a monolayer-by-monolayer fashion using sequential evaporation of Fe under high vacuum, followed by sulfidation at high S pressures (typically > 1 mTorr to 1 Torr). Thin films were synthesized using two different growth processes; a one-step process in which a constant growth temperature is maintained throughout growth, and a three-step process in which an initial low temperature seed layer is deposited, followed by a high temperature layer, and then finished with a low temperature capping layer. Analysis methods to analyze the properties of the films included Glancing Angle X-Ray Diffraction (GAXRD), Rutherford Back-scattering Spectroscopy (RBS), Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectroscopy (SIMS), 2-point IV measurements, and Hall effect measurements. Our results show that crystallinity of the pyrite thin film improves and grain size increases with increasing substrate temperature. The sticking coefficient of Fe was found to increase with increasing growth temperature, indicating that the Fe incorporation into the growing film is a thermally activated process.
Thermoluminescence kinetics of pyrite (FeS2)
NASA Astrophysics Data System (ADS)
Silverman, A. N.; Levy, P. W.; Kierstead, J. A.
Thermoluminescence of pyrite (FeS2) was 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 approximately 90 and 250 C, and two chemiluminescence (CL) peaks at approximately 350 and 430 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(sub max)) with dose, and the retrapping to recombination cross section ratio (sigma) of the large 250 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, than by the 1st and 2nd order equations.
Matrix composition and community structure analysis of a novel bacterial pyrite leaching community.
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.
REACTOR PHYSICS QUARTERLY REPORT JANUARY, FEBRUARY, MARCH 1970
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schmid, L. C.; Clayton, E. D.; Heineman, R. E.
1970-05-01
The objective of the Reactor Physics Quarterly Report is to inform the scientific community in a timely manner of the technical progress made on the many phases of reactor physics work within the laboratory. The report contains brief technical discussions of accomplishments in all areas where significant progress has been made during the quarter.
George A. Olah, Carbocation and Hydrocarbon Chemistry
. Final Technical Report. [HF:BF{sub 2}/H{sub 2}] , DOE Technical Report, 1980 Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984 , DOE Technical Report, 1984 Superacid Catalyzed Coal Conversion Chemistry. Final Technical Report
Bors, Philip A; Kemner, Allison; Fulton, John; Stachecki, Jessica; Brennan, Laura K
2015-01-01
As part of Robert Wood Johnson Foundation's Healthy Kids, Healthy Communities (HKHC) national grant program, a technical assistance team designed the HKHC Community Dashboard, an online progress documentation and networking system. The Dashboard was central to HKHC's multimethod program evaluation and became a communication interface for grantees and technical assistance providers. The Dashboard was designed through an iterative process of identifying needs and priorities; designing the user experience, technical development, and usability testing; and applying visual design. The system was created with an open-source content management system and support for building an online community of users. The site developer trained technical assistance providers at the national program office and evaluators, who subsequently trained all 49 grantees. Evaluators provided support for Dashboard users and populated the site with the bulk of its uploaded tools and resource documents. The system tracked progress through an interactive work plan template, regular documentation by local staff and partners, and data coding and analysis by the evaluation team. Other features included the ability to broadcast information to Dashboard users via e-mail, event calendars, discussion forums, private messaging, a resource clearinghouse, a technical assistance diary, and real-time progress reports. The average number of Dashboard posts was 694 per grantee during the grant period. Technical assistance providers and grantees uploaded a total of 1304 resource documents. The Dashboard functions with the highest grantee satisfaction were its interfaces for sharing and progress documentation. A majority of Dashboard users (69%) indicated a preference for continued access to the Dashboard's uploaded resource documents. The Dashboard was a useful and innovative tool for participatory evaluation of a large national grant program. While progress documentation added some burden to local project staff, the system proved to be a useful resource-sharing technology.
Zhai, Shiyan; Song, Genxin; Qin, Yaochen; Ye, Xinyue; Lee, Jay
2017-01-01
This study aims to evaluate the impacts of climate change and technical progress on the wheat yield per unit area from 1970 to 2014 in Henan, the largest agricultural province in China, using an autoregressive distributed lag approach. The bounded F-test for cointegration among the model variables yielded evidence of a long-run relationship among climate change, technical progress, and the wheat yield per unit area. In the long run, agricultural machinery and fertilizer use both had significantly positive impacts on the per unit area wheat yield. A 1% increase in the aggregate quantity of fertilizer use increased the wheat yield by 0.19%. Additionally, a 1% increase in machine use increased the wheat yield by 0.21%. In contrast, precipitation during the wheat growth period (from emergence to maturity, consisting of the period from last October to June) led to a decrease in the wheat yield per unit area. In the short run, the coefficient of the aggregate quantity of fertilizer used was negative. Land size had a significantly positive impact on the per unit area wheat yield in the short run. There was no significant short-run or long-run impact of temperature on the wheat yield per unit area in Henan Province. The results of our analysis suggest that climate change had a weak impact on the wheat yield, while technical progress played an important role in increasing the wheat yield per unit area. The results of this study have implications for national and local agriculture policies under climate change. To design well-targeted agriculture adaptation policies for the future and to reduce the adverse effects of climate change on the wheat yield, climate change and technical progress factors should be considered simultaneously. In addition, adaptive measures associated with technical progress should be given more attention.
Qin, Yaochen; Lee, Jay
2017-01-01
This study aims to evaluate the impacts of climate change and technical progress on the wheat yield per unit area from 1970 to 2014 in Henan, the largest agricultural province in China, using an autoregressive distributed lag approach. The bounded F-test for cointegration among the model variables yielded evidence of a long-run relationship among climate change, technical progress, and the wheat yield per unit area. In the long run, agricultural machinery and fertilizer use both had significantly positive impacts on the per unit area wheat yield. A 1% increase in the aggregate quantity of fertilizer use increased the wheat yield by 0.19%. Additionally, a 1% increase in machine use increased the wheat yield by 0.21%. In contrast, precipitation during the wheat growth period (from emergence to maturity, consisting of the period from last October to June) led to a decrease in the wheat yield per unit area. In the short run, the coefficient of the aggregate quantity of fertilizer used was negative. Land size had a significantly positive impact on the per unit area wheat yield in the short run. There was no significant short-run or long-run impact of temperature on the wheat yield per unit area in Henan Province. The results of our analysis suggest that climate change had a weak impact on the wheat yield, while technical progress played an important role in increasing the wheat yield per unit area. The results of this study have implications for national and local agriculture policies under climate change. To design well-targeted agriculture adaptation policies for the future and to reduce the adverse effects of climate change on the wheat yield, climate change and technical progress factors should be considered simultaneously. In addition, adaptive measures associated with technical progress should be given more attention. PMID:28950027
Supply Chain Sustainability Analysis of Whole Algae Hydrothermal Liquefaction and Upgrading
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pegallapati, Ambica Koushik; Dunn, Jennifer B.; Frank, Edward D.
2015-04-01
The Department of Energy's Bioenergy Technology Office (BETO) collaborates with a wide range of institutions towards the development and deployment of biofuels and bioproducts. To facilitate this effort, BETO and its partner national laboratories develop detailed techno-economic assessments (TEA) of biofuel production technologies as part of the development of design cases and state of technology (SOT) analyses. A design case is a TEA that outlines a target case for a particular biofuel pathway. It enables preliminary identification of data gaps and research and development needs and provides goals and targets against which technology progress is assessed. On the other hand,more » an SOT analysis assesses progress within and across relevant technology areas based on actual experimental results relative to technical targets and cost goals from design cases and includes technical, economic, and environmental criteria as available. (SOT) analyses. A design case is a TEA that outlines a target case for a particular biofuel pathway. It enables preliminary identification of data gaps and research and development needs and provides goals and targets against which technology progress is assessed. On the other hand, an SOT analysis assesses progress within and across relevant technology areas based on actual experimental results relative to technical targets and cost goals from design cases and includes technical, economic, and environmental criteria as available. (SOT) analyses. A design case is a TEA that outlines a target case for a particular biofuel pathway. It enables preliminary identification of data gaps and research and development needs and provides goals and targets against which technology progress is assessed. On the other hand, an SOT analysis assesses progress within and across relevant technology areas based on actual experimental results relative to technical targets and cost goals from design cases and includes technical, economic, and environmental criteria as available.« less
NASA Astrophysics Data System (ADS)
Kobayashi, Y.; Yamaguchi, K. E.; Sakamoto, R.; Naraoka, H.; Kiyokawa, S.; Ikehara, M.; Ito, T.
2012-12-01
Co-evolution of early life and surface environment has been one of the most important events on Earth. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 billion years ago. But geological and geochemical evidence suggest possibility of much earlier (by hundreds of millions of years) existence of oxic atmosphere and oceans. In order to further investigate the mystery of biological and environmental evolution, we conducted continental drilling in northwestern Pilbara, Western. Australia, to obtain 3.2 billion-years-old least-metamorphosed drillcore black shale samples (DXCL-DP:Dixon Island - Cleaverville Drilling Project; Yamaguchi et al., 2009). Preliminary stable isotope analyses using these samples suggested that photosynthetic organisms produced organic matter (Hosoi et al., 2011), nitrogen fixing bacteria were intermittently active (Yamada et al., 2011), and sulfate-reducing bacteria were active in environment with a limited supply of sulfate (Sakamoto et al., 2011) in the 3.2 Ga ocean. Bulk S isotope compositions could only provide limited information on the biogeochemical cycling of sedimentary S, because it is normally present as different facies (acid-volatile sulfur: AVS, pyrite: FeS2, sulfate, organic sulfur: Sorg, and elemental sulfur: S0) that depend on physicochemical and biological conditions. Therefore, abundance and isotope ratios of these species possess very useful information on oceanic and diagenetic conditions such as redox state and microbiological activity. In order to constrain biogeochemical cycling of S in the 3.2 Ga ocean, we conducted sequential extraction analysis using the DXCL-DP black shales to obtain different S-bearing species and S isotopic analysis. Average S contents for each form of S-bearing species were: ΣS = 2.56 wt.%, AVS = 0.02 wt.%, pyrite = 1.61 wt.%, and sulfate = 0.57 wt%. Relationship between amounts of pyrite-S and organic C suggest presence of syngenetic pyrite (formed in water column) as well as diagenetic pyrite. Average S isotope compositions are: pyrite = 12.3±6.3 ‰, sulfate = 17.3 ± 7.1 ‰, and difference between them are up to as high as 16.8 ‰. These results show that depositional environment was probably close to the modern Black Sea, where sulfate-reducing bacteria are active in anaerobic water mass in semi-closed deep basin, with a limited supply of sulfate from the oxic surface ocean.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brown, R.C.; Dawson, M.R.; Noble, S.D.
Agglomerates formed in laboratory coal combustion tests were analyzed to determine the chemical and mineral reactions which lead to the cohesion of bed particles. Combustion tests were conducted at 75, 90, 100, and 120% theoretical air values. The test at 75% theoretical air resulted in the formation of bed agglomerates within 30 minutes. Agglomerates which formed at the lower theoretical air values were compared to unagglomerated bed samples by X-ray diffraction analyses. Polished thin sections of the agglomerates were made for optical and scanning electron microscopy. The results of these analyses indicate there were, in a broad sense, two typesmore » of mineralogic reactions which lead to the cohesion of bed particles in the agglomerates. One mechanism of cohesion resulted from the melting of bed particles to form a viscous material which bridged other bed particles. Based on the chemical composition of the glass (which resulted from the melt), this material was probably derived from aluminosilicate minerals in the sand bed or from clays within the coal. Because of the high iron content in these glasses (4 to 5 wt%), it is likely that iron pyrites in the coal were involved in fluxing reactions. In addition, MgO appears to be relatively high in the glasses. It is suspected that Ca-Mg carbonates (dolomite) from the bed sand are also involved in mineralogic reactions with the aluminosilicate melt. The second type of mineralogic reaction appears to be a reaction involving calcium and magnesium with other bed particles and with the aluminosilicate melt to form new mineral phases. Although the composition of these phases is somewhat variable, some resemble single-chain silicates or pyroxenes.« less
JPRS Report, Science & Technology, USSR: Materials Science
1988-02-22
on 55 a known precision flotation method of denstiy measurement. Closed porosity- was determined by measuring the density of specimens, subsequent...for producing sulphuric acid from pyrite concentrates, which are waste of various production processes and are stored in large quantities in the...Buryat ASSR as a result of centralized processing thereof. In order to do this, one should create a territorial center for processing pyrite
NASA Astrophysics Data System (ADS)
Andre, B. J.; Rajaram, H.; Silverstein, J.
2010-12-01
Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction diffusion model at the scale of a single rock is developed incorporating the proposed kinetic rate expressions. Simulations of initiation, washout and AMD flows are discussed to gain a better understanding of the role of porosity, effective diffusivity and reactive surface area in generating AMD. Simulations indicate that flow boundary conditions control generation of acid rock drainage as porosity increases.
Sulphur cycling in a Neoarchaean microbial mat.
Meyer, N R; Zerkle, A L; Fike, D A
2017-05-01
Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass-independent fractionation (S-MIF) signal in rocks <~2.4 Ga has been used to date a dramatic rise in atmospheric oxygen levels. However, intricacies of the S-cycle before the Great Oxidation Event remain poorly understood. For example, the isotope composition of coeval atmospherically derived sulphur species is still debated. Furthermore, variation in Archaean pyrite δ 34 S values has been widely attributed to microbial sulphate reduction (MSR). While petrographic evidence for Archaean early-diagenetic pyrite formation is common, textural evidence for the presence and distribution of MSR remains enigmatic. We combined detailed petrographic and in situ, high-resolution multiple S-isotope studies (δ 34 S and Δ 33 S) using secondary ion mass spectrometry (SIMS) to document the S-isotope signatures of exceptionally well-preserved, pyritised microbialites in shales from the ~2.65-Ga Lokammona Formation, Ghaap Group, South Africa. The presence of MSR in this Neoarchaean microbial mat is supported by typical biogenic textures including wavy crinkled laminae, and early-diagenetic pyrite containing <26‰ μm-scale variations in δ 34 S and Δ 33 S = -0.21 ± 0.65‰ (±1σ). These large variations in δ 34 S values suggest Rayleigh distillation of a limited sulphate pool during high rates of MSR. Furthermore, we identified a second, morphologically distinct pyrite phase that precipitated after lithification, with δ 34 S = 8.36 ± 1.16‰ and Δ 33 S = 5.54 ± 1.53‰ (±1σ). We propose that the S-MIF signature of this secondary pyrite does not reflect contemporaneous atmospheric processes at the time of deposition; instead, it formed by the influx of later-stage sulphur-bearing fluids containing an inherited atmospheric S-MIF signal and/or from magnetic isotope effects during thermochemical sulphate reduction. These insights highlight the complementary nature of petrography and SIMS studies to resolve multigenerational pyrite formation pathways in the geological record. © 2017 The Authors Geobiology Published by John Wiley & Sons Ltd.
Graham, Garth; Hitzman, Murray W.; Zieg, Jerry
2012-01-01
The northern margin of the Helena Embayment contains extensive syngenetic to diagenetic massive pyrite horizons that extend over 25 km along the Volcano Valley-Buttress fault zone and extend up to 8 km basinward (south) within the Mesoproterozoic Newland Formation. The Sheep Creek Cu-Co deposit occurs within a structural block along a bend in the fault system, where replacement-style chalcopyrite mineralization is spatially associated mostly with the two stratigraphically lowest massive pyrite zones. These mineralized pyritic horizons are intercalated with debris flows derived from synsedimentary movement along the Volcano Valley-Buttress fault zone. Cominco American Inc. delineated a geologic resource of 4.5 Mt at 2.5% Cu and 0.1% Co in the upper sulfide zone and 4 Mt at 4% Cu within the lower sulfide zone. More recently, Tintina Resources Inc. has delineated an inferred resource of 8.48 Mt at 2.96% Cu, 0.12% Co, and 16.4 g/t Ag in the upper sulfide zone. The more intact upper sulfide zone displays significant thickness variations along strike thought to represent formation in at least three separate subbasins. The largest accumulation of mineralized sulfide in the upper zone occurs as an N-S–trending body that thickens southward from the generally E trending Volcano Valley Fault and probably occupies a paleograben controlled by normal faults in the hanging wall of the Volcano Valley Fault. Early microcrystalline to framboidal pyrite was accompanied by abundant and local barite deposition in the upper and lower sulfide zones, respectively. The sulfide bodies underwent intense (lower sulfide zone) to localized (upper sulfide zone) recrystallization and overprinting by coarser-grained pyrite and minor marcasite that is intergrown with and replaces dolomite. Silicification and paragenetically late chalcopyrite, along with minor tennantite in the upper sulfide zone, replaces fine-grained pyrite, barite, and carbonate. The restriction of chalcopyrite to inferred synsedimentary E- and northerly trending faults and absence of definitive zonation with respect to the Laramide Volcano Valley Fault in the lower sulfide zone suggest a diagenetic age related to basin development for the Sheep Creek Cu-Co-Ag deposit.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Moncur, Michael C.; Paktunc, Dogan; Jean Birks, S.
Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrationsmore » in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(-I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.« less
Lithologically controlled invisible gold, Yukon, Canada
NASA Astrophysics Data System (ADS)
MacKenzie, Doug; Craw, Dave; Finnigan, Craig
2015-02-01
The newly discovered Cretaceous Coffee orogenic gold deposit (>4 Moz resource) consists of an extensive oxidised zone developed on primary sulphidic rock. The primary mineralised rock is characterised by invisible gold in arsenian pyrite that has replaced biotite in selected host rocks. The deposit has a cryptic surface expression and is an example of an extremely subtle exploration target. Hydrothermal emplacement was controlled by extensional fractures, with breccias, but most mineralisation was focused on biotite-bearing granitic gneiss, metasedimentary gneisses, and younger biotite granite. Fine-grained (<0.1 mm) arsenian pyrite replaced biotite along mineral cleavage planes and followed biotite-rich metamorphic and post-metamorphic structural fabrics. Arsenian pyrite also formed overgrowths on earlier coarse-grained (up to 2 mm) barren hydrothermal pyrite. Arsenian pyrite is concentrically zoned on the 1-10-μm scale with respect to As, Sb, and Au contents and typically contains ˜5 wt% As, ˜500 mg/kg Sb, and ˜500 mg/kg Au, in solid solution. Biotite replacement was accompanied by sericitisation, silicification, and ankerite impregnation. Hydrothermal alteration involved dilution and localised depletion of K, Na, and Al in silicified host rocks, but most Ca, Mg, and Fe concentrations remained broadly constant. Magnesium-rich ultramafic host rocks were only weakly mineralised with auriferous arsenian pyrite and have fuchsite and magnesite alteration. Near-surface oxidation has liberated nanoparticulate and microparticulate supergene gold, which remains essentially invisible. Varying degrees of oxidation extend as deep as 250 m below the present subdued topographic surface, well beyond the present vadose zone, and this deep oxidation may have occurred during post-mineralisation uplift and erosion in the Cretaceous. Oxidation has leached some As from the surficial mineralised rocks, decreasing the geochemical signal, which is also obscured by the localised presence of high background As (up to 100 mg/kg) in metasedimentary quartzites in the region. Antimony provides more reliable soil anomalies than As, but most Sb anomalies are <100 mg/kg. The persistence of invisible gold into the extensive supergene zone, with little gold particle size enhancement, has ensured that no placer deposits have formed in nearby streams, further restricting the surface footprint and Au dispersal halo of this subtle exploration target.
Hower, J.C.; Robertson, J.D.; Wong, A.S.; Eble, C.F.; Ruppert, L.F.
1997-01-01
The Middle Pennsylvanian Breathitt Formation (Westphalian B) Pond Creek and Fire Clay coal beds are the 2 largest producing coal beds in eastern Kentucky. Single channel samples from 22 localities in the Pond Creek coal bed were obtained from active coal mines in Pike and Martin Countries, Kentucky, and a total of 18 Fire Clay coal bed channel samples were collected from localities in the central portion of the coal field. The overall objective of this study was to investigate the concentration and distribution of potentially hazardous elements in the Fire Clay and Pond Creek coal beds, with particular emphasis on As and Pb, 2 elements that are included in the 1990 Clean Air Act Amendments as potential air toxics. The 2 coals are discussed individually as the depositional histories are distinct, the Fire Clay coal bed having more sites where relatively high-S lithologies are encountered. In an effort to characterize these coals, 40 whole channel samples, excluding 1-cm partings, were analyzed for major, minor and trace elements by X-ray fluorescence and proton-induced X-ray emission spectroscopy. Previously analyzed samples were added to provide additional geographic coverage and lithotype samples from one site were analyzed in order to provide detail of vertical elemental trends. The As and Pb levels in the Fire Clay coal bed tend to be higher than in the Pond Creek coal bed. One whole channel sample of the Fire Clay coal bed contains 1156 ppm As (ash basis), with a single lithotype containing 4000 ppm As (ash basis). Most of the As and Pb appears to be associated with pyrite, which potentially can be removed in beneficiation (particularly coarser pyrite). Disseminated finer pyrite may not be completely removable by cleaning. In the examination of pyrite conducted in this study, it does not appear that significant concentration of As or Pb occurs in the finer pyrite forms. The biggest potential problem of As- or Pb-enriched pyrite is, therefore, one of refuse disposal.
Geological controls on refractory ore in an orogenic gold deposit, Macraes mine, New Zealand
NASA Astrophysics Data System (ADS)
Petrie, B. S.; Craw, D.; Ryan, C. G.
2005-07-01
The Macraes mine is hosted in an orogenic (mesothermal) gold deposit in metasedimentary rocks of the Otago Schist belt. Much gold occurs within altered schist with minimal silica-addition, and this study focuses on altered schist ore types. The unmineralized host schists are chemically and mineralogically uniform in composition, but include two end-member rock types: feldspathic schist and micaceous schist. Both rock types have undergone hydrothermal alteration along a shallow-dipping foliation-parallel shear zone, but their different rheological properties have affected the style of mineralisation. Micaceous schist has been extensively recrystallized and hydrothermally altered during ductile deformation, to form ores characterized by abundant, disseminated millimetre-scale pyrite cubes (typically 1 2 wt% S) and minor silicification. The earliest pyrite contained Ni and/or As in solid solution and no gold was imaged in these pyrites or later arsenopyrite grains. The ore type is refractory and gold recovery by cyanide leaching is less than 50%, with lowest recovery in rocks that have been less affected by later brittle deformation. In contrast, hydrothermally altered feldspathic schist is characterized by mineralised black microshears and veinlets formed during shear-zone related brittle deformation. Microsheared ore has relatively low sulphur content (<0.7 wt%) and muscovite has been illitised during hydrothermal alteration. Pyrite and arsenopyrite in microshears are fractured and deformed, and contain 1 10 μm blebs of gold. Later pyrite veinlets also contain micron- to submicron-scale inclusions of sphalerite, chalcopyrite, galena, and gold (≤10 microns). Gold in microsheared ore is more readily recoverable than in the refractory ore, although encapsulation of the fine gold grains inhibits cyanidation. Both microsheared ore and disseminated pyritic ore pass laterally into mineralised black shears, which contain hydrothermal graphite and late-stage cataclastic sulphides. This black, sheared ore releases gold readily, but the gold is then adsorbed on to gangue minerals (preg-robbed) and net cyanidation recovery can be less than 50%. Hence, low gold recovery during cyanidation results from (1) poor liberation of gold encapsulated in microcrystalline quartz and unfractured sulphide grains, and (2) preg-robbing of liberated gold during cyanidation. Introduction of pressure-oxidation of ore prior to cynidation has mitigated these issues.
ERIC Educational Resources Information Center
Van Norman, Ethan R.; Nelson, Peter M.; Parker, David C.
2017-01-01
Computer adaptive tests (CATs) hold promise to monitor student progress within multitiered systems of support. However, the relationship between how long and how often data are collected and the technical adequacy of growth estimates from CATs has not been explored. Given CAT administration times, it is important to identify optimal data…
Education, Industrialization and Technical Progress in Mexico. IIEP Research Report No. 6.
ERIC Educational Resources Information Center
Padua, Jorge
This report attempts to analyze the contributions of the educational system and job training programs to industrialization and technical progress in the Conubal zone of the Lower Balsas River of Mexico. The first of the study's three sections consists of two chapters that provide general background. Chapter 1, "Theories of Development and the…
ERIC Educational Resources Information Center
January, Stacy-Ann A.; Ardoin, Scott P.
2015-01-01
Curriculum-based measurement in reading (CBM-R) and the Measures of Academic Progress (MAP) are assessment tools widely employed for universal screening in schools. Although a large body of research supports the validity of CBM-R, limited empirical evidence exists supporting the technical adequacy of MAP or the acceptability of either measure for…
Annual Technical Progress Report for Emergency School Assistance Program, Title 45, 1970-71.
ERIC Educational Resources Information Center
Lindsey, Randall B.
This paper presents a technical progress report of two programs conducted with funds provided under the Emergency School Assistance Program. One, the Mobile Learning Unit, said to have been designed to measure changes in fourth and fifth grade students' self-concept in a reorganized desegregated school environment, focuses on whether a positive…
Third Progress and Information Report of the Vocational-Technical Education Consortium of States.
ERIC Educational Resources Information Center
Lee, Connie W.; And Others
This description of major activities and accomplishments of the Vocational-Technical Education Consortium of the States (V-TECS) since the second progress report of May, 1975, is designed to provide the reader with a basic understanding of the processes and procedures used by the consortium in achieving its major goal: The production of catalogs…
A PSFI-based analysis on the energy efficiency potential of China’s domestic passenger vehicles
NASA Astrophysics Data System (ADS)
Chen, Chuan; Ren, Huanhuan; Zhao, Dongchang
2017-01-01
In this article, China’s domestic passenger vehicles (excluding new energy vehicles) are categorized into two groups: local brand vehicles and vehicles manufactured by joint ventures. Performance-Size-Fuel economy Index (PSFI) will be applied to analyse the speed of technical progress and the future trends of these vehicles. In addition, a forecast on energy efficiency potential of domestic passenger vehicles from 2016 to 2020 will be made based on different Emphasis on Reducing Fuel Consumption (ERFC) scenarios. According to the study, if the process of technical progress continues at its current speed, domestic ICE passenger vehicles will hardly meet Phase IV requirements by 2020 even though companies contribute as much technical progress to fuel consumption reduction as possible.
Advanced Thermal Emission Imaging Systems Definition and Development
NASA Technical Reports Server (NTRS)
Blasius, Karl; Nava, David (Technical Monitor)
2002-01-01
Santa Barbara Remote Sensing (SBRS), Raytheon Company, is pleased to submit this quarterly progress report of the work performed in the third quarter of Year 2 of the Advanced THEMIS Project, July through September 2002. We review here progress in the proposed tasks. During July through September 2002 progress was made in two major tasks, Spectral Response Characterization and Flight Instrument Definition. Because of staffing problems and technical problems earlier in the program we have refocused the remaining time and budget on the key technical tasks. Current technical problems with a central piece of test equipment has lead us to request a 1 quarter extension to the period of performance. This request is being made through a separate letter independent of this report.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stout, D.K.
Flaws are noted in equilibrium growth models which ignore the facts that labor is no longer homogeneous, national governments can no longer guarantee a managed demand, and technical progress is not an independent force. The pace of technical progress is the major variable and increases with competition and certainty in the growth of demand. The outlook for technical progress is examined in the context of productivity, using microprocessor development for illustration. The author takes an optimistic view of new developments in that they do not bring the self-destructive possibility of overpopulation, irreversible damage to the environment, or nuclear war anymore » closer, while having a positive chance to promote a more rewarding relationship between education, work, and life style. The opportunities for positive humanistic changes through microprocessing are confirmed. (DCK)« less
NASA Astrophysics Data System (ADS)
Peng, Xiaotong; Guo, Zixiao; Chen, Shun; Sun, Zhilei; Xu, Hengchao; Ta, Kaiwen; Zhang, Jianchao; Zhang, Lijuan; Li, Jiwei; Du, Mengran
2017-05-01
The microbial anaerobic oxidation of methane (AOM), a key biogeochemical process that consumes substantial amounts of methane produced in seafloor sediments, can lead to the formation of carbonate deposits at or beneath the sea floor. Although Fe oxide-driven AOM has been identified in cold seep sediments, the exact mode by which it may influence the formation of carbonate deposits remains poorly understood. Here, we characterize the morphology, petrology and geochemistry of a methane-derived Fe-rich carbonate pipe in the northern Okinawa Trough (OT). We detect abundant authigenic pyrites, as well as widespread trace Fe, within microbial mat-like carbonate veins in the pipe. The in situ δ34S values of these pyrites range from -3.9 to 31.6‰ (VCDT), suggesting a strong consumption of seawater sulfate by sulfate-driven AOM at the bottom of sulfate reduction zone. The positive δ56Fe values of pyrite and notable enrichment of Fe in the OT pipe concurrently indicate that the pyrites are primarily derived from Fe oxides in deep sediments. We propose that the Fe-rich carbonate pipe formed at the bottom of sulfate reduction zone, below which Fe-driven AOM, rather than Fe-oxide reduction coupled to organic matter degradation, might be responsible for the abundantly available Fe2+ in the fluids from which pyrites precipitated. The Fe-rich carbonate pipe described in this study probably represents the first fossil example of carbonate deposits linked to Fe-driven AOM. Because Fe-rich carbonate deposits have also been found at other cold seeps worldwide, we infer that similar processes may play an essential role in biogeochemical cycling of sub-seafloor methane and Fe at continental margins.
Liu, Juan; Wang, Jin; Chen, Yongheng; Shen, Chuan-Chou; Jiang, Xiuyang; Xie, Xiaofan; Chen, Diyun; Lippold, Holger; Wang, Chunlin
2016-06-01
Thallium (Tl) is a non-essential element in humans and it is considered to be highly toxic. In this study, the contents, sources, and dispersal of Tl were investigated in surface sediments from a riverine system (the western Pearl River Basin, China), whose catchment has been contaminated by mining and roasting of Tl-bearing pyrite ores. The isotopic composition of Pb and total contents of Tl and other relevant metals (Pb, Zn, Cd, Co, and Ni) were measured in the pyrite ores, mining and roasting wastes, and the river sediments. Widespread contamination of Tl was observed in the sediments across the river, with the highest concentration of Tl (17.3 mg/kg) measured 4 km downstream from the pyrite industrial site. Application of a modified Institute for Reference Materials and Measurement (IRMM) sequential extraction scheme in representative sediments unveiled that 60-90% of Tl and Pb were present in the residual fraction of the sediments. The sediments contained generally lower (206)Pb/(207)Pb and higher (208)Pb/(206)Pb ratios compared with the natural Pb isotope signature (1.2008 and 2.0766 for (206)Pb/(207)Pb and (208)Pb/(206)Pb, respectively). These results suggested that a significant fraction of non-indigenous Pb could be attributed to the mining and roasting activities of pyrite ores, with low (206)Pb/(207)Pb (1.1539) and high (208)Pb/(206)Pb (2.1263). Results also showed that approximately 6-88% of Tl contamination in the sediments originated from the pyrite mining and roasting activities. This study highlights that Pb isotopic compositions could be used for quantitatively fingerprinting the sources of Tl contamination in sediments. Copyright © 2016 Elsevier Ltd. All rights reserved.
X-ray photoelectron spectroscopic study of water adsorption on iron sulphide minerals
NASA Astrophysics Data System (ADS)
Knipe, S. W.; Mycroft, J. R.; Pratt, A. R.; Nesbitt, H. W.; Bancroff, G. M.
1995-03-01
Samples of natural pyrrhotite and pyrite were fractured within the analytical chamber of an X-ray photoelectron spectrometer. The pristine mineral surfaces were then exposed, in the absence of oxygen, to total doses of 100, 200, 400, 800, 1400, 28,000, and 300,000 Langmuirs (L) of D2O. X-ray photoelectron spectroscopic (XPS) analyses were performed between each water dose, to investigate the interaction of these iron sulphide surfaces with water vapour. Recorded Fe and S photoelectron spectra showed no evidence of oxidation products on either mineral, even at highest D2O doses, nor could an oxide oxygen signal be fitted in the spectra for either mineral. On pyrrhotite, the O 1s spectra are composed of contributions from dominantly hydroxyl (at 532.0 ± 0.2 eV ) and subordinate chemisorbed water (at 533.5 ± 0.2 eV) signals. The main O is peak on pyrite is also formed from hydroxyl (531.0 ± 0.3 eV) and adsorbed water/hydroxyl (at 532.3 eV) signals. However, some O is spectra recorded on pyrite have peaks at anomalously high binding energies (>535 eV ). The anomalous high binding energy species are attributed to electrically-isolated OH/H2O, as reported elsewhere, and to liquid-like water, which has not previously been described in the literature. Pyrrhotite and pyrite interact with water via fundamentally different processes. Pyrrhotite reaction involves the donation of electron charge through Fe vacancies, whereas the water species detected on pyrite interact with the Fe 3d (eg) molecular orbital, and it is suggested that hydrogen bonding with the disulphide moiety may be important.
On a phase transformation produced by mechanical activation in iron pyrite
NASA Astrophysics Data System (ADS)
Eymery, J.-P.
1999-02-01
The behaviour of pyrite in the process of mechanical milling in air has been examined. Milled powders were characterized by scanning electron microscopy, Mössbauer spectroscopy working in transmission geometry and X-ray diffraction. In the presence of oxygen, pyrite can readily be transformed to ferrous sulphate monohydrate, which indicates that the Fe(II) goes from a low-spin state to to a high-spin state. The transformation mechanism is saturated after about 60hours milling, but however it can be markedly prolonged by further ageing at room temperature. The results also indicate that mechanical milling is a useful room temperature process of material production. On a étudié le comportement de la pyrite au cours de broyages mécaniques réalisés à l'air. Les poudres broyées ont été analysées par microscopie électronique à balayage, spectroscopie Mössbauer fonctionnant en géométrie de transmission et diffraction des rayonsX. En présence d'oxygène, la pyrite se transforme immédiatement en sulfate de fer monohydraté, ce qui correspond pour Fe(II) au passage de l'état bas spin à l'état haut spin. Le mécanisme de la transformation est saturé après 60heures de broyage environ, mais cependant il peut être notablement prolongé par un vieillissement ultérieur à la température ambiante. Les résultats montrent aussi que le broyage mécanique constitue un processus utile de fabrication des matériaux à l'ambiante.
Venus mountain-top mineralogy: Misconceptions about pyrite as the high radar-reflecting phase
NASA Technical Reports Server (NTRS)
Burns, Roger G.; Straub, Darcy W.
1993-01-01
Altitude-dependent, high radar-reflectivity surfaces on Venus are observed on most mountainous volcanic terranes above a planetary radius of about 6054 km. However, high radar-reflectivity areas also occur at lower altitudes in some impact craters and plain terranes. Pyrite (FeS2) is commonly believed to be responsible for the high radar reflectivities at high elevations on Venus, on account of large dielectric constants measured for sulfide-bearing rocks that were erroneously attributed to pyrite instead of pyrrhotite. Pentlandite-pyrrhotite assemblages may be responsible for high reflectivities associated with impact craters on the Venusian surface, by analogy with Fe-Ni sulfide deposits occurring in terrestrial astroblemes. Mixed-valence Fe(2+)-Fe(3+) silicates, including oxyhornblende, oxybiotite, and ilvaite, may contribute to high radar reflecting surfaces on mountain-tops of Venus.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cottrell, W.B.; Klein, A.
1977-02-23
This index to Nuclear Safety covers articles in Nuclear Safety Vol. 11, No. 1 (Jan.-Feb. 1970), through Vol. 17, No. 6 (Nov.-Dec. 1976). The index includes a chronological list of articles (including abstract) followed by KWIC and Author Indexes. Nuclear Safety, a bimonthly technical progress review prepared by the Nuclear Safety Information Center, covers all safety aspects of nuclear power reactors and associated facilities. The index lists over 350 technical articles in the last six years of publication.
Mössbauer analysis of BIOX treatment of ores at Wiluna gold mine, Western Australia
NASA Astrophysics Data System (ADS)
Gagliardi, F. M.; Cashion, J. D.
2013-04-01
Mössbauer phase analysis of samples taken from nine stages of the bacterial oxidation processing of gold ore at the Wiluna Gold Mine followed the transformation of the arsenopyrite/pyrite minerals. The principal end-stage phases were szomolnokite, ferric oxyhydroxides, ferric arsenates, jarosite and incompletely transformed pyrite, with higher hydrates of ferrous sulphate being created and then dehydrating to szomolnokite during the processing.
The Fe removal in pyrophyllite by physical method
NASA Astrophysics Data System (ADS)
Cho, Kanghee; Jo, Jiyu; Bak, GeonYeong; Choi, NagChoul; Park*, CheonYoung
2015-04-01
The presence of Fe in ingredient material such as limestone, borax and pyrophyllite can prevent their use mainly in the glass fiber manufacturing industry. The red to yellow pigmentation in pyrophyllite is mainly due to the associated oxides and sulfides of Fe such as hematite, pyrite, etc. The removal of Fe in the pyrophyllite was investigated using high frequency treatment and magnetic separation under various alumina grades in pyrophyllite. The hematite and pyrite were observed in the pyrophyllite from photomicrograph and XRD analysis results. On the decrease of Al2O3 content in pyrophyllite was showed that SiO2, Fe2O3 and TiO2 content were increased by XRF analysis. The high frequency treatment experiment for the pyrophyllite showed that the (1) pyrite phase was transformed hematite and magnetite, (2) mass loss of the sample by volatilization of included sulfur(S) in pyrite. The results of magnetic separation for treated sample by high frequency were identified that Fe removal percent were in the range of 97.6~98.8%. This study demonstrated that physical method (high frequency treatment and magnetic separation) was effective for the removal of Fe in pyrophyllite. This subject is supported by Korea Ministry of Environment(MOE) as "Advanced Technology Program for Environmental Industry".
Friedlander, Lonia R.; Puri, Neha; Schoonen, Martin A.A.; Karzai, A. Wali
2015-01-01
We present proof-of-concept results for the elimination of waterborne bacteria by reactive minerals. We exposed E.coli MG1655 suspended in water to the reactive mineral pyrite (FeS2) at room temperature and ambient light. This slurry eliminates 99.9% of bacteria in fewer than 4 hours. We also exposed E. coli to pyrite leachate (supernatant liquid from slurry after 24-hours), which eliminates 99.99% of bacteria over the same time-scale. Unlike SOlar water DISinfection (SODIS) our results do not depend on the presence of ultraviolet (UV) light. We confirmed this by testing proposed SODIS additive and known photo-catalyst anatase (TiO2) for antibacterial properties and found that, in contrast to pyrite, it does not eliminate E. coli under our experimental conditions. Previous investigations of naturally antibiotic minerals have focused on the medical applications of antibiotic clays, and thus have not been conducted under experimental conditions resembling those found in water purification. In our examination of the relevant literature, we have not found previously reported evidence for the use of reactive minerals in water sanitization. The results from this proof-of-concept experiment may have important implications for future directions in household water purification research. PMID:25719464
NASA Astrophysics Data System (ADS)
Kantar, Cetin; Urken, Ozge; Oral, Ozlem; Kaplan, Iremsu; Ayman Oz, Nilgun
2017-04-01
Oxidative dehalogenation has been shown to be a viable and cost effective process for dealing with a particularly persistent class of contaminants (e.g., chlorophenolic compounds (CP)) often found in contaminated soil and ground water. Here, the degradation of various chlorophenolic compounds (e.g., 2-CP, 4-CP, 2,3-di CP, 2,4-di CP, 2,4,6-tri CP, 2,3,4,6-Tetra CP) was investigated by modified Fenton process using pyrite as source of Fe2+ (catalyst) . The effects of different parameters such as chlorophenol type, pH and chlorophenol, pyrite and H2O2 concentrations on the degradation kinetics of chlorophenols were studied in batch reactors. Our results show that while the rate of chloropehenol degradation increased with decreasing solution pH, no direct correlation was observed between H2O2 concentration and chlorophenol degradation, indicating a complex mechanism involved in CP degradation by modified Fenton process. The batch results also show that the CP degradation was highly dependent on CP type, the number and location of chloride ions in the structure. Overall, the results of this study suggest that pyrite can be effectively used in reactive treatment barriers for in-situ treatment of subsurface systems contaminated with chlorophenols.
Enzyme-Linked Immunofiltration Assay To Estimate Attachment of Thiobacilli to Pyrite
Dziurla, Marie-Antoinette; Achouak, Wafa; Lam, Bach-Tuyet; Heulin, Thierry; Berthelin, Jacques
1998-01-01
An enzyme-linked immunofiltration assay (ELIFA) has been developed in order to estimate directly and specifically Thiobacillus ferrooxidans attachment on sulfide minerals. This method derives from the enzyme-linked immunosorbent assay but is performed on filtration membranes which allow the retention of mineral particles for a subsequent immunoenzymatic reaction in microtiter plates. The polyclonal antiserum used in this study was raised against T. ferrooxidans DSM 583 and recognized cell surface antigens present on bacteria belonging to the genus Thiobacillus. This antiserum and the ELIFA allowed the direct quantification of attached bacteria with high sensitivity (104 bacteria were detected per well of the microtiter plate). The mean value of bacterial attachment has been estimated to be about 105 bacteria mg−1 of pyrite at a particle size of 56 to 65 μm. The geometric coverage ratio of pyrite by T. ferrooxidans ranged from 0.25 to 2.25%. This suggests an attachment of T. ferrooxidans on the pyrite surface to well-defined limited sites with specific electrochemical or surface properties. ELIFA was shown to be compatible with the measurement of variable levels of adhesion. Therefore, this method may be used to establish adhesion isotherms of T. ferrooxidans on various sulfide minerals exhibiting different physicochemical properties in order to understand the mechanisms of bacterial interaction with mineral surfaces. PMID:9687454
Ultrafast band-gap oscillations in iron pyrite
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kolb, B; Kolpak, AM
2013-12-20
With its combination of favorable band gap, high absorption coefficient, material abundance, and low cost, iron pyrite, FeS2, has received a great deal of attention over the past decades as a promising material for photovoltaic applications such as solar cells and photoelectrochemical cells. Devices made from pyrite, however, exhibit open circuit voltages significantly lower than predicted, and despite a recent resurgence of interest in the material, there currently exists no widely accepted explanation for this disappointing behavior. In this paper, we show that phonons, which have been largely overlooked in previous efforts, may play a significant role. Using fully self-consistentmore » GW calculations, we demonstrate that a phonon mode related to the oscillation of the sulfur-sulfur bond distance in the pyrite structure is strongly coupled to the energy of the conduction-band minimum, leading to an ultrafast (approximate to 100 fs) oscillation in the band gap. Depending on the coherency of the phonons, we predict that this effect can cause changes of up to +/- 0.3 eV relative to the accepted FeS2 band gap at room temperature. Harnessing this effect via temperature or irradiation with infrared light could open up numerous possibilities for novel devices such as ultrafast switches and adaptive solar absorbers.« less
Selby, D.; Kelley, K.D.; Hitzman, M.W.; Zieg, J.
2009-01-01
New Re-Os data for chalcopyrite, bornite, and pyrite from the carbonate-hosted Cu deposit at Ruby Creek (Bornite), Alaska, show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the carbonate-hosted Ruby Creek Cu-(Co) deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization pre dominantly occurred at 384 ?? 4.2 Ma, with an earlier phase possibly at ???400 Ma. The Re-Os data are consistent with the observed paragenetic sequence and coincide with zircon U-Pb ages from igneous rocks within the Ambler metallogenic belt, some of which are spatially and genetically associated with regional volcanogenic massive sulfide deposits. The latter may suggest a temporal link between regional magmatism and hydrothermal mineralization in the Ambler district. The utility of bornite and chalcopyrite, in addition to pyrite, contributes to a new understanding of Re-Os geochronology and permits a refinement of the genetic model for the Ruby Creek deposit. ?? 2009 Society of Economices Geologists, Inc.
NASA Astrophysics Data System (ADS)
Reinhard, C. T.; Planavsky, N.; Bolton, E. W.
2016-12-01
Earth's crust stores extremely large reservoirs of organic carbon and pyrite sulfur, and transient or secular changes in the sizes of these reservoirs have the capacity to dramatically alter atmospheric composition, climate, seawater acid-base chemistry, and the propagation of isotopic signals into the geologic record. This talk will present and discuss new quantitative approaches toward better understanding the factors that control organic carbon and pyrite sulfur weathering under a wide range of Earth surface conditions, as well as their downstream effects on seawater chemistry, stability of atmospheric pO2, and conventional interpretations of stable carbon isotope mass balance during pivotal events in Earth's biogeochemical evolution. In particular, we will focus on (1) development of a weathering-driven scaling between atmospheric pO2 and geologic carbon isotope signals that explains the relative stability of marine δ13C through time and provides a mechanism for protracted negative δ13C excursions during transient increases in atmospheric pO2; (2) experimental and theoretical approaches aimed at better understanding the role of pyrite sulfur weathering in stabilizing atmospheric pO2; and (3) the importance of redox balance in the sedimentary rock cycle for controlling the marine carbonate system and atmospheric pCO2.
Ab initio study of phonon dispersion and thermodynamic properties of pure and doped pyrites
NASA Astrophysics Data System (ADS)
Musari, Abolore A.; Joubert, Daniel P.; Olowofela, Joseph A.; Akinwale, Adio T.; Adebayo, Gboyega A.
2017-12-01
Pyrites (FeS2) are solid minerals that are found abundantly in Nigeria and are easy to prepare in laboratories. In this work, FeS2 is studied extensively in its pure state as well as when iron is substitutionally doped with zinc and calcium at concentrations of 0, 0.25, 0.5, 0.75 and 1. Using density functional theory, the eectronic, dynamic and thermodynamic properties were calculated. The results revealed that the lattice parameters and bulk modulus increases with increasing concentration and the obtained values are in agreement with available experimental and theoretical values. Though pyrite, when doped with zinc, obeys Vegard's law, doping with calcium revealed pronounced deviation from this law. The calculated band structures showed that FeS2 has an indirect band gap whose size decreases after introducing zinc while doping with calcium increases the band gap. The phonon dispersion of the end members FeS2 and ZnS2 indicate that the systems are dynamically stable while CaS2 is dynamically unstate. Also, the thermodynamic properties of the pure and doped pyrites were calculated and the ranges of temperature at which the lattice and electronic degrees of freedom contribute to the specific heat capacity are presented.
ARSENIC MINERALS AS INDICATORS OF CONDITIONS OF GOLD DEPOSITION IN CARLIN-TYPE GOLD DEPOSITS.
Rytuba, James J.
1984-01-01
Arsenic minerals commonly occurring in Carlin-type gold deposits include orpiment and realgar and, more rarely, native arsenic and arsenopyrite. Other arsenic-bearing phases present include arsenian pyrite and stibnite and a number of thallium and mercury sulfides. Under conditions of constant temperature and pressure, the relative stability of arsenic minerals is a function of sulfur activity. At high sulfur activity, orpiment is the stable phase. As sulfur activity is decreased, more sulfur-deficient arsenic phases become stable with the progressive formation of realgar, native arsenic, arsenopyrite, and finally, loellingite at very low sulfur activity. Three univariant equilibrium assemblages: orpiment plus realgar, realgar plus native arsenic and native arsenic plus arsenopyrite are useful indicators of sulfur activity and commonly occur in the epithermal environment.
ERIC Educational Resources Information Center
Lutzin, Sidney G.
The United States has made striking technical advances in recent years, but there has not been comparable progress in social services. Greater affluence and leisure for some have been one result of technical progress, but problems of poverty and urban development are more pressing. New developments to improve the condition of society can be…
ERIC Educational Resources Information Center
HANKIN, EDWARD K.; AND OTHERS
THIS TECHNICAL PROGRESS REPORT COVERS THE FIRST THREE MONTHS OF A PROJECT TO DEVELOP COMPUTER ASSISTED PREVOCATIONAL READING AND ARITHMETIC COURSES FOR DISADVANTAGED YOUTHS AND ADULTS. DURING THE FIRST MONTH OF OPERATION, PROJECT PERSONNEL CONCENTRATED ON SUCH ADMINISTRATIVE MATTERS AS TRAINING STAFF AND PREPARING FACILITIES. AN ARITHMETIC PROGRAM…
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hammer, D.A.; Kusse, B.R.; Sudan, R.N.
1983-07-01
The progress on this contract is described in two parts. The first deals with the technical operation of the LION accelerator which is the exact equivalent to one line of PBFA-I. The second part is concerned with the experimental results on the ion diode mounted at the front end of the LION accelerator.
ERIC Educational Resources Information Center
National Foundation for the Improvement of Education, Washington, DC.
Reported is the third quarter, fiscal year 1974 (March 1, 1974-May 31, 1974) technical progress of Project LIFE (Language Improvement to Facilitate Education), toward developing an instructional system in which filmstrips in the areas of perceptual training, perceptual thinking, and language/reading are used to assist hearing impaired children in…
Progress Towards Microwave Ignition of Explosives
NASA Astrophysics Data System (ADS)
Curling, Mark; Collins, Adam; Dima, Gabriel; Proud, William
2009-06-01
Microwaves could provide a method of propellant ignition that does away with a traditional primer, making ammunition safer and suitable for Insensitive Munitions (IM) applications. By embedding a suitable material inside a propellant, it is postulated that microwaves could be used to stimulate hotspots, through direct heating or electrostatic discharge (arcing) across the energetic material. This paper reports on progress in finding these suitable materials. Graphite rod, magnetite cubes and powders of graphite, aluminium, copper oxide, and iron were irradiated in a conventional microwave oven. Temperature measurements were made using a shielded thermocouple and thermal paints. Only graphite rod and magnetite showed significant heating upon microwave exposure. The light output from arcing of iron, steel, iron pyrite, magnetite and graphite was measured in the same microwave oven as above. Sample mass and shape were correlated with arcing intensity. A strategy is proposed to create a homogeneous igniter material by embedding arcing materials within an insulator, Polymethylpentene (TPX). External discharges were transmitted through TPX, however no embedded samples were successful in generating an electrical breakdown suitable for propellant ignition.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ulm, Franz-Josef
2000-06-30
OAK-B135 Monitoring the Durability Performance of Concrete in Nuclear Waste Containment. Technical Progress Report No. 4. The analysis of the effect of cracks on the acceleration of the calcium leaching process of cement-based materials has been pursued. During the last period (Technical Progress Report No 3), we have introduced a modeling accounting for the high diffusivity of fractures in comparison with the weak solid material diffusivity. It has been shown through dimensional and asymptotic analysis that small fractures do not significantly accelerate the material aging process. This important result for the overall structural aging kinetics of containment structure has beenmore » developed in a paper submitted to the international journal ''Transport in Porous Media''.« less
Mössbauer study of the effect of gamma irradiation on the removal of pyrite from Colombian coals
NASA Astrophysics Data System (ADS)
Mejía, J. A.; Reyes Caballero, F.; Palacio, C. A.; de Grave, E.; Olaya Dávila, H.; Martínez Ovalle, S. A.
2014-04-01
The removal of sulfur from the coals is necessary before using it. It is due to the environmental and technological problems that it causes. In this work, the results of the study by Mössbauer spectroscopy of the gamma-irradiation effect on the pyrite in three Colombian coals are analyzed. They were exposed to different gamma-irradiation doses using a 60Co source.
NASA Astrophysics Data System (ADS)
Filippova, I.; Chanturiya, V.; Filippov, L.; Ryazantseva, M.; Bunin, I.
2013-03-01
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.
Mössbauer study of the inorganic sulfur removal from coals
NASA Astrophysics Data System (ADS)
Reyes Caballero, F.; Martínez Ovalle, S. A.
2014-01-01
Mössbauer Spectroscopy (MS) was applied to study the occurrence and behavior of the iron-sulfur-containing minerals in coal and coal fractions obtained by different separation methods: hydrocyclonic, flotation and chemical removal process. Samples of one high sulfur coal from Guachinte mine (Valle, Colombia) and three low sulfur coals from the El Salitre zone (Paipa-Boyacá, Colombia) were analyzed. MS evidenced only the presence of pyrite in Esmeralda and Las Casitas coals, while it identified pyrite and siderite on Cerezo coal. MS and SEM- EDX confirm the inorganic sulfur removal on Guachinte coal submitted to hydrocyclonic removal process. MS of the precipitated coal fraction from Las Casitas mine obtained by flotation in water showed the presence of ferrous sulfate because of coal-weathering process. Treatment with hot diluted HNO3 equal to 27 acid on raw coal sample from Las Casitas mine showed that almost all of the pyrite in raw coal was removed.
Protein footprinting by pyrite shrink-wrap laminate.
Leser, Micheal; Pegan, Jonathan; El Makkaoui, Mohammed; Schlatterer, Joerg C; Khine, Michelle; Law, Matt; Brenowitz, Michael
2015-04-07
The structure of macromolecules and their complexes dictate their biological function. In "footprinting", the solvent accessibility of the residues that constitute proteins, DNA and RNA can be determined from their reactivity to an exogenous reagent such as the hydroxyl radical (·OH). While ·OH generation for protein footprinting is achieved by radiolysis, photolysis and electrochemistry, we present a simpler solution. A thin film of pyrite (cubic FeS2) nanocrystals deposited onto a shape memory polymer (commodity shrink-wrap film) generates sufficient ·OH via Fenton chemistry for oxidative footprinting analysis of proteins. We demonstrate that varying either time or H2O2 concentration yields the required ·OH dose-oxidation response relationship. A simple and scalable sample handling protocol is enabled by thermoforming the "pyrite shrink-wrap laminate" into a standard microtiter plate format. The low cost and malleability of the laminate facilitates its integration into high throughput screening and microfluidic devices.
Comparative study on the passivation layers of copper sulphide minerals during bioleaching
NASA Astrophysics Data System (ADS)
Fu, Kai-bin; Lin, Hai; Mo, Xiao-lan; Wang, Han; Wen, Hong-wei; Wen, Zi-long
2012-10-01
The bioleaching of copper sulphide minerals was investigated by using A. ferrooxidans ATF6. The result shows the preferential order of the minerals bioleaching as djurleite>bornite>pyritic chalcopyrite>covellite>porphyry chalcopyrite. The residues were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is indicated that jarosite may not be responsible for hindered dissolution. The elemental sulfur layer on the surface of pyritic chalcopyrite residues is cracked. The compact surface layer of porphyry chalcopyrite may strongly hinder copper extraction. X-ray photoelectron spectroscopy (XPS) further confirms that the passivation layers of covellite, pyritic chalcopyrite, and porphyry chalcopyrite are copper-depleted sulphide Cu4S11, S8, and copper-rich iron-deficient polysulphide Cu4Fe2S9, respectively. The ability of these passivation layers was found as Cu4Fe2S9>Cu4S11>S8>jarosite.
Superparamagnetic Fe3O4 particles formed by oxidation of pyrite heated in an anoxic atmosphere
Thorpe, A.N.; Senftle, F.E.; Talley, R.; Hetherington, S.; Dulong, F.
1990-01-01
As a follow-up to previous gas analysis experiments in which pyrite was heated to 681 K in an anoxic (oxygen starved) atmosphere, the first oxidation product, FeSO4, was studied as a bulk material. No decomposition of FeSO4 to Fe3O4 was observed in the temperature range studied. The lack of decomposition of bulk FeSO4 to Fe3O4 suggests that FeS2 oxidizes directly to Fe3O4, or that FeSO4, FeS2 and O2 react together to form Fe3O4. Magnetic susceptibility and magnetization measurements, along with magnetic hysteresis curves, show that small particles of Fe3O4 form on the pyrite surface, rather than a continuous layer of bulk Fe3O4. A working model describing the oxidation steps is presented. ?? 1990.
Department of Clinical Investigation Annual Research Progress Report, Fiscal Year 1984. Volume 1,
1984-10-01
on a low dosage of medication . Technical Approach: None. Progress: The placebo has not been received from the company. Since the drug company...determine the effect of high dose Ar-C intensification therapy on the -. incidence of CNS relapse. - Technical Approach: All patients with a new...Enrolled to Date: 7 Date of Periodic Review Results Objective(s): To determine the incidence of
NASA Astrophysics Data System (ADS)
Phuong, Vu Hung
2018-03-01
This research applies Data Envelopment Analysis (DEA) approach to analyze Total Factor Productivity (TFP) and efficiency changes in Vietnam coal mining industry from 2007 to 2013. The TFP of Vietnam coal mining companies decreased due to slow technological progress and unimproved efficiency. The decadence of technical efficiency in many enterprises proved that the coal mining industry has a large potential to increase productivity through technical efficiency improvement. Enhancing human resource training, technology and research & development investment could help the industry to improve efficiency and productivity in Vietnam coal mining industry.
Ilgen, A. G.; Cygan, R. T.
2015-12-07
During the Frio-I Brine Pilot CO 2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO 2 were recorded in samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. We explore in this modeling study possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite andmore » oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). The one-dimensional reactive transport model predicts carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses towards chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. Furthermore, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.« less
Arsenic contamination of the environment: a new perspective from central-east India.
Pandey, Piyush Kant; Yadav, Sushma; Nair, Sumita; Bhui, Ashish
2002-09-01
This paper reports a regional contamination of the environment in central-east India that does not share geology or boundary with the Bengal Delta Plain. About 30,000 people residing in 30 villages and towns are directly exposed to arsenic and more than 200,000 people are "at risk." Complete geographical extent of this contamination is being established, and this newly reported contaminated area could be quite large. This paper further reports that the mechanisms involved in arsenic mobilisation are complex and the two theories of arsenic mobilisation, i.e., pyrite oxidation and oxyhydroxides reduction, do not fully explain the high levels of arsenic contamination. This paper also proposes the "oxidation-reduction theory" for arsenic mobilisation where the arsenic originates from the arsenopyrite oxidation and the arsenic thus mobilised forms the minerals and gets reduced underground in favourable Eh conditions. The stoppage of water withdrawal from the contaminated sources did not result in lowering of arsenic levels as expected according to the heavy groundwater extraction theory (pyrite oxidation theory). Cases of arsenicosis in the region are on the rise and the switchover to less contaminated water has not reversed the arsenicosis progression in the affected persons even after 2 years. Surface water of the rivers is also being contaminated because of the probable dislocation of contaminated groundwater due to the heavy rains in monsoon season, which indicates that the river water could be a major carrier of arsenic in dissolved or adsorbed forms that may be a cause of contamination of the delta plains.
Geochemical and mineralogical studies of a South Texas roll-front uranium deposit
Goldhaber, Martin B.; Reynolds, Richard L.
1977-01-01
Core samples from a roll-front uranium deposit in south Texas have been analyzed for iron sulfide content and mineralogy, organic carbon content and the abundance of carbonate, iron, manganese and titanium. Sulfide occurs almost exclusively as the iron disulfides pyrite and marcasite, in concentrations as high as 2 percent of the coarse (>62 ?m) fraction. Marcasite is particularly abundant relative to pyrite in the vicinity of the roll front. Because marcasite precipitation requires acidic pH's and the most likely mechanism for generating a low pH is oxidation of preore sulfide, it is argued that marcasite formation is, at least in part, related to roll-front development. Organic carbon analyses from various representative parts of the deposit are uniformly low (<0.1 percent C). This is taken to imply that sulfate reducing bacteria were not involved in either initial sulfidation of the host rock or during later sulfidization that was related to the ore-forming episode. carbonate minerals, such as calcite, are quite abundant, but appear to have formed after the ore. The overall abundance of iron apparently is not systematically related to position with respect to the roll front, whereas manganese probably is concentrated near the redox interface. Titanium like iron does not show a systematic relationship to position about the roll. However, titanium is systematically more abundant in the fine fraction (462 ?m) relative to the coarse fraction with distance downdip. This reflects a progressively more intense alteration of precursor iron titanium oxide minerals to fine-grained TiO2.
Geology and geochemistry of the shear-hosted Julie gold deposit, NW Ghana
NASA Astrophysics Data System (ADS)
Amponsah, Prince Ofori; Salvi, Stefano; Béziat, Didier; Siebenaller, Luc; Baratoux, Lenka; Jessell, Mark W.
2015-12-01
The Leo Man Craton in West Africa is host to numerous economic gold deposits. If some regions, such as the SW of Ghana, are well known for world-class mineralizations and have been extensively studied, gold occurrences elsewhere in the craton have been discovered only in the last half a century or so, and very little is known about them. The Julie gold deposit, located in the Paleoproterozoic Birimian terrane of NW Ghana, is one such case. This deposit is hosted in a series of granitoid intrusives of TTG composition, and consists of a network of deformed, boudinaged quartz lodes (A-type veins) contained within an early DJ1 E-W trending shear zone with dextral characteristics. A conjugate set of veins (C-type) perpendicular to the A-type veins contains low grade mineralization. The main ore zone defines a lenticular corridor about 20-50 m in width and about 3.5 km along strike, trending E-W and dipping between 30 and 60°N. The corridor is strongly altered, by an assemblage of sericite + quartz + ankerite + calcite + tourmaline + pyrite. This is surrounded by a second alteration assemblage, consisting of albite + sericite + calcite + chlorite + pyrite + rutile, which marks a lateral alteration that fades into the unaltered rock. Mass balance calculations show that during alteration overall mass was conserved and elemental transfer is generally consistent with sulfidation, sericitization and carbonatization of the host TTG. Gold is closely associated with pyrite, which occurs as disseminated grains in the veins and in the host rock, within the mineralized corridor. SEM imagery and LA-ICP-MS analyses of pyrites indicate that in A-type veins gold is associated with bismuth, tellurium, lead and silver, while in C-type veins it is mostly associated with silver. Pyrites in A-type veins contain gold as inclusions and as free gold on its edges and fractures, while pyrites from C-type veins contains mostly free gold. Primary and pseudosecondary fluid inclusions from both type veins indicate circulation in the system of an aqueous-carbonic fluid of low to moderate salinity, which entered the immiscibility PT region of the H2O-CO2-NaCl system, at about 220 °C and <1 kbar.
Fe and S redox states during serpentinite dehydration in subduction settings
NASA Astrophysics Data System (ADS)
Merkulova, Margarita; Munoz, Manuel; Vidal, Olivier; Brunet, Fabrice
2016-04-01
Serpentinite rocks formed by hydrothermal alteration of oceanic peridotites compose ~70% of the oceanic crust (Hacker et al., 2003), which later sinks into subduction zone and experiences metamorphic reactions. Serpentinites carry ~12 wt.% H2O and thereby introduces large amount of water in the upper mantle during dehydration in subduction (Ulmer and Trommsdorff, 1995). In addition, serpentinites are known to contain such minerals as magnetite Fe3O4 and pyrite FeS2 in the amounts of ~5 wt.% (Debret et al., 2014) and 1.5 wt.% (Alt et al., 2013), respectively. During metamorphic reactions speciations of Fe and S are tended to change and affect oxygen fugacity. In turn, oxygen fugacity influences the mobility of fluid mobile elements and metals (Pokrovski and Dubrovinsky 2011). We characterized Fe and S speciation and amount of released water during serpentinite dehydration at different temperature and pressure intervals along a subduction zone. We performed three sets of experiments using piston-cylinder apparatus. Three different starting materials composed of powdered mineral mixtures were used: Fe(III)-antigorite (atg), atg + magnetite, atg + pyrite. Experimental runs were performed at 2 GPa, between 400 and 900°C. Experimental products were first characterized by X-ray diffraction and electron microprobe. Speciation of Fe and S were characterized by X-ray absorption spectroscopy (XANES) at iron and sulfur K-edges. In addition, thermodynamic modeling was applied in this work with constrained thermodynamical data for Fe-bearing antigorite. The results demonstrate the continuous dehydration of serpentinites with the main water releasing domain between 670 and 700°C, which is happening due to breakdown of antigorite. Fe K-edge XANES measurements show that the amount of ferric iron dramatically decreases between 550-650°C, leading to a release of free oxygen in the system. As a result, we show that the first fluids released from the slab dehydration most likely present highly oxidizing properties. At higher P-T conditions, higher amounts of water are released with minor oxygen release. In addition, sulfur is shown to be progressively reduced at temperature 450-500°C due to pyrite to pyrrhotite transition. The reaction of pyrite reduction was observed to happen with sequestration of Fe from silicates and a release of oxygen. Effectively, the presence of sulphides in serpentinites contribute additional oxygen to the fluid, whereas the release of S may be negligible. The detailed study of the evolution of redox conditions during serpentinite dehydration in subduction zones will help constraining, 1) the behavior and mobility, from slab to the upper mantle, of elements of economical interest, as well as 2) the global geochemical cycling of elements. References: 1. Hacker et al. (2003) J. Geophys. Res. 108, article number 2029. 2. Ulmer & Trommsdorff (1995) Science 268, 858-861. 3. Debret et al. (2014) EPSL 400, 206-218. 4. Alt et al. (2013) Lithos 178, 40-54. 5. Pokrovski & Dubrovinsky (2011) Science 331, 1052-1056.
NASA Astrophysics Data System (ADS)
Watanabe, Y.; Ohmoto, H.
2010-12-01
As part of the Archean Biosphere Drilling Project (ABDP), we have determined the multiple sulfur isotope ratios and examined the mineralogical and geochemical characteristics of the sulfur-bearing minerals (e.g., pyrite, sphalerite, barite) and the host rocks (e.g., major and trace element chemistry; Corg, Ccarb and S contents; δ13Corg and δ13Ccarb) of >100 samples of sedimentary rocks from five ABDP drill cores in the Pilbara Craton, Western Australia. The total ranges of Δ33S and δ34S values of the studied samples are -0.9 to +1.2‰ and -4 to +8‰, respectively. We have found that the Δ33S and δ34S relationships show unique values depending on their depositional environment: (1) Pyrites in the 3.46 Ga Marble Bar Chert Member (ABDP #1), which were formed by submarine hydrothermal fluids, show no AIF-S (anomalously fractionated sulfur isotope) signatures: Δ33S = -0.08 to +0.08‰ and δ34S = -3.3 to +0.6‰ (n = 5). This indicates that the H2S presented in the submarine hydrothermal fluid, which was partly generated through seawater sulfate reduction by Fe2+, did not possess AIF-S signatures. (2) Pyrites in organic C-poor lacustrine shales of the 2.76 Ga Hardey Formation (ABDP #3) also show no or very little AIF-S signatures: Δ33S = -0.38 to +0.25‰ and δ34S = -2.7 to +1.9‰ (n = 18). (3) Pyrites in organic C-poor marine shales of the 2.92 Ga Mosquito Creek Formation (ABDP#5) show no or small negative AIF-S signatures: Δ33S = -0.59 to 0.19 ‰ and all positive δ34S = +1.4 to +7.7‰ (n = 24). (4) Pyrites in organic C-rich (> 1 wt%) and hydrothermally altered marine shales in the 3.46 Ga Panorama Formation (ABDP #2) show constant and small positive AIF-S signatures (+0.44 to +0.61‰) and the smallest variation in δ34S (-1.1 to +1.6‰) (n = 35). In contrast, pyrites in organic C-rich shales in the 2.72 Ga Mt. Roe Basalt show negative Δ33S = -0.50 to -0.10‰ and δ34S = -3.7 to 1.8‰ (n = 10). (5) Pyrites in stromatolitic carbonates of the 2.7 Ga Tumbiana Formation (ABDP #10), which deposited in shallow evaporating marine basins, possess the largest variation in AIF-S signatures among five ABDP cores: Δ33S = -0.86 to 1.19‰ and δ34S = -3.2 to +1.5‰ (n = 10). (6) Compared to the negative Δ33S values (-1.28 to -0.47‰) of barites in the 3.2 Ga Dresser Formation (e.g., Ueno et al., 2009), Δ33S values of barites in the 3.46 Ga Panorama Formation (ABDP #2) are all positive (+0.55 to +0.61‰) and identical to those of reduced sulfur species (sphalerite and pyrite) in the same sample. The observed relationships between AIF-S signatures and depositional environments, and the abundance of samples with no AIF-S signatures, are difficult to explain by the current popular model that links AIF-S to atmospheric UV reactions. However, the data can be best explained by our model that links AIF-S to thermochemical sulfate reduction (TSR) by various solid phases and S-bearing aqueous/gaseous species (e.g., TSR by organic matter; replacement of iron oxides by pyrite) under hydrothermal conditions in a local and/or regional (basin wide) scale. Therefore, the AIF-S record of sedimentary rocks may be linked to the Earth’s thermal and biological evolution, rather than to the atmospheric evolution.
Brown, C.J.; Misut, P.E.
2010-01-01
The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4??10-6M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O2 (DO) and increase in acidity. Simulations with more than 0.0037M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation.The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe2+ (FeX2). Results indicate that ASR in pyrite-beari
Cross flow cyclonic flotation column for coal and minerals beneficiation
Lai, Ralph W.; Patton, Robert A.
2000-01-01
An apparatus and process for the separation of coal from pyritic impurities using a modified froth flotation system. The froth flotation column incorporates a helical track about the inner wall of the column in a region intermediate between the top and base of the column. A standard impeller located about the central axis of the column is used to generate a centrifugal force thereby increasing the separation efficiency of coal from the pyritic particles and hydrophillic tailings.
Effect of some metal chlorides on the transformation of pyrite to pyrrhotite
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shiley, R.H.; Konopka, K.L.; Hinckley, C.C.
1982-08-01
Samples of the iron-sulfide mineral pyrrhotite were prepared using a procedure designed to closely model the pyrite-to-pyrrhotite conversion that occurs during coal-conversion processing. Pyrite mixed with graphite converts to mixtures of monoclinic and hexagonal pyrrhotite when heated at 500C for 4.5 hours, and an iron-rich pyrrhotite (Fe10S11) forms at 600 to 700C. In addition to temperature effects, the pyrrhotites formed from pyrite in graphite are also dependent on additives or impurities in the form of metal salts. The pyrrhotites used in this study were prepared in the presence of selected transition metal chlorides: PdCl2, NiCl2, CoCl2, ZnCl2, MoCl5, and ZrCl4.more » When these metal salts were used, pyrrhotites with an increased number of iron vacancies were produced. For example, in the presence of ZrCl4 at temperatures as high as 700C, a pyrrhotite was produced that exhibited Moessbauer magnetic-splitting values characteristic of pyrrhotite with a high number of iron vacancies (iron-poor). These pyrrhotites were then converted to troilite at 400C in the presence of CO and H2; and this troilite is an active catalyst for the Fischer-Tropsch synthesis, alkene hydrogenation, the Boudouard reaction, the water-gas shift reaction, and the hydrodesulfurization of organic sulfur compounds.« less
Korehi, H; Blöthe, M; Sitnikova, M A; Dold, B; Schippers, A
2013-03-05
The marine shore sulfidic mine tailings dump at the Chañaral Bay in the Atacama Desert, northern Chile, is characterized by extreme acidity, high salinity, and high heavy metals concentrations. Due to pyrite oxidation, metals (especially copper) are mobilized under acidic conditions and transported toward the tailings surface and precipitate as secondary minerals (Dold, Environ. Sci. Technol. 2006, 40, 752-758.). Depth profiles of total cell counts in this almost organic-carbon free multiple extreme environment showed variable numbers with up to 10(8) cells g(-1) dry weight for 50 samples at four sites. Real-time PCR quantification and bacterial 16S rRNA gene diversity analysis via clone libraries revealed a dominance of Bacteria over Archaea and the frequent occurrence of the acidophilic iron(II)- and sulfur-oxidizing and iron(III)-reducing genera Acidithiobacillus, Alicyclobacillus, and Sulfobacillus. Acidophilic chemolithoautotrophic iron(II)-oxidizing bacteria were also frequently found via most-probable-number (MPN) cultivation. Halotolerant iron(II)-oxidizers in enrichment cultures were active at NaCl concentrations up to 1 M. Maximal microcalorimetrically determined pyrite oxidation rates coincided with maxima of the pyrite content, total cell counts, and MPN of iron(II)-oxidizers. These findings indicate that microbial pyrite oxidation and metal mobilization preferentially occur in distinct tailings layers at high salinity. Microorganisms for biomining with seawater salt concentrations obviously exist in nature.
Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E
2018-05-17
Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .
Preservation of Early Cambrian animals of the Chengjiang biota
NASA Astrophysics Data System (ADS)
Gabbott, Sarah E.; Xian-Guang, Hou; Norry, Michael J.; Siveter, David J.
2004-10-01
The Chengjiang biota of Yunnan, China, documents the earliest extensive radiation of the Metazoa recorded in the fossil record. Gauging preservational bias is crucial in providing an assessment of the completeness of this biota and thereby elucidating whether it represents a comprehensive depiction of Early Cambrian life. We here present a model to explain the nature of the exceptional preservation of the Chengjiang biota and details of the decay process. This study indicates that Chengjiang fossils were preserved through two taphonomic pathways that may have captured tissues of distinct compositions, and this finding should provide a foundation for the interpretation of Chengjiang fossils. Many Chengjiang fossils are preserved by pyrite (later pseudomorphed by iron oxides); the clay-rich host sediment was deficient in organic carbon but replete in available Fe, and this composition ensured that a decaying carcass acted as a local substrate for Fe- and S-reducing bacteria. Pyrite morphology probably reflects contrasts in the decay rate, and hence the H2S production rate, of different tissues in a carcass. Reactive, rapidly decaying tissues would have quickly supplied H2S, producing many pyrite nuclei, resulting in framboidal habits. More recalcitrant tissues would have produced H2S more slowly, so that crystal growth operated on fewer nuclei, resulting in larger euhedral pyrite crystals. Reflective films, especially common on Chengjiang arthropods, represent the remains of degraded carbon.
Belkin, H.E.; Luo, K.
2008-01-01
The Ni-Mo Huangjiawan mine, Guizhou Province, People's Republic of China, occurs in Lower Cambrian black shale (stone coal) in an area where other mines have recently extracted ore from the same horizon. Detailed electron microprobe (EMPA) and scanning electron microscope (SEM) analyses of representative thin sections have revealed a complex assemblage of sulfides and sulfarsenides. Early sulfidic and phosphatic nodules and host matrix have been lithified, somewhat fractured, and then mineralized with later-stage sulfides and sulfarsenides. Gersdorffite, millerite, polydymite, pyrite, sphalerite, chalcopyrite, galena, and clausthalite have been recognized. EMPA data are given for the major phases. Pyrite trace-element distributions and coeval Ni-, As-sulfides indicate that in the main ore layer, the last sulfide deposition was Ni-As-Co-rich. Mo and V deposition were early in the petrogenesis of these rocks. The assemblages gersdorffite-millerite-polydymite (pyrite) and millerite-gersdorffite (pyrite) and the composition of gersdorffite indicate a formation temperature of between 200?? and 300??C suggesting that the last solutions to infiltrate and mineralize the samples were related to hydrothermal processes. Environmentally sensitive elements such as As, Cd, and Se are hosted by sulfides and sulfarsenides and are the main source of these elements to residual soil. Crops grown on them are enriched in these elements, and they may be hazardous for animal and human consumption. ?? Springer-Verlag 2007.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hahn, H
This paper discusses the ISABELLE project, which has the objective of constructing a high-energy proton colliding beam facility at Brookhaven National Laboratory. The major technical features of the intersecting storage accelerators with their projected performance are described. Application of over 1000 superconducting magnets in the two rings represents the salient characteristic of the machine. The status of the entire project, the technical progress made so far, and difficulties encountered are reviewed.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bender, W.
2013-01-01
Final technical progress report of SunShot Incubator Solaflect Energy. The project succeeded in demonstrating that the Solaflect Suspension Heliostat design is viable for large-scale CSP installations. Canting accuracy is acceptable and is continually improving as Solaflect improves its understanding of this design. Cost reduction initiatives were successful, and there are still many opportunities for further development and further cost reduction.
NASA Astrophysics Data System (ADS)
John, David A.; Sisson, Thomas W.; Breit, George N.; Rye, Robert O.; Vallance, James W.
2008-08-01
Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8 km 3 Osceola Mudflow (5600 y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz-alunite, quartz-topaz, quartz-pyrophyllite, quartz-dickite/kaolinite, and quartz-illite (all with pyrite). Clasts of smectite-pyrite and steam-heated opal-alunite-kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite-pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite-pyrite assemblages, whereas the proximal Electron Mudflow and a < 100 y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite-pyrite alteration within 1 km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H 2S in the unsaturated zone above the water table. Weakly developed smectite-pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal-mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (≥ 8 km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1-1.5 km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower west flanks are not intensely altered and probably have not significantly weakened the rock, and thus do not present significant collapse hazards. (6) Alteration developed most intensely within breccia units, because of their high permeability and porosity. Volcanoes with abundant near-conduit upper-edifice breccias are prone to alteration increasing the possibility of collapse, whereas those that are breccia-poor (e.g., massive domes) are less prone to alteration.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, M.M.; Chao, B.T.
This technical progress report covers the progress made during the fifth quarter of the project entitled Measurements of Solids Motion in Gas Fluidized Beds under Grant No. DOE-F22-81PC40804 during the period 1 October through 31 December 1982. The research concerns the measurement of solids particle velocity distribution and residence time distribution using the Computer-Aided Particle Tracking Facility (CAPTF) at the University of Illinois at Urbana-Champaign. The experimental equipment and measuring methods used to determine particle size distribution and particle motion and the results obtained are presented.
Post-depositional tectonic modification of VMS deposits in Iberia and its economic significance
NASA Astrophysics Data System (ADS)
Castroviejo, Ricardo; Quesada, Cecilio; Soler, Miguel
2011-07-01
The original stratigraphic relationships and structure of VMS deposits are commonly obscured by deformation. This can also affect their economic significance, as shown by several Iberian Pyrite Belt (IPB, SW Iberia) examples. The contrasting rheologic properties of the different lithologies present in an orebody (massive sulphide, feeder stockwork, alteration envelope, volcanic and sedimentary rocks) play a major role in determining its overall behaviour. Variscan thin-skinned tectonics led to stacking of the massive pyrite and stockwork bodies in duplex structures, resulting in local thickening and increased tonnage of minable mineralization. Furthermore, differential mechanical behaviour of the different sulphide minerals localised the detachments along relatively ductile sulphide-rich bands. The result was a geochemical and mineralogical reorganisation of most deposits, which now consist of barren, massive pyrite horses, bounded by base metal-rich ductile shear zones. Metal redistribution was enhanced by mobilisation of the base metal sulphides from the initially impoverished massive pyrite, through pressure-solution processes, to tensional fissures within the already ductile shear zones. In NW Iberia, VMS deposits were also strongly overprinted by the Variscan deformation during emplacement of the Cabo Ortegal and Órdenes allochthonous nappe complexes, but no stacking of the orebodies was produced. Original contacts were transposed, and the orebodies, their feeder zones and the country rock acquired pronounced laminar geometry. In lower-grade rocks (greenschist facies, Cabo Ortegal Complex), solution transfer mechanisms are common in pyrite, which remains in the brittle domain, while chalcopyrite shows ductile behaviour. In higher-grade rocks (amphibolite facies, Órdenes Complex), metamorphic recrystallisation overprints earlier deformation textures. The contrasting behaviour of the IPB and NW Iberian deposits is explained by key factors that affect their final geometry, composition and economics, such as pre-deformation structure, size and mineralogical composition of the orebody and associated lithologies, temperature, crustal level, deviatoric stress and availability of a fluid phase during deformation and the style and rate of deformation.
Diehl, S.F.; Smith, Kathleen S.; Desborough, G.A.; White, W.W.; Lapakko, K.A.; Goldhaber, Martin B.; Fey, David L.
2003-01-01
To assess the potential impact of metal and acid contamination from mine-waste piles, it is important to identify the mineralogic source of trace metals and their mode of occurrence. Microscopic analysis of mine-waste samples from both hard-rock and coalmine waste samples demonstrate a microstructural control, as well as mineralogic control, on the source and release of trace metals into local water systems. The samples discussed herein show multiple periods of sulfide mineralization with varying concentrations of trace metals. In the first case study, two proprietary hard-rock mine-waste samples exposed to a series of humidity cell tests (which simulate intense chemical weathering conditions) generated acid and released trace metals. Some trace elements of interest were: arsenic (45-120 ppm), copper (60-320 ppm), and zinc (30-2,500 ppm). Untested and humidity cell-exposed samples were studied by X-ray diffraction, scanning electron microscope with energy dispersive X-ray (SEM/EDX), and electron microprobe analysis. Studies of one sample set revealed arsenic-bearing pyrite in early iron- and magnesium-rich carbonate-filled microveins, and iron-, copper-, arsenic-, antimony-bearing sulfides in later crosscutting silica-filled microveins. Post humidity cell tests indicated that the carbonate minerals were removed by leaching in the humidity cells, exposing pyrite to oxidative conditions. However, sulfides in the silica-filled veins were more protected. Therefore, the trace metals contained in the sulfides within the silica-filled microveins may be released to the surface and (or) ground water system more slowly over a greater time period. In the second case study, trace metal-rich pyrite-bearing coals from the Warrior Basin, Alabama were analyzed. Arsenic-bearing pyrite was observed in a late-stage pyrite phase in microfaults and microveins that crosscut earlier arsenic.
Full potential calculations on the electron bandstructures of Sphalerite, Pyrite and Chalcopyrite
NASA Astrophysics Data System (ADS)
Edelbro, R.; Sandström, Å.; Paul, J.
2003-02-01
The bulk electronic structures of Sphalerite, Pyrite and Chalcopyrite have been calculated within an ab initio, full potential, density functional approach. The exchange term was approximated with the Dirac exchange functional, the Vosko-Wilk-Nusair parameterization of the Cepler-Alder free electron gas was used for correlation and linear combinations of Gaussian type orbitals were used as basis functions. The Sphalerite (zinc blende) band gap was calculated to be direct with a width of 2.23 eV. The Sphalerite valence band was 5.2 eV wide and composed of a mixture of sulfur and zinc orbitals. The band below the valence band located around -6.2 eV was mainly composed of Zn 3d orbitals. The S 3s orbitals gave rise to a band located around -12.3 eV. Pyrite was calculated to be a semiconductor with an indirect band gap of 0.51 eV, and a direct gap of 0.55 eV. The valence band was 1.25 eV wide and mainly composed of non-bonding Fe 3d orbitals. The band below the valence band was 4.9 eV wide and composed of a mixture of sulfur and iron orbitals. Due to the short inter-atomic distance between the sulfur dumbbells, the S 3s orbitals in Pyrite were split into a bonding and an anti-bonding range. Chalcopyrite was predicted to be a conductor, with no band-crossings at the Fermi level. The bands at -13.2 eV originate from the sulfur 3s orbitals and were quite similar to the sulfur 3s bands in Sphalerite, though somewhat shifted to lower energy. The top of the valence band consisted of a mixture of orbitals from all the atoms. The lower part of the same band showed metal character. Computational modeling as a tool for illuminating the flotation and leaching processes of Pyrite and Chalcopyrite, in connection with surface science experiments, is discussed.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bachhuber, Frederik; School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland; Krach, Alexander
2015-03-15
Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine theirmore » stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.« less
NASA Technical Reports Server (NTRS)
Beier, J. A.; Hayes, J. M.
1989-01-01
The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.
NASA Astrophysics Data System (ADS)
Wohlgemuth-Ueberwasser, Cora C.; Viljoen, Fanus; Petersen, Sven; Vorster, Clarisa
2015-06-01
The key for understanding the trace metal inventory of currently explored VHMS deposits lies in the understanding of trace element distribution during the formation of these deposits on the seafloor. Recrystallization processes already occurring at the seafloor might liberate trace elements to later hydrothermal alteration and removement. To investigate the distribution and redistribution of trace elements we analyzed sulfide minerals from 27 black smoker samples derived from three different seafloor hydrothermal fields: the ultramafic-hosted Logatchev hydrothermal field on the Mid-Atlantic Ridge, the basaltic-hosted Turtle Pits field on the mid-atlantic ridge, and the felsic-hosted PACMANUS field in the Manus basin (Papua New Guinea). The sulfide samples were analyzed by mineral liberation analyser for the modal abundances of sulfide minerals, by electron microprobe for major elements and by laser ablation-inductively coupled plasma-mass spectrometry for As, Sb, Se, Te, and Au. The samples consist predominantly of chalcopyrite, sphalerite, pyrite, galena and minor isocubanite as well as inclusions of tetrahedrite-tennantite. Laser ablation spectra were used to evaluate the solubility limits of trace elements in different sulfide minerals at different textures. The solubility of As, Sb, and Au in pyrite decreases with increasing degree of recrystallization. When solubility limits are reached these elements occur as inclusions in the different sulfide phases or they are expelled from the mineral phase. Most ancient VHMS deposits represent felsic or bimodal felsic compositions. Samples from the felsic-hosted PACMANUS hydrothermal field at the Pual ridge (Papua New Guinea) show high concentrations of Pb, As, Sb, Bi, Hg, and Te, which is likely the result of an additional trace element contribution derived from magmatic volatiles. Co-precipitating pyrite and chalcopyrite are characterized by equal contents of Te, while chalcopyrite that replaced pyrite (presumably during black smoker growth) is enriched in Te relative to pyrite. These higher Te concentrations may be related to higher fluid temperature.
Equation of state of pyrite to 80 GPa and 2400 K
Thompson, Elizabeth C.; Chidester, Bethany A.; Fischer, Rebecca A.; ...
2016-05-02
The high-cosmic abundance of sulfur is not reflected in the terrestrial crust, implying it is either sequestered in the Earth’s interior or was volatilized during accretion. As it has widely been suggested that sulfur could be one of the contributing light elements leading to the density deficit of Earth’s core, a robust thermal equation of state of iron sulfide is useful for understanding the evolution and properties of Earth’s interior. We performed X-ray diffraction measurements on FeS 2 achieving pressures from 15 to 80 GPa and temperatures up to 2400 K using laser-heated diamond-anvil cells. No phase transitions were observedmore » in the pyrite structure over the pressure and temperature ranges investigated. Combining our new P-V-T data with previously published room-temperature compression and thermochemical data, we fit a Debye temperature of 624(14) K and determined a Mie-Grüneisen equation of state for pyrite having bulk modulus K T = 141.2(18) GPa, pressure derivative K' T = 5.56(24), Grüneisen parameter γ 0 = 1.41, anharmonic coefficient A 2 = 2.53(27) × 10 –3 J/(K 2·mol), and q = 2.06(27). These findings are compared to previously published equation of state parameters for pyrite from static compression, shock compression, and ab initio studies. This revised equation of state for pyrite is consistent with an outer core density deficit satisfied by 11.4(10) wt% sulfur, yet matching the bulk sound speed of PREM requires an outer core composition of 4.8(19) wt% S. Here, this discrepancy suggests that sulfur alone cannot satisfy both seismological constraints simultaneously and cannot be the only light element within Earth’s core, and so the sulfur content needed to satisfy density constraints using our FeS 2 equation of state should be considered an upper bound for sulfur in the Earth’s core.« less
NASA Astrophysics Data System (ADS)
Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu
2015-01-01
We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.
Equation of state of pyrite to 85 GPa and 2400 K
NASA Astrophysics Data System (ADS)
Thompson, E. C.; Chidester, B.; Campbell, A. J.; Prakapenka, V.
2014-12-01
Pyrite (FeS2), a Pa3 space group non-magnetic semiconductor, is the most abundant iron sulfide in nature, yet the high cosmic abundance of sulfur is not reflected in the terrestrial crust, implying it is either sequestered in the Earth's interior or was volatilized during accretion. As it has widely been suggested that sulfur could be one of the contributing light elements leading to the density deficit of Earth's core, a robust thermal equation of state of FeS2 is vital for understanding the evolution and properties of Earth's interior. We performed X-ray diffraction measurements on FeS2 at the GSECARS sector 13-ID-D and HPCAT sector 16-ID-B beamlines at the Advanced Photon Source. Pressures from 17 to 85 GPa and temperatures up to 2400 K were achieved using laser-heated diamond anvil cells. Pressures were determined from the lattice parameters of KBr [1], which served as an insulator and pressure medium, and temperatures were determined by spectroradiometry. No phase transitions were observed in the pyrite structure over the pressure and temperature ranges investigated. By combining our new P-V-T data with previously published room temperature compression data [2], we have determined a thermal equation of state for FeS2, with bulk modulus K=182.6(74) GPa, pressure derivative K'=3.82(25), and αKT=0.00329(45). Our revised equation of state for pyrite is consistent with a core density deficit satisfied by 9-10 wt.% sulfur. We compare these findings to previously published ab intio equation of state parameters for pyrite under a similar range of pressures [3]. [1] Fischer et al. (2012) EPSL 357-358, 268-276. [2] Merkel et al. (2002) PCM 29, 1-9. [3] Le Page and Rodgers (2005) PCM 32, 564-567.
Mineralogy of Copper-Gold Deposit, Masjid Daghi Area, Jolfa, IRAN
NASA Astrophysics Data System (ADS)
Zenoozi, Roya
2010-05-01
The Copper-Gold deposit of Masjid Daghi area is located in the Jolfa quadrangle (scale 1:100,000), East Azerbaijan Province, north-west Iran. The deposit, hosting by sub-volcanic bodies comprise of quartz monzonite composition whose intruded the Tertiary volcanic and volcanic-sedimentary rocks and turbidities. The Tertiary volcanic rocks consist of andesite, trachy andesite and quartz andesite. These mineral-bearing bodies related to Late Eocene sub-volcanic activities which intrudded the Eocene volcanic rocks. Mineralography, XRD and SEM studies showed that the variations in mineralization of the area. The main agent of mineralization is the intrusion of Late Eocene sub volcanic bodies inside the Tertiary volcanic units. The mineralography studies revealed two main groups of mineralization as oxides and sulfides. The sulfide minerals formed as veins, vein lets and stock work.The economic minerals comprise of native gold, copper sulfides. The native gold occurring in siliceous veins and almost as inclusions inside the sulfides minerals such as chalcopyrite. The copper sulfides, contain pyrite, chalcopyrite and chalco-pyrrhoyite. Pyrite is main sulfide in the area and formed as disseminations, cavity filling and colloform. The amount of pyrite, chalcopyrite and chalco-pyrrhoyite increases with depth. Supergene alteration produced digenite, covellite, bornite, and malachite. The alteration occurred as potassic, phyllic, argillic and propylitic minerals. Furthermore, selective sercitic, sericitic-chloritic and alunitic alterations are seen around the mineralized veins. The mineralography studies indicate that pyrite is main mineral phase and native gold occurred in silicious vein almost as inclusions inside the sulfide mineral. Most of economic mineral formed as veins, vein lets, disseminated, cavity filling and colloform which related to intrusions of Late Eocene quartz monzonite bodies into the Eocene volcanic rocks and turbiditse. Some types of alterations such as potassic, phillic, argillic and prophylitic in the area and silicious alteration near the mineralized veins, indicate probable existence of porphyry copper ore and imply epithermal gold in the Jolfa area, north west of Iran. Key words: Masjid Dagi, Alteration, Pyrite, Sulfide, Mineralography, Stock work.
The 1996 NAEP Technical Report.
ERIC Educational Resources Information Center
Allen, Nancy L.; Carlson, James E.; Zelenak, Christine A.
This report documents the design, administration, and data analysis procedure of the National Assessment of Education Progress (NAEP) for 1996. It indicates the technical decisions that were made and the rationale behind them. Detailed substantive findings are not presented in this report. These chapters provide technical information about the…
Lincoln County nuclear waste project. Quarterly progress report, October 1, 1991--December 31, 1991
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-03-01
This document included the following three progress reports to the Yucca Mountain Project Office on radioactive waste storage in Lincoln County, Nevada: financial status report; federal cash transactions report; and technical progress report.
Lincoln County nuclear waste project. Quarterly progress report, January 1, 1992--March 31, 1992
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-03-01
This document included the following three progress reports to the Yucca Mountain Project Office on radioactive waste storage in Lincoln County, Nevada: financial status report; federal cash transactions report; and technical progress report.
Lincoln County nuclear waste project quarterly progress report, April 1, 1992--June 30, 1992
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
1996-03-01
This document included the following three progress reports to the Yucca Mountain Project Office on radioactive waste storage in Lincoln County, Nevada: financial status report; federal cash transactions report; and technical progress report.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cottrell, W.B.; Passiakos, M.
This index to Nuclear Safety covers articles published in Nuclear Safety, Volume 18, Number 1 (January-February 1977) through Volume 22, Number 6 (November-December 1981). The index is divided into three section: a chronological list of articles (including abstracts), a permuted-title (KWIC) index, and an author index. Nuclear Safety, a bimonthly technical progress review prepared by the Nuclear Safety Information Center, covers all safety aspects of nuclear power reactors and associated facilities. Over 300 technical articles published in Nuclear Safety in the last 5 years are listed in this index.
Federal Register 2010, 2011, 2012, 2013, 2014
2012-03-20
... Information Collection for Public Comment; Office of Native American Programs (ONAP) Training and Technical... subject proposal. The data required by Office of Native American Programs Training and Technical... progress. The data identifies needs, outputs and outcomes of the training and technical assistance. DATES...
Delgado, Guilherme Costa
2017-07-01
This paper aims to conduct a conceptual analysis of the relationship between scientific and technical progress and social equality, or the reduction of inequalities. We examine this relationship by drawing on three theoretical perspectives: 1) ethical economics, championed by classical economic thinkers and centered on utilitarian self-interest, 2) Mainstream theories of economic development espousing the endogenous link between labor productivity growth and technical progress, 3) the critique of theories of economic development that emerged in the second half of the twentieth century, including Celso Furtado's critique of the theory of underdevelopment, emphasizing the prevalence of egalitarian tendencies, and ecological economics, which suggest alternative paths to those set by "classical" theories of development. The fundamental antinomy posed by the title of this article, characterized by an intrinsic contradiction between technical progress and social equality, strictly presupposes the ethical economics perspective, dominated by the social relations that constitute the "social order".
Atomic Layer Deposition of the Metal Pyrites FeS2 , CoS2 , and NiS2.
Guo, Zheng; Wang, Xinwei
2018-05-14
Atomic layer deposition (ALD) of the pyrite-type metal disulfides FeS 2 , CoS 2 , and NiS 2 is reported for the first time. The deposition processes use iron, cobalt, and nickel amidinate compounds as the corresponding metal precursors and the H 2 S plasma as the sulfur source. All the processes are demonstrated to follow ideal self-limiting ALD growth behavior to produce fairly pure, smooth, well-crystallized, stoichiometric pyrite FeS 2 , CoS 2 , and NiS 2 films. By these processes, the FeS 2 , CoS 2 , and NiS 2 films can also be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which thereby highlights the broad and promising applicability of these ALD processes for conformal film coatings on complex high-aspect-ratio 3D architectures in general. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Chen, Xuliang; Shao, Dexi; Gu, Chuanchuan; Zhou, Yonghui; An, Chao; Zhou, Ying; Zhu, Xiangde; Chen, Tong; Tian, Mingliang; Sun, Jian; Yang, Zhaorong
2018-05-01
We report on the discovery of pressure-induced superconductivity in the compensated semimetal pyrite PtB i2 , which exhibits extreme magnetoresistance (XMR) and nontrivial band structure at ambient pressure. The appearance of superconductivity, first observed at PC˜13 GPa with an onset critical temperature TC of ˜2.2 K , is accompanied by a pronounced enhancement of the density of electrons and holes based on Hall-effect measurements. Upon further compression, TC remains almost unchanged up to 50.0 GPa; remarkably, the perfect electron-hole compensation still holds, while the carrier mobility greatly reduces. No evident trace of structural phase transitions is detected through synchrotron x-ray diffraction over the measured pressure range of 1.5-51.2 GPa. These results highlight a multiband characteristic of the observed superconductivity, making pyrite PtB i2 unique among the compensated XMR materials where the pressure-induced superconductivity usually links to structural transitions and carrier imbalance.
Extremely Large Magnetoresistance in a Topological Semimetal Candidate Pyrite PtBi2
NASA Astrophysics Data System (ADS)
Gao, Wenshuai; Hao, Ningning; Zheng, Fa-Wei; Ning, Wei; Wu, Min; Zhu, Xiangde; Zheng, Guolin; Zhang, Jinglei; Lu, Jianwei; Zhang, Hongwei; Xi, Chuanying; Yang, Jiyong; Du, Haifeng; Zhang, Ping; Zhang, Yuheng; Tian, Mingliang
2017-06-01
While pyrite-type PtBi2 with a face-centered cubic structure has been predicted to be a three-dimensional (3D) Dirac semimetal, experimental study of its physical properties remains absent. Here we report the angular-dependent magnetoresistance measurements of a PtBi2 single crystal under high magnetic fields. We observed extremely large unsaturated magnetoresistance (XMR) up to (11.2 ×106)% at T =1.8 K in a magnetic field of 33 T, which is comparable to the previously reported Dirac materials, such as WTe2 , LaSb, and NbP. The crystals exhibit an ultrahigh mobility and significant Shubnikov-de Hass quantum oscillations with a nontrivial Berry phase. The analysis of Hall resistivity indicates that the XMR can be ascribed to the nearly compensated electron and hole. Our experimental results associated with the ab initio calculations suggest that pyrite PtBi2 is a topological semimetal candidate that might provide a platform for exploring topological materials with XMR in noble metal alloys.
Miller, W.R.; Ficklin, W.H.; Learned, R.E.
1982-01-01
A hydrogeochemical survey utilizing waters from streams and springs was conducted in the area of two known porphyry copper deposits in the tropical-marine climate of westcentral Puerto Rico. The most important pathfinder for regional hydrogeochemical surveys is sulfate which reflects the associated pyrite mineralization. Because of increased mobility due to intense chemical weathering and the low pH environment, dissolved copper can also be used as a pathfinder for regional surveys and has the advantage of distinguishing barren pyrite from pyrite associated with copper mineralization. For follow-up surveys, the most important pathfinders are copper, sulfate, pH, zinc, and fluoride. High concentrations of dissolved copper and moderate concentrations of sulfate is a diagnostic indication of nearby sources of copper minerals. An understanding of the geochemical processes taking place in the streambeds and the weathering environment, such as the precipitation of secondary copper minerals, contributes to the interpretation of the geochemical data and the selection of the most favorable areas for further exploration. ?? 1982.
Technological and economic aspects of coal biodesulfurisation.
Klein, J
1998-01-01
The sulfur found in coal is either part of the molecular coal structure (organically bound sulfur), is contained in minerals such as pyrite (FeS2), or occurs in minor quantities in the form of sulfate and elemental sulfur. When pyrite crystals are finely distributed within the coal matrix, mechanical cleaning can only remove part of the pyrite. It can, however, be removed by microbial action requiring only mild conditions. The process involves simple equipment, almost no chemicals, but relatively long reaction times, and treatment of iron sulfate containing process water. Different process configurations are possible, depending on the coal particle size. Coal with particle sizes of less than 0.5 mm is preferably desulfurised in slurry reactors, while lump coal (> 0.5 mm) should be treated in heaps. Investment and operating costs are estimated for different process configurations on an industrial scale. Concerning the organically bound sulfur in coal there is up to now no promising biochemical pathway for the degradation and/or desulfurisation of such compounds.
NASA Astrophysics Data System (ADS)
Bustos Rodríguez, H.; Rojas Martínez, Y.; Oyola Lozano, D.; Pérez Alcázar, G. A.; Fajardo, M.; Mojica, J.; Molano, Y. J. C.
2005-02-01
In this work a study on gold mineral samples is reported, using optical microscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The auriferous samples are from the El Diamante mine, located in Guachavez-Nariño (Colombia) and were prepared by means of polished thin sections. The petrography analysis registered the presence, in different percentages that depend on the sample, of pyrite, quartz, arsenopyirite, sphalerite, chalcopyrite and galena. The XRD analysis confirmed these findings through the calculated cell parameters. One typical Rietveld analysis showed the following weight percent of phases: 85.0% quartz, 14.5% pyrite and 0.5% sphalerite. In this sample, MS demonstrated the presence of two types of pyrite whose hyperfine parameters are δ 1 = 0.280 ± 0.002 mm/s and Δ 1 = 0.642 ± 0.002 mm/s, δ 2 = 0.379 ± 0.002 mm/s and Δ 2 = 0.613 ± 0.002 mm/s.
Bradley, Michael W.; Worland, Scott C.
2015-01-01
Acid-rock drainage occurs through the interaction of rainfall on pyrite-bearing formations. When pyrite (FeS2) is exposed to oxygen and water in mine workings or roadcuts, the mineral decomposes and sulfur may react to form sulfuric acid, which often results in environmental problems and potential damage to the transportation infrastructure. The accelerated oxidation of pyrite and other sulfidic minerals generates low pH water with potentially high concentrations of trace metals. Much attention has been given to contamination arising from acid mine drainage, but studies related to acid-rock drainage from road construction are relatively limited. The U.S. Geological Survey, in cooperation with the Tennessee Department of Transportation, is conducting an investigation to evaluate the occurrence and processes controlling acid-rock drainage and contaminant transport from roadcuts in Tennessee. The basic components of acid-rock drainage resulting from transportation activities are described and a bibliography, organized by relevant categories (remediation, geochemical, microbial, biological impact, and secondary mineralization) is presented.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jodeiri Shokri, Behshad, E-mail: b.jodeiri@hut.ac.ir; Doulati Ardejani, Faramarz; Ramazi, Hamidreza
In this paper, an abandoned waste coal pile, which is resulted from Alborz-Sharghi coal washing plant, NE of Iran was mineralogically and geochemically characterized to evaluate pyrite oxidation, acid mine drainage (AMD) generation, and trace element mobility. After digging ten trenches and vertical sampling, a quantitative method including the atomic absorption test, and the quality-based methods including optical study were carried out for determination of pyrite fractions in the waste pile. The geochemical results revealed that the fraction of remaining pyrite increased with depth, indicating that pyrite oxidation is limited to the shallower depths of the pile which were confirmedmore » by variations of sulfate, pH, EC, and carbonate with depth of the pile. To evaluate the trend of trace elements and mineralogical constituents of the waste particles, the samples were analyzed by using XRD, ICP-MS, and ICP-OES methods. The results showed the secondary and neutralizing minerals comprising gypsum have been formed below the oxidation zone. Besides, positive values of net neutralization potential indicated that AMD generation has not taken in the waste pile. In addition, variations of trace elements with depth reveal that Pb and Zn exhibited increasing trends from pile surface toward the bottom sampling trenches while another of them such as Cu and Ni had decreasing trends with increasing depth of the waste pile.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Over, D.J.
In western New York State interbedded pyritic silty green and dark grey shales and siltstone of the Hanover Member, Java Formation, West Falls Group, are overlain by thick pyritic dark grey-black shale of the Dunkirk Member of the Canadaway formation. The dark shales in the upper Hanover and Dunkirk contain a diverse and well preserved conodont fauna which allows precise placement of the Frasnian-Famennian boundary at several described sections. At Pt. Gratiot, in far western New York State, the contact between the Hanover and Dunkirk is disconformable. The Frasnian-Famennian boundary is marked by a pyritic lag deposit at the basemore » of the Dunkirk which contains Palmatolepis triangularis and Pa. subperlobata. The underlying upper Hanover is characterized by Pa. bogartensis , Pa. cf. Pa. rhenana, Pa. winchelli, and Ancyrognathus (asymmetricus/calvini) Eastward, in the direction of the paleo-source area, the Frasnian-Famennian boundary is within the upper Hanover Member. At Irish Gulf the boundary is recognized within a 10 cm thick laminated pyritic dark grey shale bed 3.0 m below the base of the Dunkirk. Palmatolepis triangularis and Pa. subperlobata occur below a conodont-rich lag layer in the upper 2 cm of the bed. Palmatolepis bogartensis , Pa. cf. Pa. rhenana, Ancyrodella curvata, and Icriodus alternatus occur in the underlying 8 cm. Palmatolepis triangularis and Pa. winchelli occur in an underlying dark shale bed separated from the boundary bed by a hummocky cross-bedded siltstone layer.« less
Grimes, David J.; Earhart, Robert L.; de Carvalho, Delfim; Oliveira, Vitor; Oliveira, Jose T.; Castro, Paulo
1998-01-01
This report describes geochemical and geological studies which were conducted by the U.S. Geological Survey (USGS) and the Servicos Geologicos de Portugal (SPG) in the Portuguese pyrite belt (PPB) in southern Portugal. The studies included rare earth element (REE) distributions and geological and geochemical controls on the distribution of gold. Rare earth element distributions were determined in representative samples of the volcanic rocks from five west-trending sub-belts of the PPB in order to test the usefulness of REE as a tool for the correlation of volcanic events, and to determine their mobility and application as hydrothermal tracers. REE distributions in felsic volcanic rocks show increases in the relative abundances of heavy REE and a decrease in La/Yb ratios from north to south in the Portuguese pyrite belt. Anomalous amounts of gold are distributed in and near massive and disseminated sulfide deposits in the PPB. Gold is closely associated with copper in the middle and lower parts of the deposits. Weakly anomalous concentrations of gold were noted in exhalative sedimentary rocks that are stratigraphically above massive sulfide deposits in a distal manganiferous facies, whereas anomalously low concentrations were detected in the barite-rich, proximal-facies exhalites. Altered and pyritic felsic volcanic rocks locally contain highly anomalous concentrations of gold, suggesting that disseminated sulfide deposits and the non-ore parts of massive sulfide deposits should be evaluated for their gold potential.
NASA Astrophysics Data System (ADS)
Miotliński, Konrad; Postma, Dieke; Kowalczyk, Andrzej
2012-01-01
SummaryThe changes in groundwater quality occurring in a buried valley aquifer following a reduction in groundwater exploitation and enhanced infiltration due to extensive flooding of the Odra River in 1997 were investigated. Long-time series data for the chemical composition of groundwater in a large well field for drinking water supply indicated the deterioration of groundwater quality in the wells capturing water from the flooded area, which had been intensively cultivated since the 1960s. Infiltration of flooded river water into the aquifer is suggested by an elevated chloride concentration, although salt flushing from the rewatered unsaturated zone due to the enhanced recharge event is much more feasible. Concomitantly with chloride increases in the concentrations of sulphate, ferrous iron, manganese, and nickel imply the oxidation of pyrite (FeS 2) which is abundant in the aquifer. The proton production resulting from pyrite oxidation is buffered by the dissolution of calcite, while the Ca:SO 4 stoichiometry of the groundwater indicates that pyrite oxidation coupled with nitrate reduction is the dominant process occurring in the aquifer. The pyritic origin of SO42- is confirmed by the sulphur isotopic composition. The resultant Fe 2+ increase induces Mn-oxide dissolution and the mobilisation of Ni 2+ previously adsorbed to Mn-oxide surfaces. The study has a major implication for groundwater quality prediction studies where there are considerable variations in water level associated with groundwater management and climate change issues.
U-Pb isotope systematics and age of uranium mineralization, Midnite mine, Washington.
Ludwig, K. R.; Nash, J.T.; Naeser, C.W.
1981-01-01
Uranium ores at the Midnite mine, near Spokane, Washington, occur in phyllites and calcsilicates of the Proterozoic Togo Formation, near the margins of an anomalously uraniferous, porphyritic quartz monzonite of Late Cretaceous age. The present geometry of the ore zones is tabular, with the thickest zones above depressions in the pluton-country rock contact. Analyses of high-grade ores from the mine define a 207 Pb/ 204 Pb- 235 U/ 204 Pb isochron indicating an age of mineralization of 51.0 + or - 0.5 m.y. This age coincides with a time of regional volcanic activity (Sanpoil Volcanics), shallow intrusive activity, erosion, and faulting. U-Th-Pb isotopic ages of zircons from the porphyritic quartz monzonite in the mine indicate an age of about 75 m.y., hence the present orebodies were formed about 24 m.y. after its intrusion. The 51-m.y. time of mineralization probably represents a period of mobilization and redeposition of uranium by supergene ground waters, perhaps aided by mild heating and ground preparation and preserved by a capping of newly accumulated, impermeable volcanic rocks. It seems most likely that the initial concentration of uranium occurred about 75 m.y. ago, probably from relatively mild hydrothermal fluids in the contact-metamorphic aureole of the U-rich porphyritic quartz monzonite.Pitchblende, coffinitc, pyrite, marcasite, and hisingerite are the most common minerals in the uranium-bearing veinlets, with minor sphalerite and chalcopyrite. Coffinitc with associated marcasite is paragenetically later than pitchblende, though textural and isotopic evidence suggests no large difference in the times of pitchblende and colfinite formation.The U-Pb isotope systematics of total ores and of pitchblende-coffinite and pyrite-marcasite separates show that whereas open system behavior for U and Pb is essentially negligible for large (200-500 g) ore samples, Pb migration has occurred on a scale of 1 to 10 mm (out of pitchblende and coffinite and into pyrite and marcasite). Also, long-term continuous leakage of radioactive daughters of 238 U (probably 222 Rn) has occurred on scales of from approximately 100 mu m approximately 10 cm. The isotopic composition of unsupported radiogenic Pb in pyrite-marcasite seems to depend on the mineralogical microenvironment of the grains, so that the radiogenic Pb in pyrite-marcasite intimately intermixed with pitchblende-coffinite tends to be deficient in 206 Pb, and the radiogenic Pb in pyrite-marcasite in gangue tends to have excess 206 Pb. These systematics probably reflect differences between the average distances of Pb and 222 Rn diffusion since the formation of the ores.
Conceptual models of the formation of acid-rock drainage at road cuts in Tennessee
Bradley, Michael W.; Worland, Scott; Byl, Tom
2015-01-01
Pyrite and other minerals containing sulfur and trace metals occur in several rock formations throughout Middle and East Tennessee. Pyrite (FeS2) weathers in the presence of oxygen and water to form iron hydroxides and sulfuric acid. The weathering and interaction of the acid on the rocks and other minerals at road cuts can result in drainage with low pH (< 4) and high concentrations of trace metals. Acid-rock drainage can cause environmental problems and damage transportation infrastructure. The formation and remediation of acid-drainage from roads cuts has not been researched as thoroughly as acid-mine drainage. The U.S Geological Survey, in cooperation with the Tennessee Department of Transportation, is conducting an investigation to better understand the geologic, hydrologic, and biogeochemical factors that control acid formation at road cuts. Road cuts with the potential for acid-rock drainage were identifed and evaluated in Middle and East Tennessee. The pyrite-bearing formations evaluated were the Chattanooga Shale (Devonian black shale), the Fentress Formation (coal-bearing), and the Precambrian Anakeesta Formation and similar Precambrian rocks. Conceptual models of the formation and transport of acid-rock drainage (ARD) from road cuts were developed based on the results of a literature review, site reconnaissance, and the initial rock and water sampling. The formation of ARD requires a combination of hydrologic, geochemical, and microbial interactions which affect drainage from the site, acidity of the water, and trace metal concentrations. The basic modes of ARD formation from road cuts are; 1 - seeps and springs from pyrite-bearing formations and 2 - runoff over the face of a road cut in a pyrite-bearing formation. Depending on site conditions at road cuts, the basic modes of ARD formation can be altered and the additional modes of ARD formation are; 3 - runoff over and through piles of pyrite-bearing material, either from construction or breakdown material weathered from shale, and 4 - the deposition of secondary-sulfate minerals can store trace metals and, during rainfall, result in increased acidity and higher concentrations of trace metals in storm runoff. Understanding the factors that control ARD formation and transport are key to addressing the problems associated with the movement of ARD from the road cuts to the environment. The investigation will provide the Tennessee Department of Transportation with a regional characterization of ARD and provide insights into the geochemical and biochemical attributes for the control and remediation of ARD from road cuts.
Developments in Technical Education in the British Caribbean, 1940-60.
ERIC Educational Resources Information Center
Pemberton, S. Macpherson
The paper discusses developments in technical education in the British West Indies from 1940-1960 emphasizing the relation between education and economic development. The objective is to analyze the economic basis of progress in technical education. The document is presented in four chapters. Chapter I summarizes historical background prior to…
Programs of Study: Year 2 Joint Technical Report. Research Snapshot
ERIC Educational Resources Information Center
National Research Center for Career and Technical Education, 2010
2010-01-01
In January 2010, the National Research Center for Career and Technical Education (NRCCTE) issued a progress report on three studies being conducted by the Center that examine the implementation and outcomes of Programs of Study (POS), which were required in the 2006 reauthorization of the federal legislation for career and technical education…
Valentín-Vargas, Alexis; Neilson, Julia W; Root, Robert A; Chorover, Jon; Maier, Raina M
2018-03-15
Direct revegetation, or phytostabilization, is a containment strategy for contaminant metals associated with mine tailings in semiarid regions. The weathering of sulfide ore-derived tailings frequently drives acidification that inhibits plant establishment resulting in materials prone to wind and water dispersal. The specific objective of this study was to associate pyritic mine waste acidification, characterized through pore-water chemistry analysis, with dynamic changes in microbial community diversity and phylogenetic composition, and to evaluate the influence of different treatment strategies on the control of acidification dynamics. Samples were collected from a highly instrumented one-year mesocosm study that included the following treatments: 1) unamended tailings control; 2) tailings amended with 15% compost; and 3) the 15% compost-amended tailings planted with Atriplex lentiformis. Tailings samples were collected at 0, 3, 6 and 12months and pore water chemistry was monitored as an indicator of acidification and weathering processes. Results confirmed that the acidification process for pyritic mine tailings is associated with a temporal progression of bacterial and archaeal phylotypes from pH sensitive Thiobacillus and Thiomonas to communities dominated by Leptospirillum and Ferroplasma. Pore-water chemistry indicated that weathering rates were highest when Leptospirillum was most abundant. The planted treatment was most successful in disrupting the successional evolution of the Fe/S-oxidizing community. Plant establishment stimulated growth of plant-growth-promoting heterotrophic phylotypes and controlled the proliferation of lithoautotrophic Fe/S-oxidizers. The results suggest the potential for eco-engineering a microbial inoculum to stimulate plant establishment and inhibit proliferation of the most efficient Fe/S-oxidizing phylotypes. Copyright © 2017 Elsevier B.V. All rights reserved.
Moore, J.N.; Christenson, B.W.; Allis, R.G.; Browne, P.R.L.; Lutz, S.J.
2004-01-01
Acidic steam condensates in volcanic systems or shallow, oxygenated geothermal environments are typically enriched in SO4 and poor in Cl. These fluids produce distinctive alteration-induced assemblages as they descend. At Karaha - Telaga Bodas, located on the flank of Galunggung Volcano, Indonesia, neutralization of descending acid waters has resulted in the successive appearance of 1) advanced argillic alteration characterized by alunite, clay minerals and pyrite, 2) anhydrite, pyrite and interlayered sheet silicates, and 3) carbonates. Minor tourmaline, fluorite and native sulfur also are present locally, reflecting interactions with discharging magmatic gases. Water rock interactions were modeled at temperatures up to 250??C using the composition of acidic lake water from Telaga Bodas and that of a typical andesite as reactants. The simulations predict mineral distributions consistent with the observed assemblages and a decrease in the freezing-point depression of the fluid with increasing temperature. Fluids trapped in anhydrite, calcite and fluorite display a similar decrease in their freezing-point depressions, from 2.8?? to 1.5??C, as homogenization temperatures increase from 160?? to 205??C. The simulations indicate that the progressive change in fluid composition is due mainly to the incorporation of SO4 into the newly formed hydrothermal minerals. The salinities of fluid inclusions containing Cl-deficient steam condensates are better expressed in terms of H2SO4 equivalents than the commonly used NaCl equivalents. At solute concentrations >1.5 molal, freezing-point depressions represented as NaCl equivalents overestimate the salinity of Cl-poor waters. At lower concentrations, differences between apparent salinities calculated as NaCl and H2SO 4 equivalents are negligible.
Proceedings: Computer Science and Data Systems Technical Symposium, volume 1
NASA Technical Reports Server (NTRS)
Larsen, Ronald L.; Wallgren, Kenneth
1985-01-01
Progress reports and technical updates of programs being performed by NASA centers are covered. Presentations in viewgraph form are included for topics in three categories: computer science, data systems and space station applications.
Flotation machine and process for removing impurities from coals
Szymocha, K.; Ignasiak, B.; Pawlak, W.; Kulik, C.; Lebowitz, H.E.
1995-12-05
The present invention is directed to a type of flotation machine that combines three separate operations in a single unit. The flotation machine is a hydraulic separator that is capable of reducing the pyrite and other mineral matter content of a coal. When the hydraulic separator is used with a flotation system, the pyrite and certain other mineral particles that may have been entrained by hydrodynamic forces associated with conventional flotation machines and/or by the attachment forces associated with the formation of microagglomerates are washed and separated from the coal. 4 figs.
Flotation machine and process for removing impurities from coals
Szymocha, Kazimierz; Ignasiak, Boleslaw; Pawlak, Wanda; Kulik, Conrad; Lebowitz, Howard E.
1995-01-01
The present invention is directed to a type of flotation machine that combines three separate operations in a single unit. The flotation machine is a hydraulic separator that is capable of reducing the pyrite and other mineral matter content of a coal. When the hydraulic separator is used with a flotation system, the pyrite and certain other minerals particles that may have been entrained by hydrodynamic forces associated with conventional flotation machines and/or by the attachment forces associated with the formation of microagglomerates are washed and separated from the coal.
Flotation machine and process for removing impurities from coals
Szymocha, K.; Ignasiak, B.; Pawlak, W.; Kulik, C.; Lebowitz, H.E.
1997-02-11
The present invention is directed to a type of flotation machine that combines three separate operations in a single unit. The flotation machine is a hydraulic separator that is capable of reducing the pyrite and other mineral matter content of a coal. When the hydraulic separator is used with a flotation system, the pyrite and certain other minerals particles that may have been entrained by hydrodynamic forces associated with conventional flotation machines and/or by the attachment forces associated with the formation of microagglomerates are washed and separated from the coal. 4 figs.
Flotation machine and process for removing impurities from coals
Szymocha, Kazimierz; Ignasiak, Boleslaw; Pawlak, Wanda; Kulik, Conrad; Lebowitz, Howard E.
1997-01-01
The present invention is directed to a type of flotation machine that combines three separate operations in a single unit. The flotation machine is a hydraulic separator that is capable of reducing the pyrite and other mineral matter content of a coal. When the hydraulic separator is used with a flotation system, the pyrite and certain other minerals particles that may have been entrained by hydrodynamic forces associated with conventional flotation machines and/or by the attachment forces associated with the formation of microagglomerates are washed and separated from the coal.
All that glitters: fool's gold in the early-modern era.
Roos, Anna Marie
2008-12-01
Natural philosophers of the early-modern period perceived fool's gold or iron pyrites as a substance required for the formation of metals, and chemists such as Johann Glauber speculated the vitriol produced from pyrites was the source of the legendary philosopher's stone. The sulphurous exhalations of fool's gold were also thought by members of the early Royal Society to be the basis of a variety of meteorological, geological and medical effects, including the production of thunder, lightning, earthquakes and volcanoes, fossilisation and petrifaction, as well as the principal cause of bladder and gallstones.
Technical progress in silicon sheet growth under DOE/JPL FSA program, 1975-1986
NASA Technical Reports Server (NTRS)
Kalejs, J. P.
1986-01-01
The technical progress made in the Silicon Sheet Growth Program during its 11 years was reviewed. At present, in 1986, only two of the original 9 techniques have survived to the start-up, pilot-plant stage in industry. These two techniques are the edge-defined, film-fed growth (EFG) technique that produces closed shape polygons, and the WEB dendritic technique that produces single ribbons. Both the status and future concerns of the EFG and WEB techniques were discussed.
1991-01-24
Molecular Graphics, vol. 6, No. 4 (Dec. 1988), p. 223. Turk, Greg, "Interactive Collision Detection for Molecular Graphics," M.S. thesis , UNC-Chapel Hill...Problem," Master’s thesis , UNC Department of Computer Science Technical Report #TR87-013, May 1987. Pique, ME., "Technical Trends in Molecular Graphics...AD-A236 598 Seventeenth Annual Progress Report and 1992-97 Renewal Proposal Interactive Graphics for Molecular Studies TR91-020 January 24, 1991 red
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fortmann, R.G.; Walker, J.P.
1993-07-10
Sierra Energy Company`s targeted goals during the third quarter of this Cooperative Agreement included the following objectives from the Statement of Work: in Phase 2A, completion of subtask 2.1.2--acquire best possible field data in the 3-D seismic program; and initiation of Subtask 2.1.3--process acquired 3-D seismic data. Technical progress is described for these tasks.
10 CFR 603.1100 - Contracting officer's post-award responsibilities.
Code of Federal Regulations, 2011 CFR
2011-01-01
... technical progress, financial status, and future program plans. (b) Tracking and processing of reports... progress reports, and patent reports. (c) Handling payment requests and related matters. For a TIA using advance payments, that includes reviews of progress to verify that there is continued justification for...
7 CFR 3402.23 - Documentation of progress on funded projects.
Code of Federal Regulations, 2011 CFR
2011-01-01
... the academic program due to unsatisfactory academic progress; or voluntarily withdraws from the Fellowship or the academic program. If a Fellow has not completed all degree requirements at the end of the... database contains narrative project information, progress/impact statements, and final technical reports...
7 CFR 3402.23 - Documentation of progress on funded projects.
Code of Federal Regulations, 2014 CFR
2014-01-01
... the academic program due to unsatisfactory academic progress; or voluntarily withdraws from the Fellowship or the academic program. If a Fellow has not completed all degree requirements at the end of the... database contains narrative project information, progress/impact statements, and final technical reports...
7 CFR 3402.23 - Documentation of progress on funded projects.
Code of Federal Regulations, 2012 CFR
2012-01-01
... the academic program due to unsatisfactory academic progress; or voluntarily withdraws from the Fellowship or the academic program. If a Fellow has not completed all degree requirements at the end of the... database contains narrative project information, progress/impact statements, and final technical reports...
7 CFR 3402.23 - Documentation of progress on funded projects.
Code of Federal Regulations, 2013 CFR
2013-01-01
... the academic program due to unsatisfactory academic progress; or voluntarily withdraws from the Fellowship or the academic program. If a Fellow has not completed all degree requirements at the end of the... database contains narrative project information, progress/impact statements, and final technical reports...
Veins in the northern part of the Boulder batholith, Montana
Pinckney, D.M.
1965-01-01
About 20 miles north of Butte and extending nearly to Helena, is an area of 350 square miles containing hundreds of veins and altered zones. The bedrock of the area is 1) late Cretaceous volcanic rocks, forerunners of the Boulder batholith, 2) the Boulder batholith of late Cretaceous to early Tertiary age and 3) two groups of Tertiary volcanic rocks lying on the eroded batholith. The veins are post-batholith and pre-Tertiary in age. The veins are largely either quartz-sulfide veins of mesothermal type or chalcedony veins of epithermal type. The relations of these two types of veins have been the subject of conflicting ideas for 60 years. Three workers have proposed three different genetic classifications. This report shows that the quartz veins and the chalcedony veins are closely related parts of a strongly zoned hypogene vein system. Strong zonal patterns were established using the grain size of quartz (or pyrite vs. carbonate in one district) as well as features of the altered rocks. The scale of the zoning ranges from single veins through groups of veins or mining districts to the entire mineralized area. Single veins are zoned around a core of coarse-grained quartz; the quartz outward from the core becoming progressively finer-grained. The cores are zoned around eight major centers and several lesser ones. The centers and their nearby related veins are assigned to central, intermediate, and peripheral zones. Nearly all of the veins around the edge of the mineralized area are chalcedony. Envelopes of altered rocks consist of seven major bands representing three major groups of constituents, aluminum silicates, iron-bearing minerals, and silica. Plagioclase altered successively to montomorillite, kaolinite, and sericite; potassium feldspar altered to sericite (aluminum silicate group). Biotite released iron which formed successively, iron oxides, iron-bearing carbonate, and pyrite (iron-bearing minerals). Excess silica formed silicified bands. Constituents for which no stable phase occurs were largely leached from the rocks. A model has been constructed showing the arrangement of zoned veins and altered rocks in which the minerals produced by alteration are arranged in bands on each side of the vein, similar to the Butte pattern. Along strike from the cores, the inner bands thin and pinch out against the vein so that the vein becomes enclosed successively in the next outer bands. The sequence of alteration minerals along the veins is sericite, kaolinite, and montmorillonite for the aluminum silicates; and pyrite, carbonate, and iron oxides for the iron-bearing minerals. Alteration is thought to be controlled by reactions between wallrock minerals and the pore solution. In the aluminum silicate reactions, H+ was added to the rock and Na+ and Ca++ were removed. Carbon and sulfur from the vein were added to iron of the wallrock to produce pyrite and iron carbonate. Carbon, sulfur, and hydrogen moved into the wallrock, while Ca++, Na+, and some SiO2 moved toward the vein along concentration or activity gradients. Temperatures during mineralization ranged from below 200? C to about 350? C.
ERIC Educational Resources Information Center
Allen, Nancy L.; McClellan, Catherine A.; Stoeckel, Joan J.
2005-01-01
This report provides an update to the technical analysis procedures documenting the 1996 National Assessment of Educational Progress (NAEP) as presented in "The NAEP 1996 Technical Report" (Allen, Carlson, and Zelenak, 1999). It describes how the 1999 long-term trend data were incorporated into the trend analyses. Since no national main…
Sulfide scaling in low enthalpy geothermal environments; A survey
DOE Office of Scientific and Technical Information (OSTI.GOV)
Criaud, A.; Fouillac, C.
1989-01-01
A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are farmore » less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.« less
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.
NASA Astrophysics Data System (ADS)
Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.
2017-09-01
Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting enhanced formation of secondary sulfur containing species and release of copper and iron. This in turn suggests accelerated supergene formation and enhanced metalliferous drainage under these conditions.
Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.
Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai
2016-02-15
Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.
Viets, J.G.; Leach, D.L.; Lichte, F.E.; Hopkins, R.T.; Gent, C.A.; Powell, J.W.
1996-01-01
Paragenetic and minor- and trace-element studies were conducted on samples of epigenetic ore and gangue minerals collected from mines and drill core in the Silesian-Cracow (S-C) district of southern Poland. Four discrete mineral suites representing four mineralizing stages can be identified throughout the district. The earliest epigenetic minerals deposited during stage 1 consist of a late dolomite cement together with minor pyrite and marcasite. Stage 2 was the first ore-forming stage and included repetitive deposition of sphalerite and galena in a variety of morphologies. Stage 3 abruptly followed the first ore stage and deposited marcasite and pyrite with variable amounts of late sphalerite and galena. In the samples studied, minerals deposited during stage 3 are predominately marcasite-pyrite with minor sphalerite and galena in the Pomorzany and Olkusz mines, whereas, at the Trzebionka mine, stage 3 mineralization deposited mostly galena and sphalerite with little marcasite or pyrite. Stage 4 minerals include contains barite, followed by calcite, with very minor pyrite and a rare, late granular sphalerite. Compared to other major Mississippi Valley-type (MVT) districts of the world, the Silesian-Cracow district contains sphalerite with the second largest range in Ag concentrations and the largest range in Fe and Cd concentrations of any district. Unlike in other districts, very wide ranges in minor- and trace-element concentrations are also observed in paragenetically equivalent samples collected throughout the district. This wide range indicates that the minor- and trace-element content of the ore-forming environment was highly variable, both spatially and temporally, and suggests that the hydrologic system that the ore fluids traversed from their basinal source was very complex. Throughout the district, a significant increase in Tl, Ge, and As concentrations is accompanied by a lightening of sulfur isotopes between stage 2 and stage 3 minerals. This change appears to record a major district-scale hydrologic event that probably reflects the introduction of fluids with significantly different geochemistry than that of earlier ore-forming fluids.
Liu, Gaisheng; Yang, P.; Peng, Z.; Chou, C.-L.
2004-01-01
The Yanzhou mining area in west Shandong Province, China contains coals of Permian and Carboniferous age. The 31 and 32 seams of the Permian Shanxi Formation and seams 6, 15-17 of the Carboniferous Taiyuan Formation were analyzed for coal petrology, mineralogy and geochemical parameters. The parameters indicate that the coal is high volatile bituminous in rank. The coal is characterized by high vitrinite and low to medium inertinite and liptinite contents. These properties may be related to evolution of the coal forming environment from more reducing conditions in a marine influenced lower delta plain environment for the early Taiyuan coals to more oxidizing paleoenvironments in an upper delta plain for the upper Shanxi coal seams. The major mineral phases present in the coal are quartz, kaolinite, pyrite and calcite. Sulfur is one of the hazardous elements in coal. The major forms of sulfur in coal are pyritic, organic and sulfate sulfur. Pyritic and organic sulfur generally account for the bulk of the sulfur in coal. Elemental sulfur also occurs in coal, but only in trace to minor amounts. In this paper, the distribution and concentration of sulfur in the Yanzhou mining district are analyzed, and the forms of sulfur are studied. The sulfur content of the Taiyuan coal seams is considerably higher than that of the Shanxi coals. Organic sulfur content is positively correlated to total and pyritic sulfur. The vertical variation of Cu, Zn, Pb, As, Th, U and sulfur contents in coal seam 3 of the Shanxi Formation in the Xinglongzhuang mine show that all these trace elements, with the exception of Th, are enriched in the top and bottom plies of the seam, and that their concentrations are also relatively high in the dirt bands within the seam. The pyritic sulfur is positively correlated with total sulfur, and both are enriched in the top, bottom and parting plies of the seam. The concentrations of the trace elements are closely related to sulfur and ash contents. Most of the trace elements are correlated with the ash content, and may be associated with the mineral matter in the coal. ?? 2004 Elsevier Ltd. All rights reserved.
Solubility relationships of aluminum and iron minerals associated with acid mine drainage
NASA Astrophysics Data System (ADS)
Sullivan, Patrick J.; Yelton, Jennifer L.; Reddy, K. J.
1988-06-01
The ability to properly manage the oxidation of pyritic minerals and associated acid mine drainage is dependent upon understanding the chemistry of the disposal environment. One accepted disposal method is placing pyritic-containing materials in the groundwater environment. The objective of this study was to examine solubility relationships of Al and Fe minerals associated with pyritic waste disposed in a low leaching aerobic saturated environment. Two eastern oil shales were used in this oxidizing equilibration study, a New Albany Shale (unweathered, 4.6 percent pyrite), and a Chattanooga Shale (weathered, 1.5 percent pyrite). Oil shale samples were equilibrated with distilled-deionized water from 1 to 180 d with a 1∶1 solid-to-solution ratio. The suspensions were filtered and the clear filtrates were analyzed for total cations and anions. Ion activities were calculated from total concentrations. Below pH 6.0, depending upon SO{4/2-} activity, Al3+ solubility was controlled by AlOHSO4 (solid phase) for both shales. Initially, Al3+ solubility for the New Albany Shale showed equilibrium with amorphous Al(OH)3. The pH decreased with time, and Al3+ solubility approached equilibrium with AlOHSO4(s). Below pH 6.0, Fe3+ solubility appeared to be regulated by a basic iron sulfate solid phase with the stoichiometric composition of FeOHSO4(s). The results of this study indicate that below pH 6.0, Al3+ solubilities, are limited by basic Al and Fe sulfate solid phases (AlOHSO4(s) and FeHSO4(s)). The results from this study further indicate that the acidity in oil shale waters is produced from the hydrolysis of Al3+ and Fe3+ activities in solution. These results indicate a fundamental change in the stoichiometric equations used to predict acidity from iron sulfide oxidation. The results of this study also indicate that water quality predictions associated with acid mine drainage can be based on fundamental thermodynamic relationships. As a result, waste management decisions can be based on waste-specific/site-specific test methods.
NASA Astrophysics Data System (ADS)
Gallego-Torres, David; Reolid, Matías; Nieto-Moreno, Vanesa; Martínez-Casado, Francisco Javier
2015-12-01
The Early Toarcian Oceanic Anoxic Event (T-OAE) represents one of the major alterations of the carbon cycle of the Mesozoic period. Despite being globally recognized, and particularly represented within the Tethys realm, its expression in the sedimentary record is highly variable depending on the studied section, which suggests local environmental factors exert a major control on the resulting lithological appearance of the event. We investigated the Fuente Vidriera section, in the eastern External Subbetic of the Betic Cordillera (Spain), where the Lower Jurassic is represented by alternate layers of marls and marly limestones, and the T-OAE is identified by a major δ13C excursion, micropalaeontological, ichnofacies and geochemical evidences. For this study, we analyzed pyrite framboid size distribution of the sedimentary sequence in Fuente Vidriera. The outcome, according to previous studies on pyrite framboid distribution, is contradictory when compared to all other evidences, suggesting oxygen depletion during the T-OAE. The results have been reinterpreted in the light of Crystal Size Distribution Theory and we conclude that not only growth time but also geochemical environment controls pyrite formation. Since growth time is directly related to burial rates, this approach allows us to reconstruct relative variations of sedimentation rates during the Early Jurassic in this location. Based on the obtained results, we provide new evidences for wide-spread transgression during the Early Toarcian in the South Iberian palaeomargin, which induced low sedimentation rate and lower energetic conditions, as well as favored oxygen impoverished bottom waters.
NASA Astrophysics Data System (ADS)
Havig, Jeff R.; Grettenberger, Christen; Hamilton, Trinity L.
2017-06-01
Streams impacted by acid mine drainage (AMD, also known as acid rock drainage) represent local environmental and ecological disasters; however, they may also present an opportunity to study microbial communities in environments analogous to past conditions. Neoarchean continents had streams and rivers replete with detrital pyrites. Following the emergence of oxygenic photosynthesis, Cyanobacteria colonized streams and rivers on continental surfaces. The combination of labile detrital pyrite grains and locally produced O2 generated by Cyanobacteria produced ideal conditions for pyrite oxidation similar to that found at modern AMD-impacted sites. To explore the connection of modern sites to ancient conditions, we sampled sites that exhibited a range of AMD-impact (e.g., pH from 2.1 to 7.9 [Fe2+] up to 5.2 mmol/L [SO42-] from 0.3 to 52.4 mmol/L) and found (i) nearly all analytes correlated to sulfate concentration; (ii) all sites exhibited the predominance of a single taxon most closely related to Ferrovum myxofaciens, an Fe-oxidixing betaproteoabacterium capable of carbon and nitrogen fixation, and (iii) signs of potential inorganic carbon limitation and nitrogen cycling. From these findings and building on the work of others, we present a conceptual model of continental surfaces during the Neoarchean and Paleoproterozoic linking local O2 production to pyrite oxidation on continental surfaces to sulfate production and delivery to nearshore environments. The delivery of sulfate drives sulfate reduction and euxinia—favoring anoxygenic photosynthesis over cyanobacterial O2 generation in near-continent/shelf marine environments.
Arsenic transformation and mobilization from minerals by the arsenite oxidizing strain WAO
Rhine, E.D.; Onesios, K.M.; Serfes, M.E.; Reinfelder, J.R.; Young, L.Y.
2008-01-01
Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 ??g L-1, with a maximum of 215 ??g L-1. In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers. ?? 2008 American Chemical Society.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.
2015-06-01
In the first part of this paper, a Scanning Electron Microscopy and contact angle study of a pyrite surface (100) is reported describing the relationship between surface oxidation and the hydrophilic surface state. In addition to these experimental results, the following simulated surface states were examined using Molecular Dynamics Simulation (MDS): fresh unoxidized (100) surface; polysulfide at the (100) surface; elemental sulfur at the (100) surface. Crystal structures for the polysulfide and elemental sulfur at the (100) surface were simulated using Density Functional Theory (DFT) quantum chemical calculations. The well known oxidation mechanism which involves formation of a metal deficientmore » layer was also described with DFT. Our MDS results of the behavior of interfacial water at the fresh and oxidized pyrite (100) surfaces without/with the presence of ferric hydroxide include simulated contact angles, number density distribution for water, water dipole orientation, water residence time, and hydrogen-bonding considerations. The significance of the formation of ferric hydroxide islands in accounting for the corresponding hydrophilic surface state is revealed not only from experimental contact angle measurements but also from simulated contact angle measurements using MDS. The hydrophilic surface state developed at oxidized pyrite surfaces has been described by MDS, on which basis the surface state is explained based on interfacial water structure. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE funded work performed by Liem X. Dang. Battelle operates the Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.« less
Factors affecting the transformation of a pyritic tailing: scaled-up column tests.
García, C; Ballester, A; González, F; Blázquez, M L
2005-02-14
Two different methods for predicting the quality of the water draining from a pyritic tailing are compared; for this, a static test (ABA test) and a kinetic test in large columns were chosen. The different results obtained in the two experimental set-ups show the necessity of being careful in selecting both the adequate predictive method and the conclusions and extrapolations derived from them. The tailing chosen for the weathering tests (previously tested in shake flasks and in small weathering columns) was a pyritic residue produced in a flotation plant of complex polymetallic sulphides (Huelva, Spain). The ABA test was a modification of the conventional ABA test reported in bibliography. The modification consisted in the soft conditions employed in the digestion phase. For column tests, two identical methacrylate columns (150 cm high and 15 cm diameter) were used to study the chemical and microbiological processes controlling the leaching of pyrite. The results obtained in the two tests were very different. The static test predicted a strong potential acidity for the tailing. On the contrary, pH value in the effluents draining from the columns reached values of only 5 units, being the concentration of metals (<600 mg/L) and sulphate ions (<17,000 mg/L) very small and far from the values of a typical acid mine drainage. In consequence, the static test may oversize the potential acidity of the tailing; whereas large columns may be saturated in water, displacing the oxygen and inhibiting the microbial activity necessary to catalyse mineral oxidation.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Song, S.; Perkson, A.; Trass, O.
1996-12-31
Oil agglomeration is an excellent technique for the beneficiation of fine coal. For separation of the spherical agglomerates by screening, a high level of oil must be used, however. When the subsequent separation is done by flotation, this disadvantage is eliminated. Better pyrite removal is also possible. In this paper, such a fine coal beneficiation process, also called hydrophobic flocculation-flotation (HFF), is described. It features low non-polar oil consumption, intensive mechanical energy input, and smaller agglomerates or looser flocs. This process can be simplified by grinding the coal in water with small amounts of oil added. The excess grinding energymore » is then used for agglomerating the coal. The Prince coal from Nova Scotia contained 13.3% ash and 3.3% total sulfur, 1.4% pyritic. After four stages of flotation, ash and pyrite removal were 93% and 66% respectively, with 87% combustibles recovery. The parameters affecting the HFF process, such as particle size, dosage of non-polar oil, pH value of the slurry and duration of agitation, were investigated. Simultaneous grinding and agglomeration (SGA) utilizing the Szego Mill was also explored at the very low oil levels used. The intensive agitation/preconditioning step prior to flotation was eliminated. When the other parameters established from the sequential process were used with the SGA process, virtually identical beneficiation results were obtained, but with slightly lower combustibles recovery. While further testing is required to properly optimize the SGA process conditions, significant equipment simplification and energy savings are possible.« less
Nóbrega, G N; Ferreira, T O; Romero, R E; Marques, A G B; Otero, X L
2013-09-01
Iron and sulfur are key elements in the biogeochemistry of estuarine soils, in which Fe and sulfate reduction (SR) pathways are important for organic matter decomposition. In the semi-arid coast of NE Brazil, mangroves are characterized by large seasonal variations in weather and the presence of numerous shrimp farms. The objective was to determine the impacts of shrimp farm effluents on iron and sulfur geochemistry in mangrove soils under the semi-arid climate of NE Brazil. A seasonal study was made of two mangrove forest soils (SF, a mangrove forest that directly receives wastewater from shrimp ponds and CS, a control site). Pyrite Fe, oxyhydroxides Fe, acid volatile sulfide, degree of pyritization (DOP), pH, Eh, total organic carbon (TOC) and total S were determined. There was a clear decrease in pyritic Fe and DOP in the SF soils, which may be related to the anaerobic oxidation of pyrite coupled with nitrate reduction, or to the dominance of denitrification over SR. Lower TOC contents in the SF site suggest that below ground decomposition increased in response to eutrophication. The seasonal variations led to important changes in the semi-arid mangrove soils. During the dry period, both soils experienced oxidizing conditions with remarkable loss of reduced and oxidized forms of Fe, which may have important environmental implications as Fe is biolimiting for marine primary production. The data show that both factors (seasonal weather variations and shrimp effluents) play important roles in the geochemical processes that occur in these soils and, thus, may affect their functioning and maintenance.
Technologies for diagnosis and treatment of acute stroke
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fitch, J.P.
1998-02-09
From October 1994 to June 1997, a multidisciplinary team of scientists and engineers at Lawrence Livermore National Laboratory were funded through LDRD to develop and integrate technologies for diagnosis and treatment of acute stroke. The project was summarized in a Science and Technology Review article `Brain Attack` that appeared in June 1997 and again in the Center for Healthcare Technologies Report (UCRL-LR-124761). This article is the best overview of the project, epidemiology of stroke and technical progress. Most of the technical progress has been documented in conference papers and presentations and refereed journal articles. Additional technical publication can be expectedmore » as our remaining patent applications progress through the US Patent and Trademark Office. The purpose of this report is to provide an appropriate introduction and organization to the numerous publications so that interested readers can quickly find information. Because there is no documentation for the history of this project, this report provides a summary. It also provides the final status report for the LDRD funding.« less
Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide
NASA Astrophysics Data System (ADS)
Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.; Thomas, Joseph G.; Ding, Qi; Chang, Hung-Chih; Tsai, Meng-Lin; He-Hau, Jr.; Jin, Song
2015-12-01
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 (CoS2), 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-2 at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n+-p-p+ silicon micropyramids achieved photocurrents up to 35 mA cm-2 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.
Chelate-assisted phytoextraction of heavy metals in a soil contaminated with a pyritic sludge.
Peñalosa, Jesus Manuel; Carpena, Ramón O; Vázquez, Saúl; Agha, Ramsy; Granado, Ana; Sarro, María José; Esteban, Elvira
2007-05-25
The occurrence of many polluted areas as that affected by the accident of the Aznalcóllar pyrite mine has promoted phytoremediation as a technology able to reduce the risk of heavy metal contamination at low cost. White lupin plant has been considered a good candidate for phytoremediation. We studied the capacity of several complexing agents to improve the ability of white lupin for heavy metal phytoremediation in soils with multi-elemental pollution from acid pyritic sludge. Solution-soil interaction was studied and pot experiments with sludge-affected soil were carried out to this end. The interaction experiments indicated that EDTA and NTA were more efficient than malate and citrate in solubilizing metals (Fe, Mn, Cu, Zn, Cd), with minimum differences between EDTA and NTA. The pot trial showed that NTA was able to mobilize toxic elements from sludge-polluted soil and hence increasing their concentrations in plant (Mn, Cu, Zn, As, Cd). However, the NTA treatment promoted an increase of toxic elements concentrations, especially for As, Cd, Pb, in the lixiviates exceeding the maximum permissible levels, so a careful management of chelate is necessary.
Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media
Ma, Yingqun; Lin, Chuxia
2013-01-01
At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria. PMID:23760258
Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media
NASA Astrophysics Data System (ADS)
Ma, Yingqun; Lin, Chuxia
2013-06-01
At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.
Microbial oxidation of Fe²⁺ and pyrite exposed to flux of micromolar H₂O₂ in acidic media.
Ma, Yingqun; Lin, Chuxia
2013-01-01
At an initial pH of 2, while abiotic oxidation of aqueous Fe(2+) was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe(2+) could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe(2+) to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe(2+)-Fe(3+) conversion rate in the solution (due to reduced microbial activity) weakened the Fe(3+)-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.
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.
Dean, W.E.; Arthur, M.A.
1989-01-01
Cretaceous marine strata deposited in shallow to intermediate depths in the Western Interior seaway of North America show considerable variation in organic-carbon enrichment and degree of pyrite formation. The extreme range of paleoceanographic and depositional conditions that occurred in this seaway provide a unique opportunity to examine the effects of iron-, carbon-, and sulfur-limitation on pyrite formation in one region over about 30 my. Ternary diagrams of the system Fe-S-OC, together with some measure of the reactivity of organic matter (pyrolysis hydrogen index), provide a rapid means of recognizing iron-, carbon-, and sulfur-limitation on pyrite formation in a series of samples from a single lithologic unit. Iron limitation is indicated by a concentration of data along a line of constant S/Fe ratio on a Fe-S-OC ternary diagram. Carbon limitation is indicated by a concentration of data along a line of constant S/OC ratio. Sulfur-limitation is suggested by the lack of a systematic Fe-S-OC relationship and residual organic matter that is high in abundance and reactivity. -from Authors
Howe, S.S.
1985-01-01
The Devonian massive sulfide orebodies of the West Shasta district in N California are composed primarily of pyrite, with lesser amounts of other sulfide and gangue minerals. Examination of polished thin sections of more than 100 samples from the Mammoth, Shasta King, Early Bird, Balaklala, Keystone, and Iron Mountain mines suggests that mineralization may be divided into 6 paragenetic stages, the last 5 each separated by an episode of deformation: 1) precipitation of fine-grained, locally colloform and framboidal pyrite and sphalerite; 2) deposition of fine-grained arsenopyrite and coarse-grained pyrite; 3) penetration and local replacement of sulfide minerals of stages 1 and 2 along growth zones and fractures by chalcopyrite, sphalerite, galena, tennantite, pyrrhotite, bornite, and idaite; 4) recrystallization and remobilization of existing minerals; 5) deposition of quartz, white mica, chlorite, and calcite; and 6) formation of bornite, digenite, chalcocite, and covellite during supergene enrichment of several orebodies at the Iron Mountain mine. Mineralogic and textural evidence do not support a second major episode of massive sulfide mineralization during the Permian. -from Author
Proceedings: Computer Science and Data Systems Technical Symposium, volume 2
NASA Technical Reports Server (NTRS)
Larsen, Ronald L.; Wallgren, Kenneth
1985-01-01
Progress reports and technical updates of programs being performed by NASA centers are covered. Presentations in viewgraph form, along with abstracts, are included for topics in three catagories: computer science, data systems, and space station applications.
NASA Astrophysics Data System (ADS)
Wu, Zu-guang; Tian, Zhan-jun; Liu, Hui; Huang, Rui; Zhu, Guo-hua
2009-07-01
Being the only listed telecom operators of A share market, China Unicom has always been attracted many institutional investors under the concept of 3G recent years,which itself is a great technical progress expectation.Do the institutional investors or the concept of technical progress have signficant effect on the improving of firm's operating efficiency?Though reviewing the documentary about operating efficiency we find that schoolars study this problem useing the regress analyzing based on traditional production function and data envelopment analysis(DEA) and financial index anayzing and marginal function and capital labor ratio coefficient etc. All the methods mainly based on macrodata. This paper we use the micro-data of company to evaluate the operating efficiency.Using factor analyzing based on financial index and comparing the factor score of three years from 2005 to 2007, we find that China Unicom's operating efficiency is under the averge level of benchmark corporates and has't improved under the concept of 3G from 2005 to 2007.In other words,institutional investor or the conception of technical progress expectation have faint effect on the changes of China Unicom's operating efficiency. Selecting benchmark corporates as post to evaluate the operating efficiency is a characteristic of this method ,which is basicallly sipmly and direct.This method is suit for the operation efficiency evaluation of agriculture listed companies because agriculture listed also face technical progress and marketing concept such as tax-free etc.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1994-05-01
West Virginia University (WVU) and the US DOE Morgantown Energy Technology Center (METC) entered into a Cooperative Agreement on August 29, 1992 entitled ``Decontamination Systems Information and Research Programs.`` Stipulated within the Agreement is the requirement that WVU submit to METC a series of Technical Progress Reports on a quarterly basis. This report comprises the first Quarterly Technical Progress Report for Year 2 of the Agreement. This report reflects the progress and/or efforts performed on the sixteen (16) technical projects encompassed by the Year 2 Agreement for the period of January 1 through March 31, 1994. In situ bioremediation ofmore » chlorinated organic solvents; Microbial enrichment for enhancing in-situ biodegradation of hazardous organic wastes; Treatment of volatile organic compounds (VOCs) using biofilters; Drain-enhanced soil flushing (DESF) for organic contaminants removal; Chemical destruction of chlorinated organic compounds; Remediation of hazardous sites with steam reforming; Soil decontamination with a packed flotation column; Use of granular activated carbon columns for the simultaneous removal of organics, heavy metals, and radionuclides; Monolayer and multilayer self-assembled polyion films for gas-phase chemical sensors; Compact mercuric iodide detector technology development; Evaluation of IR and mass spectrometric techniques for on-site monitoring of volatile organic compounds; A systematic database of the state of hazardous waste clean-up technologies; Dust control methods for insitu nuclear and hazardous waste handling; Winfield Lock and Dam remediation; and Socio-economic assessment of alternative environmental restoration technologies.« less
ERIC Educational Resources Information Center
Guarino, Heidi; Yoder, Shaun
2015-01-01
"Seizing the Future: How Ohio's Career and Technical Education Programs Fuse Academic Rigor and Real-World Experiences to Prepare Students for College and Work," demonstrates Ohio's progress in developing strong policies for career and technical education (CTE) programs to promote rigor, including college- and career-ready graduation…
ERIC Educational Resources Information Center
Iwamoto, Muneharu
In the course of Japan's economic progress, remarkable changes have occurred in the structure of industry and employment. Workers are in extremely short supply in such occupations as mining, manufacturing and construction, services, transportation and communication, sales, and professional and technical. On the basis of recommendations of the…
25 CFR 30.104 - What is the Secretary's definition of AYP?
Code of Federal Regulations, 2011 CFR
2011-04-01
... PROGRESS Defining Adequate Yearly Progress § 30.104 What is the Secretary's definition of AYP? The... accepted by the Department of Education. The Secretary is committed to providing technical assistance to a...
25 CFR 30.104 - What is the Secretary's definition of AYP?
Code of Federal Regulations, 2010 CFR
2010-04-01
... PROGRESS Defining Adequate Yearly Progress § 30.104 What is the Secretary's definition of AYP? The... accepted by the Department of Education. The Secretary is committed to providing technical assistance to a...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Adel, G.T.; Luttrell, G.H.
Automatic control of fine coal cleaning circuits has traditionally been limited by the lack of sensors for on-line ash analysis. Although several nuclear-based analyzers are available, none have seen widespread acceptance. This is largely due to the fact that nuclear sensors are expensive and tend to be influenced by changes in seam type and pyrite content. Recently, researchers at VPI&SU have developed an optical sensor for phosphate analysis. The sensor uses image processing technology to analyze video images of phosphate ore. It is currently being used by PCS Phosphate for off-line analysis of dry flotation concentrate. The primary advantages ofmore » optical sensors over nuclear sensors are that hey are significantly cheaper, are not subject to measurement variations due to changes in high atomic number materials, are inherently safer and require no special radiation permitting. The purpose of this work is to apply the knowledge gained in the development of an optical phosphate analyzer to the development of an on-line ash analyzer for fine coal slurries. During the past quarter, the current prototype of the on-line optical ash analyzer was subjected to extensive testing at the Middlefork coal preparation plant. Initial work focused on obtaining correlations between ash content and mean gray level, while developmental work on the more comprehensive neural network calibration approach continued. Test work to date shows a promising trend in the correlation between ash content and mean gray level. Unfortunately, data scatter remains significant. Recent tests seem to eliminate variations in percent solids, particle size distribution, measurement angle and light setting as causes for the data scatter; however, equipment warm-up time and number of images taken per measurement appear to have a significant impact on the gray-level values obtained. 8 figs., 8 tabs.« less
NASA Astrophysics Data System (ADS)
Janssen, Gijs; Gunnink, Jan; van Vliet, Marielle; Goldberg, Tanya; Griffioen, Jasper
2017-04-01
Pollution of groundwater aquifers with contaminants as nitrate is a common problem. Reactive transport models are useful to predict the fate of such contaminants and to characterise the efficiency of mitigating or preventive measures. Parameterisation of a groundwater transport model on reaction capacity is a necessary step during building the model. Two Dutch, national programs are combined to establish a methodology for building a probabilistic model on reaction capacity of the groundwater compartment at the national scale: the Geological Survey program and the NHI Netherlands Hydrological Instrument program. Reaction capacity is considered as a series of geochemical characteristics that control acid/base condition, redox condition and sorption capacity. Five primary reaction capacity variables are characterised: 1. pyrite, 2. non-pyrite, reactive iron (oxides, siderite and glauconite), 3. clay fraction, 4. organic matter and 5. Ca-carbonate. Important reaction capacity variables that are determined by more than one solid compound are also deduced: 1. potential reduction capacity (PRC) by pyrite and organic matter, 2. cation-exchange capacity (CEC) by organic matter and clay content, 3. carbonate buffering upon pyrite oxidation (CPBO) by carbonate and pyrite. Statistical properties of these variables are established based on c. 16,000 sediment geochemical analyses. The first tens of meters are characterised based on 25 regions using combinations of lithological class and geological formation as strata. Because of both less data and more geochemical uniformity, the deeper subsurface is characterised in a similar way based on 3 regions. The statistical data is used as input in an algoritm that probabilistically calculates the reaction capacity per grid cell. First, the cumulative frequency distribution (cfd) functions are calculated from the statistical data for the geochemical strata. Second, all voxel cells are classified into the geochemical strata. Third, the cfd functions are used to put random reaction capacity variables into the hydrological voxel model. Here, the distribution can be conditioned on two variables. Two important variables are clay content and depth. The first is valid because more dense data is available for clay content than for geochemical variables as pyrite and probabilistic, lithological models are also built at TNO Geological Survey. The second is important to account for locally different depths at which the redox cline between NO3-rich and Fe(II)-rich groundwater occurs within the first tens of meters of the subsurface. An extensive data-set of groundwater quality analyses is used to derive criteria for depth variability of the redox cline. The result is a unique algoritm in order to obtain heterogeneous geochemical reaction capacity models of the entire groundwater compartment of the Netherlands.
NASA Astrophysics Data System (ADS)
Virtasalo, Joonas J.; Laitala, Jaakko J.; Lahtinen, Raimo; Whitehouse, Martin J.
2015-12-01
The Paleoproterozoic, 2.0-1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi-Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δ34S and δ56Fe values of the bedded pyrite (median δ34S = - 10.3 ‰ and δ56Fe = - 0.79 ‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δ34S = - 3.3 ‰ and δ56Fe = - 1.6 ‰) indicates microbial iron reduction. The Fe (oxyhydr)oxide aggregates were transported in muddy debris flows to the distal euxinic seafloor. Their Fe (oxyhydr)oxide matrix was replaced by pyrite (median δ34S = + 5.8 ‰ and δ56Fe = + 0.81 ‰) at shallow sediment depths with 34S and 56Fe-enriched porewater. Wavy-crinkly laminae of possible microbial origin developed on the euxinic seafloor during low sedimentation. These results indicate episodic deposition at seasonal to multiannual time scales. δ34S and δ56Fe values in the studied Fe-sulfides provide evidence of microbial isotope fractionation processes and syndepositional and early-diagenetic origin, finding no support for the previously proposed local hydrothermal activity in the Talvivaara mudstones.
NASA Astrophysics Data System (ADS)
Santana, Miriela María Ulloa; Moura, Márcia Abrahão; Olivo, Gema R.; Botelho, Nilson Francisquini; Kyser, T. Kurtis; Bühn, Bernhard
2011-01-01
The Camagüey district, Cuba, is known for its epithermal precious metal deposits in a Cretaceous volcanic arc setting. Recently, the La Unión prospect was discovered in the southern part of the district, containing gold and minor copper mineralization interpreted as porphyry type. Mineralization is hosted in a 73.0 ± 1.5 Ma calc-alkaline I-type oxidized porphyry quartz diorite intrusive within volcanic and volcaniclastic rocks of the early Cretaceous Guáimaro Formation. The porphyry is affected by propylitic alteration and crosscut by a network of quartz and carbonate veinlets and veins. Chlorite, epidote, sericite, quartz, and pyrite are the main minerals in the early veins which are cut by late carbonate and zeolite veins. Late barite pseudomorphously replaces pyrite. Gold is associated with pyrite as disseminations in the altered quartz diorite and in the veins, occurring as inclusions or filling fractures in pyrite with 4 g/t Au in bulk samples, and up to 900 ppm Au in in pyrite. Fluid inclusion and oxygen isotope data are consistent with a H2O-NaCl-(KCl) mineralizing fluid, derived from the quartz diorite magma, and trapped at least at 425°C and 1.2 kbar. This primary fluid unmixed into two fluid phases, a hypersaline aqueous fluid and a low-salinity vapor-rich fluid. Boiling during cooling may have played an important role in metal precipitation. Pyrite δ34S values for the La Unión prospect range between 0.71‰ and 1.31‰, consistent with a homogeneous magmatic sulfur source. The fluids in equilibrium with the mineralized rocks have estimated δ18O values from 8‰ to 11.8‰, calculated for a temperature range of 480-505°C. The tectonic environment of the La Unión prospect, its high gold and low copper contents, the physical-chemical characteristics of the mineralizing fluids and the isotopic signature of the alteration minerals and fluids indicate that the La Unión gold mineralization is similar to the porphyry gold type, even though the ore-related epidote-chlorite alteration can be classified as propylitic and not the classic potassic and/or phyllic alteration. The low copper contents in the prospect could be due to a mineralizing fluid previously saturated in copper, which is indicated by trapped chalcopyrite crystals in high-temperature fluid inclusions. The low-temperature paragenesis, represented by carbonate, zeolite and barite, indicates epithermal overprint. The study shows the potential for other gold porphyry-type deposits in the Cretaceous volcanoplutonic arc of Cuba.
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
1959-02-01
This annual report of Brookhaven National Laboratory describes its program and activities for the fiscal year 1958. The progress and trends of the research program are presented along with a description of the operational, service, and administrative activities of the Laboratory. The scientific and technical details of the many research and development activities are covered more fully in scientific and technical periodicals and in the quarterly scientific progress reports and other scientiflc reports of the Laboratory. A list of all publications for July 1, 1957 to June 30, 1958, is given. Status and progress are given in fields of physics,more » accelerator development, instrumentation, applied mathematics, chemistry, nuclear engineering, biology, and medical research. (For preceding period see BNL-462.) (W.D.M.)« less
Towards a space-borne quantum gravity gradiometer: progress in laboratory demonstration
NASA Technical Reports Server (NTRS)
Yu, Nan; Kohel, James M.; Kellogg, James R.; Maleki, Lute
2005-01-01
This paper describes the working principles and technical benefits of atom-wave interferometer-based inertial sensors, and gives a progress report on the development of a quantum gravity gradiometer for space applications at JPL.
Technical Progress of the New Worlds Observer Mission
NASA Astrophysics Data System (ADS)
Lo, Amy; Noecker, C.; Cash, W.; NWO Study Team
2009-01-01
We report on the technical progress of the New Worlds Observer (NWO) mission concept. NWO is a two spacecraft mission that is capable of detecting and characterizing extra-solar, terrestrial planets and planetary systems. NWO consists of an external starshade and an UV-optical space telescope, flying in tandem. The starshade is a petal-shaped, opaque screen that creates an extremely dark shadow large enough to shade the telescope aperture from the target star. The NWO team has been addressing the top technology challenges of the concept, and report here our progress. We will present the current mission configuration best suited to address Terrestrial Planet Finding requirements, and highlight the technological breakthroughs that we have achieved this year. In particular, we will report on progress made in precision deployables for the large starshade, and the trajectory & alignment control system for NWO. We will also briefly highlight advances in understanding the starshade optical performance.
DOE Office of Scientific and Technical Information (OSTI.GOV)
WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.
In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less
WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.; ...
2014-10-08
In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less
NASA Astrophysics Data System (ADS)
Berta, Marton; Dethlefsen, Frank; Ebert, Markus; Schäfer, Dirk
2017-04-01
Storing renewably produced energy is one of the major challenges for the energy systems of the upcoming decades. Power-to-gas technologies coupled to geological storage of compressed air, methane, and hydrogen offer a comparatively safe and cost-efficient way for large-scale energy storage. However, the stored gases can potentially escape from their geological reservoir and may thus affect protected natural goods such as groundwater. The geochemical reactions responsible for these composition changes are usually investigated separately in experiments and numerical models. Here we present the outcomes of an integrated experimental and modeling approach through the example of a compressed air leakage scenario. A main consequence of the presence of oxygen to be assessed in an aquifer is pyrite oxidation, well known from acid mine drainage sites. However, in contrast to acid mine drainage sites exhibiting unsaturated sediments and fed by meteoric low-carbonate water, aquifers such as in Northern Germany contain a considerable amount of solid and dissolved inorganic carbon species potentially buffering pH changes. High pressure flow-through column experiments representing an intrusion of compressed air into an aquifer were carried out to quantify pyrite oxidation kinetics and to incorporate the observations into a descriptive reaction model. Surface passivation was found to decrease the reactivity of pyrite by more than 90% after a few months of experimental run time. We propose that the carbonate buffer system enables the precipitation of a passivating mineral layer on the pyrite surface reducing the overall reaction rate significantly. Consequently, an established rate law from the literature was extended by a reactive surface passivation term[1]. This improved reaction rate equation was incorporated into a 3D numerical model using OpenGeoSys with parameters representing similarly typical aquifer conditions the experiments had characterized. These boundaries include pyrite content, oxygen dissolution kinetics, groundwater composition including the carbonate buffer, and diffusive and advective transport parameters. The results of site-scale multiphase reactive transport modeling revealed the expected spatial distribution of redox-sensitive species such as oxygen, pyrite, and sulfate in an aquifer following a leakage. The changes in concentration of sulfate, dissolved oxygen, and H+ observed in the lab-scale experiments were qualitatively reproduced by the models applying the same boundary conditions on a site-scale. This integrated study acknowledged that the combination of experiments and models is a powerful tool to prognose the geochemical consequences of gas leakage on site scale. However, it is yet unknown how the passivation would be effected if the carbonate buffer depleted on the long term and under what circumstances a transition from the passivating pyrite oxidation process to the non-passivating process observed for instance in acid mine drainage setups occurs. These restrictions mark the limits of validity of our experimental and modeling concept. This conclusion suggests the feasibility of the presented integrated approach also when evaluating comparable scenarios on methane and hydrogen storage based on experimental results gathered similarly[2]. [1]Berta et al. Environ Earth Sci (2016) 75:1175, DOI 10.1007/s12665-016-5985-7. [2]Berta et al. First Break (2015) 33,93-95, ISSN 1365-2397. This work is part of the ANGUS+ project funded by the BMBF-FK03EK3022.
Molecular Characterization of Bacterial Respiration on Minerals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Blake, Robert C.
2013-04-26
The overall aim of this project was to contribute to our fundamental understanding of proteins and biological processes under extreme environmental conditions. We sought to define the biochemical and physiological mechanisms that underlie biodegradative and other cellular processes in normal, extreme, and engineered environments. Toward that end, we sought to understand the substrate oxidation pathways, the electron transport mechanisms, and the modes of energy conservation employed during respiration by bacteria on soluble iron and insoluble sulfide minerals. In accordance with these general aims, the specific aims were two-fold: To identify, separate, and characterize the extracellular biomolecules necessary for aerobic respirationmore » on iron under strongly acidic conditions; and to elucidate the molecular principles whereby these bacteria recognize and adhere to their insoluble mineral substrates under harsh environmental conditions. The results of these studies were described in a total of nineteen manuscripts. Highlights include the following: 1. The complete genome of Acidithiobacillus ferrooxidans ATCC 23270 (type strain) was sequenced in collaboration with the DOE Joint Genome Institute; 2. Genomic and mass spectrometry-based proteomic methods were used to evaluate gene expression and in situ microbial activity in a low-complexity natural acid mine drainage microbial biofilm community. This was the first effort to successfully analyze a natural community using these techniques; 3. Detailed functional and structural studies were conducted on rusticyanin, an acid-stable electron transfer protein purified from cell-free extracts of At. ferrooxidans. The three-dimensional structure of reduced rusticyanin was determined from a combination of homonuclear proton and heteronuclear 15N- and 13C-edited NMR spectra. Concomitantly, the three-dimensional structure of oxidized rusticyanin was determined by X-ray crystallography to a resolution of 1.9 A by multiwavelength anomalous dispersion (MAD) phasing; 4. An acid-stable red cytochrome with a novel absorbance peak at 579 nm was purified from cell-free extracts of L. ferriphilum. Functional studies demonstrated that this cytochrome was an important component of the aerobic iron respiratory chain in this organism; 5. The specific adhesion of At. ferrooxidans to pyrite is mediated by an extracellular protein that was identified as aporusticyanin. The adhesion of At. ferrooxidans to minerals was characterized by high affinity binding that exhibited a high specificity for pyrite over other sulfide minerals. The principal biopolymer involved in this high-affinity adhesion to pyrite was isolated by mineral affinity chromatography and identified as aporusticyanin. The adhesion of purified aporusticyanin to minerals was observed to adhere to different mineral with a pattern of reactivity identical to that observed with the intact bacterium. Further, preincubation of pyrite with excess exogenous aporusticyanin served to inhibit the adherence of intact cells to the surface of the mineral, indicating that the protein and the cells adhered to the pyrite in a mutually exclusive manner. Taken together, these observations support a model where aporusticyanin located on the surface of the bacterial cell acts as a mineral-specific receptor for the initial adherence of At. ferrooxidans to solid pyrite; 6. The specific adhesion of L. ferriphilum to pyrite was mediated by a different acid-stable extracellular protein than aporusticyanin; and 7. A prototype integrating cavity absorption meter (ICAM) was assembled to determine whether this novel spectrophotometer could be used to study cellular respiration in situ.« less
Dusel-Bacon, Cynthia; Foley, Nora K.; Slack, John E.; Koenig, Alan E.; Oscarson, Robert L.
2012-01-01
Volcanogenic massive sulfide (VMS) Zn-Pb-Cu-Ag-Au deposits of the Bonnifield mining district formed during Late Devonian-Early Mississippian magmatism along the western edge of Laurentia. The largest deposits, Dry Creek and WTF, have a combined resource of 5.7 million tonnes at 10% Zn, 4% Pb, 0.3% Cu, 300 grams per tonne (g/t) Ag, and 1.6 g/t Au. These polymetallic deposits are hosted in high field strength element (HFSE)- and rare-earth element (REE)-rich peralkaline (pantelleritic) metarhyolite, and interlayered pyritic argillite and mudstone of the Mystic Creek Member of the Totatlanika Schist Formation. Mystic Creek metarhyolite and alkali basalt (Chute Creek Member) constitute a bimodal pair that formed in an extensional environment. A synvolcanic peralkaline quartz porphyry containing veins of fluorite, sphalerite, pyrite, and quartz intrudes the central footwall at Dry Creek. The Anderson Mountain deposit, located ~32 km to the southwest, occurs within calc-alkaline felsic to intermediate-composition metavolcanic rocks and associated graphitic argillite of the Wood River assemblage. Felsic metavolcanic rocks there have only slightly elevated HFSEs and REEs. The association of abundant graphitic and siliceous argillite with the felsic volcanic rocks together with low Cu contents in the Bonnifield deposits suggests classification as a siliciclastic-felsic type of VMS deposit. Bonnifield massive sulfides and host rocks were metamorphosed and deformed under greenschist-facies conditions in the Mesozoic. Primary depositional textures, generally uncommon, consist of framboids, framboidal aggregates, and spongy masses of pyrite. Sphalerite, the predominant base metal sulfide, encloses early pyrite framboids. Galena and chalcopyrite accompanied early pyrite formation but primarily formed late in the paragenetic sequence. Silver-rich tetrahedrite is a minor late phase at the Dry Creek deposit. Gold and Ag are present in low to moderate amounts in pyrite from all of the deposits; electrum inclusions occur in Dry Creek sphalerite. Contents and ratios of trace elements in graphitic argillite that serve as proxies for the redox state of the bottom waters in the basin indicate that Dry Creek mineralization took place in suboxic to periodically anoxic bottom waters. Trace element data show higher contents of Tl-Mn-As in pyrite from the Anderson Mountain deposit compared to the Dry Creek or WTF deposits and thus suggest that Anderson Mountain may have formed at lower temperatures or under slightly more oxidizing conditions. No exact modern analogue for the tectonic setting of the Bonnifield VMS deposits is known, although the back-arc regions of the Okinawa Trough and Woodlark Basin satisfy the requirement for a submarine, extensional setting adjacent to a continental margin. Limited occurrences of peralkaline volcanic rocks occur in these two potential analogues, but the peralkalinity of those rocks is much less than that of the Mystic Creek Member metarhyolites in the Bonnifield district. The highly elevated trace element (e.g., Zr, Nb) contents of Mystic Creek metarhyolites suggest that a better analogue may be a submarine rifted continental margin. The calc-alkaline composition of the host rocks to the Anderson Mountain deposit suggests that mineralization there formed in a continental margin arc, outboard of the extended continental margin setting of the peralkaline-hosted Dry Creek and WTF deposits.
NASA Astrophysics Data System (ADS)
Brantley, S. L.; Gu, X.; Sullivan, P. L.; Kim, H.; Stinchcomb, G. E.; Lebedeva, M.; Balashov, V. N.
2016-12-01
To first order, weathering is the reaction of rocks with oxidants (oxygen, nitrate, etc.), acids (carbonic, sulfuric, and organic acids), and water. To explore weathering we have been studying the depth intervals in soils, saprolite, and weathering rock where mineral reactions are localized - "reaction fronts". We limit the study to ridges or catchments in climates where precipitation is greater than potential evapotranspiration. For example, in the Susquehanna Shale Hills Critical Zone Observatory, we observe reaction fronts that generally define very rough surfaces in 3D that mimic the land surface topography, although with lower relief. Overall, the fronts form nested curved surfaces. In Shale Hills, the deepest reaction fronts are oxidation of pyrite, and dissolution of carbonate. The carbonate is inferred to dissolve at least partly due to the sulfuric acid produced by the pyrite. In addition to pyrite, chlorite also starts to oxidize at the water table. We hypothesize that these dissolution and oxidation reactions open pores and cause microfracturing that open the rock to infiltration of advecting meteoric waters. At much shallower depths, illite is observed to dissolve. In Shale Hills, these reaction fronts - pyrite, carbonate, illite - separate over meters beneath the ridges. Such separated reaction fronts have also been observed in other fractured lithologies where oxidation is the deepest reaction and is associated with weathering-induced fractures. In contrast, in some massive mafic rocks, reaction fronts are almost co-located. By studying the geometry of reaction fronts, it may be possible to elucidate the relative importance of how oxygen cracks rocks; carbonic, organic, and sulfuric acids dissolve rocks; and water mobilizes rock materials during weathering.
Acidophilic sulfur disproportionation
NASA Astrophysics Data System (ADS)
Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.
2013-07-01
Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.
Oxygen transport and pyrite oxidation in unsaturated coal-mine spoil
Guo, Weixing; Cravotta, Charles A.
1996-01-01
An understanding of the mechanisms of oxygen (02) transport in unsaturated mine spoil is necessary to design and implement effective measures to exclude 02 from pyritic materials and to control the formation of acidic mine drainage. Partial pressure of oxygen (Po2) in pore gas, chemistry of pore water, and temperature were measured at different depths in unsaturated spoil at two reclaimed surface coal mines in Pennsylvania. At mine 1, where spoil was loose, blocky sandstone, Po2 changed little with depth, decreasing from 21 volume percent (vol%) at the ground surface to a minimum of about 18 vol% at 10 m depth. At mine 2, where spoil was compacted, friable shale, Po2 decreased to less than 2 vol% at depth of about 10 m. Although pore-water chemistry and temperature data indicate that acid-forming reactions were active at both mines, the pore-gas data indicate that mechanisms for 0 2 transport were different at each mine. A numerical model was developed to simulate 02 transport and pyrite oxidation in unsaturated mine spoil. The results of the numerical simulations indicate that differences in 02 transport at the two mines can be explained by differences in the air permeability of spoil. Po2 changes little with depth if advective transport of 02 dominates as at mine 1, but decreases greatly with depth if diffusive transport of 02 dominates, as in mine 2. Model results also indicate that advective transport becomes significant if the air permeability of spoil is greater than 10-9 m2, which is expected for blocky sandstone spoil. In the advective-dominant system, thermally-induced convective air flow, as a consequence of the exothermic oxidation of pyrite, supplies the 02 to maintain high Po2 within the deep unsaturated zone.
NASA Astrophysics Data System (ADS)
Amils, R.; Fernández-Remolar, D. C.; Parro, V.; Manfredi, J. A.; Timmis, K.; Oggerin, M.; Sánchez-Román, M.; López, F. J.; Fernández, J. P.; Omoregie, E.; Gómez-Ortiz, D.; Briones, C.; Gómez, F.; García, M.; Rodríguez, N.; Sanz, J. L.
2012-09-01
Iberian Pyrite Belt Subsurface Life (IPBSL) is a drilling project specifically designed to characterize the subsurface ecosystems operating in the Iberian Pyrite Belt (IPB), in the area of Peña de Hierro, and responsible of the extreme acidic conditions existing in the Rio Tinto basin [1]. Rio Tinto is considered a good geochemical terrestrial analogue of Mars [2, 3]. A dedicated geophysical characterization of the area selected two drilling sites (4) due to the possible existence of water with high ionic content (low resistivity). Two wells have been drilled in the selected area, BH11 and BH10, of depths of 340 and 620 meters respectively, with recovery of cores and generation of samples in anaerobic and sterile conditions. Preliminary results showed an important alteration of mineral structures associated with the presence of water, with production of expected products from the bacterial oxidation of pyrite (sulfates and ferric iron). Ion chromatography of water soluble compounds from uncontaminated samples showed the existence of putative electron donors (ferrous iron, nitrite in addition of the metal sulfides), electron acceptors (sulfate, nitrate, ferric iron) as well as variable concentration of metabolic organic acids (mainly acetate, formate, propionate and oxalate), which are strong signals of the presence of active subsurface ecosystem associated to the high sulfidic mineral content of the IPB. The system is driven by oxidants that appear to be provided by the rock matrix, only groundwater is needed to launch microbial metabolism. The geological, geomicrobiological and molecular biology analysis which are under way, should allow the characterization of this ecosystem of paramount interest in the design of an astrobiological underground Mars exploration mission in the near future.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dunkerton, L.V.; Nigam, A.; Mitra, S.
1987-05-01
In preparation for using /sup 33/S NMR for characterization of organic sulfur types in coal, previously prepared substituted dibenzothiophene model compounds were converted to their corresponding sulfones and their sulfur-33 nmr recorded. The sulfur-33 NMR spectra of dibenzothiophene-5,5-dioxide (2), 2-(p-methylphenylsulfonyl) dibenzothiophene-5,5-dioxide (4), and 2-(methylsulfonyl) dibenzothiophene-5,5-dioxide (6) are reported. The chemical shifts were in the +2 to -21 ppM range. The line widths ranged 70 to 200 Hz. The changes in /sup 13/C chemical shift experienced by aromatic carbons upon oxidizing the sulfide to its sulfone were also studied and the data used to identify which sulfone was formed in multiplemore » thioether-containing aromatics after partial oxidation. Continuing results on the use of the substituted dibenzothiophenes to monitor mixing of sulfur between pyritic and organic phases are also reported. Non-isothermal hydrodesulfurization of model organic sulfur compounds was carried out in a cola-like environment. The model sulfur compounds represented different types of carbon-sulfur bonds commonly encountered in coal. Similar experiments were carried out in the presence of troilite (iron sulfide) to investigate the possibility of sulfur migration from the organic compound to the iron sulfide. Next, iron pyrite was hydrodesulfurized in the presence of some organic molecules to see if sulfur could be incorporated into the organic molecules during the process. Results show that sulfur from organic compounds can be absorbed by troilite, and, similarly, sulfur from pyrite can form new carbon-sulfur bonds during hydrodesulfurization. Based on these observations, it is suggested that during coal conversion reactions it is possible to have intermigration of sulfur between the organic and the inorganic phases.« less
Dings, M.G.; Schafer, Max
1953-01-01
During the summer of 1952 most of the mines and prospects in the Garfield and Taylor Park quadrangles of west-central Colorado were examined radiometrically by the U. S. Geological Survey to determine the extent, grade, and mode of occurrence of radioactive substances. The region contains a relatively large number of rock types, chiefly pre-Cambrian schists, gneisses, and granites; large and small isolated areas of sedimentary rocks of Paleozoic and Mesozoic ages; and a great succession of intrusive rocks of Tertiary age that range from andesite to granite and occur as stocks, chonoliths, sills, dikes, and one batholith. The prevailing structures are northwest-trending folds and faults. Ores valued at about $30,000,000 have been produced from this region. Silver, lead, zinc, and gold have accounted for most of this value, but small tonnages of copper, tungsten, and molybdenum have also been produced. The principal ore minerals are sphalerite, silver-bearing galena, cerussite, smithsonite, and gold-bearing pyrite and limonite; they occur chiefly as replacement bodies in limestone and as shoots in pyritic quartz veins. Anomalous radioactivity is uncommon and the four localities at which it is known are widely separated in space. The uranium content of samples from these localities is low. Brannerite, the only uranium-bearing mineral positively identified in the region, occurs sparingly in a few pegmatites and in one quartz-beryl-pyrite vein. Elsewhere radioactivity is associated with (l) black shale seams in the Manitou dolomite, (2) a quartz-pyrite-molybdenite vein, (3) a narrow border zone of oxidized material surrounding a small lead zinc ore body in the Manitou dolomite along a strong fault zone.
Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine
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 (<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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Baruth, A.; Manno, M.; Narasimhan, D.
2012-09-01
Transition metal disulfides crystallizing in the pyrite structure (e.g., TMS{sub 2}, with TM = Fe, Co, Ni, and Cu) are a class of materials that display a remarkably diverse array of functional properties. These properties include highly spin-polarized ferromagnetism (in Co{sub 1-x}Fe{sub x}S{sub 2}), superconductivity (in CuS{sub 2}), an antiferromagnetic Mott insulating ground state (in NiS{sub 2}), and semiconduction with close to optimal parameters for solar absorber applications (in FeS{sub 2}). Exploitation of these properties in heterostructured devices requires the development of reliable and reproducible methods for the deposition of high quality pyrite structure thin films. In this manuscript, wemore » report on the suitability of reactive sputter deposition from metallic targets in an Ar/H{sub 2}S environment as a method to achieve exactly this. Optimization of deposition temperature, Ar/H{sub 2}S pressure ratio, and total working gas pressure, assisted by plasma optical emission spectroscopy, reveals significant windows over which deposition of single-phase, polycrystalline, low roughness pyrite films can be achieved. This is illustrated for the test cases of the ferromagnetic metal CoS{sub 2} and the diamagnetic semiconductor FeS{sub 2}, for which detailed magnetic and transport characterization are provided. The results indicate significant improvements over alternative deposition techniques such as ex situ sulfidation of metal films, opening up exciting possibilities for all-sulfide heterostructured devices. In particular, in the FeS{sub 2} case it is suggested that fine-tuning of the sputtering conditions provides a potential means to manipulate doping levels and conduction mechanisms, critical issues in solar cell applications. Parenthetically, we note that conditions for synthesis of phase-pure monosulfides and thiospinels are also identified.« less
NASA Astrophysics Data System (ADS)
Kemper, Thomas; Sommer, Stefan
2004-10-01
Field and airborne hyperspectral data was used to map residual contamination after a mining accident, by applying spectral mixture modelling. Test case was the Aznalcollar Mine (Southern Spain) accident, where heavy metal bearing sludge from a tailings pond was distributed over large areas of the Guadiamar flood plain. Although the sludge and the contaminated topsoils have been removed mechanically in the whole affected area, still high abundance of pyritic material remained on the ground. During dedicated field campaigns in two subsequent years soil samples were collected for geochemical and spectral laboratory analysis and spectral field measurements were carried out in parallel to data acquisition with the HyMap sensor. A Variable Multiple Endmember Spectral Mixture Analysis (VMESMA) tool was used providing possibilities of multiple endmember unmixing, aiming to estimate the quantities and distribution of the remaining tailings material. A spectrally based zonal partition of the area was introduced to allow the application of different submodels to the selected areas. Based on an iterative feedback process, the unmixing performance could be improved in each stage until an optimum level was reached. The sludge abundances obtained by unmixing the hyperspectral spectral data were confirmed by the field observations and chemical measurements of samples taken in the area. The semi-quantitative sludge abundances of residual pyritic material could be transformed into quantitative information for an assessment of acidification risk and distribution of residual heavy metal contamination based on an artificial mixture experiment. The unmixing of the second year images allowed identification of secondary minerals of pyrite as indicators of pyrite oxidation and associated acidification.
The pyrite-type high-pressure form of FeOOH
NASA Astrophysics Data System (ADS)
Nishi, Masayuki; Kuwayama, Yasuhiro; Tsuchiya, Jun; Tsuchiya, Taku
2017-07-01
Water transported into Earth’s interior by subduction strongly influences dynamics such as volcanism and plate tectonics. Several recent studies have reported hydrous minerals to be stable at pressure and temperature conditions representative of Earth’s deep interior, implying that surface water may be transported as far as the core-mantle boundary. However, the hydrous mineral goethite, α-FeOOH, was recently reported to decompose under the conditions of the middle region of the lower mantle to form FeO2 and release H2, suggesting the upward migration of hydrogen and large fluctuations in the oxygen distribution within the Earth system. Here we report the stability of FeOOH phases at the pressure and temperature conditions of the deep lower mantle, based on first-principles calculations and in situ X-ray diffraction experiments. In contrast to previous work suggesting the dehydrogenation of FeOOH into FeO2 in the middle of the lower mantle, we report the formation of a new FeOOH phase with the pyrite-type framework of FeO6 octahedra, which is much denser than the surrounding mantle and is stable at the conditions of the base of the mantle. Pyrite-type FeOOH may stabilize as a solid solution with other hydrous minerals in deeply subducted slabs, and could form in subducted banded iron formations. Deep-seated pyrite-type FeOOH eventually dissociates into Fe2O3 and releases H2O when subducted slabs are heated at the base of the mantle. This process may cause the incorporation of hydrogen into the outer core by the formation of iron hydride, FeHx, in the reducing environment of the core-mantle boundary.
NASA Astrophysics Data System (ADS)
Huang, Xiao-Wen; Zhou, Mei-Fu; Beaudoin, Georges; Gao, Jian-Feng; Qi, Liang; Lyu, Chuan
2018-01-01
The Yamansu Fe deposit (32 Mt at 51% Fe) in the Eastern Tianshan Orogenic Belt of NW China is hosted in early Carboniferous volcano-sedimentary rocks and spatially associated with skarn. The paragenetic sequence includes garnet-diopside (I), magnetite (II), hydrous silicate-sulfide (III), and calcite-quartz (IV) stages. Pyrite associated with magnetite has a Re-Os isochron age of 322 ± 7 Ma, which represents the timing of pyrite and, by inference, magnetite mineralization. Pyrite has δ 34SVCDT values of - 2.2 to + 2.9‰, yielding δ 34SH2S values of - 3.1 to 2‰, indicating the derivation of sulfur from a magmatic source. Calcite from stages II and IV has δ 13CVPDB values from - 2.5 to - 1.2‰, and - 1.1 to 1.1‰, and δ 18OVSMOW values from 11.8 to 12.0‰ and - 7.7 to - 5.2‰, respectively. Calculated δ 13C values of fluid CO2 and water δ 18O values indicate that stage II hydrothermal fluids were derived from magmatic rocks and that meteoric water mixed with the hydrothermal fluids in stage IV. Some ores contain magnetite with obvious chemical zoning composed of dark and light domains in BSE images. Dark domains have higher Mg, Al, Ca, Mn, and Ti but lower Fe and Cr contents than light domains. The chemical zoning resulted from a fluctuating fluid composition and/or physicochemical conditions (oscillatory zoning), or dissolution-precipitation (irregular zoning) via infiltration of magmatic-hydrothermal fluids diluted by late meteoric water. Iron was mainly derived from fluids similar to that in skarn deposits.
Pilot-Scale Demonstration of Pefi's Oxygenated Transportation Fuels Production Technology
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
Coal-cleaning processes have been utilized to increase the heating value of coal by extracting ash-forming minerals in the coal. These processes involve the crushing or grinding of raw coal followed by physical separation processes, taking advantage of the density difference between carbonaceous particles and mineral particles. In addition to the desired increase in the heating value of coal, a significant reduction of the sulfur content of the coal fed to a combustion unit is effected by the removal of pyrite and other sulfides found in the mineral matter. WRI is assisting PulseWave to develop an alternate, more efficient method ofmore » liberating and separating the undesirable mineral matter from the carbonaceous matter in coal. The approach is based on PulseWave's patented resonance disintegration technology that reduces that particle size of materials by application of destructive resonance, shock waves, and vortex generating forces. Illinois No.5 coal, a Wyodak coal, and a Pittsburgh No.8 coal were processed using the resonance disintegration apparatus then subjected to conventional density separations. Initial microscopic results indicate that up to 90% of the pyrite could be liberated from the coal in the machine, but limitations in the density separations reduced overall effectiveness of contaminant removal. Approximately 30-80% of the pyritic sulfur and 30-50% of the mercury was removed from the coal. The three coals (both with and without the pyritic phase separated out) were tested in WRI's 250,000 Btu/hr Combustion Test Facility, designed to replicate a coal-fired utility boiler. The flue gases were characterized for elemental, particle bound, and total mercury in addition to sulfur. The results indicated that pre-combustion cleaning could reduce a large fraction of the mercury emissions.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
Progress summaries are provided from the Amarillo National Center for Plutonium. Programs include the plutonium information resource center, environment, public health, and safety, education and training, nuclear and other material studies.
Urology technical and non-technical skills development: the emerging role of simulation.
Rashid, Prem; Gianduzzo, Troy R J
2016-04-01
To review the emerging role of technical and non-technical simulation in urological education and training. A review was conducted to examine the current role of simulation in urology training. A PUBMED search of the terms 'urology training', 'urology simulation' and 'urology education' revealed 11,504 titles. Three hundred and fifty-seven abstracts were identified as English language, peer reviewed papers pertaining to the role of simulation in urology and related topics. Key papers were used to explore themes. Some cross-referenced papers were also included. There is an ongoing need to ensure that training time is efficiently utilised while ensuring that optimal technical and non-technical skills are achieved. Changing working conditions and the need to minimise patient harm by inadvertent errors must be taken into account. Simulation models for specific technical aspects have been the mainstay of graduated step-wise low and high fidelity training. Whole scenario environments as well as non-technical aspects can be slowly incorporated into the curriculum. Doing so should also help define what have been challenging competencies to teach and evaluate. Dedicated time, resources and trainer up-skilling are important. Concurrent studies are needed to help evaluate the effectiveness of introducing step-wise simulation for technical and non-technical competencies. Simulation based learning remains the best avenue of progressing surgical education. Technical and non-technical simulation could be used in the selection process. There are good economic, logistic and safety reasons to pursue the process of ongoing development of simulation co-curricula. While the role of simulation is assured, its progress will depend on a structured program that takes advantage of what can be delivered via this medium. Overall, simulation can be developed further for urological training programs to encompass technical and non-technical skill development at all stages, including recertification. © 2015 The Authors BJU International © 2015 BJU International Published by John Wiley & Sons Ltd.