X-ray photoelectron spectroscopic study of the interaction of xanthate with coal pyrite and mineral pyrite surfaces

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.

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.

Kinetics of the Removal of Iron Pyrite from Coal by Microbial Catalysis

PubMed Central

Hoffmann, Michael R.; Faust, Bruce C.; Panda, Fern A.; Koo, Hong H.; Tsuchiya, Henry M.

1981-01-01

Different strains of Thiobacillus ferrooxidans and Thiobacillus thiooxidans were used to catalyze the oxidative dissolution of iron pyrite, FeS2, in nine different coal samples. Kinetic variables and parametric factors that were determined to have a pronounced effect on the rate and extent of oxidative dissolution at a fixed Po2 were: the bacterial strain, the nitrogen/phosphorus molar ratio, the partial pressure of CO2, the coal source, and the total reactive surface area of FeS2. The overall rate of leaching, which exhibited a first-order dependence on the total surface area of FeS2, was analyzed mathematically in terms of the sum of a biochemical rate, ν1, and a chemical rate, ν2. Results of this study show that bacterial desulfurization (90 to 98%) of coal samples which are relatively high in pyritic sulfur can be achieved within a time-frame of 8 to 12 days when pulp densities are ≤20% and particle sizes are ≤74 μm. The most effective strains of T. ferrooxidans were those that were isolated from natural systems, and T. ferrooxidans ATCC 19859 was the most effective pure strain. The most effective nutrient media contained relatively low phosphate concentrations, with an optimal N/P molar ratio of 90:1. These results suggest that minimal nutrient additions may be required for a commercial desulfurization process. PMID:16345826

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.

Suppression of pyritic sulphur during flotation tests using the bacterium Thiobacillus ferrooxidans.

PubMed

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.

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.

Microbial acceleration of aerobic pyrite oxidation at circumneutral pH.

PubMed

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.

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

PubMed

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.

Generation of Acid Mine Lakes Associated with Abandoned Coal Mines in Northwest Turkey.

PubMed

Sanliyuksel Yucel, Deniz; Balci, Nurgul; Baba, Alper

2016-05-01

A total of five acid mine lakes (AMLs) located in northwest Turkey were investigated using combined isotope, molecular, and geochemical techniques to identify geochemical processes controlling and promoting acid formation. All of the investigated lakes showed typical characteristics of an AML with low pH (2.59-3.79) and high electrical conductivity values (1040-6430 μS/cm), in addition to high sulfate (594-5370 mg/l) and metal (aluminum [Al], iron [Fe], manganese [Mn], nickel [Ni], and zinc [Zn]) concentrations. Geochemical and isotope results showed that the acid-generation mechanism and source of sulfate in the lakes can change and depends on the age of the lakes. In the relatively older lakes (AMLs 1 through 3), biogeochemical Fe cycles seem to be the dominant process controlling metal concentration and pH of the water unlike in the younger lakes (AMLs 4 and 5). Bacterial species determined in an older lake (AML 2) indicate that biological oxidation and reduction of Fe and S are the dominant processes in the lakes. Furthermore, O and S isotopes of sulfate indicate that sulfate in the older mine lakes may be a product of much more complex oxidation/dissolution reactions. However, the major source of sulfate in the younger mine lakes is in situ pyrite oxidation catalyzed by Fe(III) produced by way of oxidation of Fe(II). Consistent with this, insignificant fractionation between δ(34) [Formula: see text] and δ(34) [Formula: see text] values indicated that the oxidation of pyrite, along with dissolution and precipitation reactions of Fe(III) minerals, is the main reason for acid formation in the region. Overall, the results showed that acid generation during early stage formation of an AML associated with pyrite-rich mine waste is primarily controlled by the oxidation of pyrite with Fe cycles becoming the dominant processes regulating pH and metal cycles in the later stages of mine lake development.

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

PubMed

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.

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

PubMed

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.

Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

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

Pyrite discs in coal: evidence for fossilized bacterial colonies

USGS Publications Warehouse

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.

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

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.

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.

[Oxidation of sulfur-containing substrates by aboriginal and experimentally designed microbial communities].

PubMed

Pivovarova, T A; Bulaev, A G; Roshchupko, P V; Belyĭ, A V; Kondrat'eva, T F

2012-01-01

Aboriginal and experimental (constructed of pure microbial cultures) communities of acidophilic chemolithotrophs have been studied. The oxidation of elemental sulfur, sodium thiosulfate, and potassium tetrathionate as sole sources of energy has been monitored. The oxidation rate of the experimental community is higher as compared to the aboriginal community isolated from a flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore. The degree of oxidation of the mentioned S substrates amounts to 17.91, 68.30, and 93.94% for the experimental microbial community and to 10.71, 56.03, and 79.50% for the aboriginal community, respectively. The degree of oxidation of sulfur sulfide forms in the ore flotation concentrate is 59.15% by the aboriginal microbial community and 49.40% by the experimental microbial community. Despite a higher rate of oxidation of S substrates as a sole source of energy by the experimental microbial community, the aboriginal community oxidizes S substrates at a higher rate in the flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore, from which it was isolated. Bacterial-chemical oxidation of the flotation concentrate by the aboriginal microbial community allows for the extraction of an additional 32.3% of gold from sulfide minerals, which is by 5.7% larger compared to the yield obtained by the experimental microbial community.

Sulfur isotopic evidence for the origin of elemental sulfur in gas hydrate-bearing sediments of the northern South China Sea

NASA Astrophysics Data System (ADS)

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

2017-04-01

Elemental sulfur is a common intermediate in the sulfur cycle and contributes significantly to the fractionation of stable sulfur isotopes in different reservoirs in shelfal marine sediments (e.g., Canfield and Thamdrup, 1994). However, no study dedicated to the isotopic composition of elemental sulfur in seep environments has been conducted to the best of our knowledge, thus limiting further insight into the biochemical pathways involving elemental sulfur in such environments. In this study, elemental sulfur and pyrite were extracted from the sediment of a 200-m long gas hydrate-bearing core, which was obtained from the gas hydrate drilling expedition to the northern South China Sea in 2013 (Zhang et al., 2015). The sulfur isotopic composition of elemental sulfur was found to vary from -16 to +23 per mill, and pyrite yielded values ranging from -34 to +18 per mill. Interestingly, elemental sulfur revealed higher 34S contents (up to 30 per mill) than the associated pyrite in most sediment layers. Since elemental sulfur is only produced during oxidative pathways in the sulfur cycle, the studied elemental sulfur apparently represents the oxidation product of hydrogen sulfide by various electron acceptors such as Mn(IV) oxides or Fe(III) oxides (e.g., Thamdrup et al., 1993; Yao and Millero, 1996). Since there is little sulfur isotope fractionation for oxidative processes (Fry et al., 1986), the enrichment of elemental sulfur in 34S points to a pool of hydrogen sulfide depleted in 32S, which is best interpreted to result from sulfate-driven anaerobic oxidation of methane. References: Canfield D.E. and Thamdrup B. (1994) The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science 266, 1973. Fry B., Cox J., Gest H. and Hayer J.M. (1986) Discrimination between 34S and32S during bacterial metabolism of inorganic sulfur compounds. J. Bacteriol. 165, 328-330. Thamdrup B., Finster K., Hansen W. and Bak F. (1993) Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron and manganese. Appl. Env. Microbiol. 59, 101-108. Yao W. and Millero F.J. (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar. Chem. 52, 1-16. Zhang G., Liang J., Lu J.A., Yang S., Zhang M., Holland M., Schultheiss P., Su X., Sha Z., Xu H., Gong Y., Fu S., Wang L. and Kuang Z. (2015) Geological features, controlling factors and potential prospects of the gas hydrate occurrence in the east part of the Pearl River Mouth Basin, South China Sea. Mar. Pet. Geol. 67, 356-367.

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

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.

Biogeochemical probing of microbial communities in a basalt-hosted hot spring at Kverkfjöll volcano, Iceland.

PubMed

Cousins, Claire R; Fogel, Marilyn; Bowden, Roxane; Crawford, Ian; Boyce, Adrian; Cockell, Charles; Gunn, Matthew

2018-06-01

We investigated bacterial and archaeal communities along an ice-fed surficial hot spring at Kverkfjöll volcano-a partially ice-covered basaltic volcano at Vatnajökull glacier, Iceland, using biomolecular (16S rRNA, apsA, mcrA, amoA, nifH genes) and stable isotope techniques. The hot spring environment is characterized by high temperatures and low dissolved oxygen concentrations at the source (68°C and <1 mg/L (±0.1%)) changing to lower temperatures and higher dissolved oxygen downstream (34.7°C and 5.9 mg/L), with sulfate the dominant anion (225 mg/L at the source). Sediments are comprised of detrital basalt, low-temperature alteration phases and pyrite, with <0.4 wt. % total organic carbon (TOC). 16S rRNA gene profiles reveal that organisms affiliated with Hydrogenobaculum (54%-87% bacterial population) and Thermoproteales (35%-63% archaeal population) dominate the micro-oxic hot spring source, while sulfur-oxidizing archaea (Sulfolobales, 57%-82%), and putative sulfur-oxidizing and heterotrophic bacterial groups dominate oxic downstream environments. The δ 13 C org (‰ V-PDB) values for sediment TOC and microbial biomass range from -9.4‰ at the spring's source decreasing to -12.6‰ downstream. A reverse effect isotope fractionation of ~3‰ between sediment sulfide (δ 34 S ~0‰) and dissolved water sulfate (δ 34 S +3.2‰), and δ 18 O values of ~ -5.3‰ suggest pyrite forms abiogenically from volcanic sulfide, followed by abiogenic and microbial oxidation. These environments represent an unexplored surficial geothermal environment analogous to transient volcanogenic habitats during putative "snowball Earth" scenarios and volcano-ice geothermal environments on Mars. © 2018 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.

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

USGS Publications Warehouse

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.

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

USGS Publications Warehouse

Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

2007-01-01

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2 O value was then used to estimate the oxygen isotope fractionation effects (??18 OSO42 - s(-) O2) between sulfate and dissolved oxygen in the aerobic experiments which were -10.0???, -10.8???, and -9.8??? for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between ??18OSO4 values in the biological and abiotic experiments, it is suggested that ??18OSO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions. ?? 2007 Elsevier Ltd. All rights reserved.

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

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.

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

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.

Oxidation of pyrite in an anoxic atmosphere

USGS Publications Warehouse

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.

Interactions of Oxygen and Water Molecules with Pyrite Surface: A New Insight.

PubMed

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.

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.

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.

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.

Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

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.

Iberian Pyrite Belt Subsurface Life (IPBSL), a drilling project in a geochemical Mars terrestrial analogue

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.

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.

A study of acid and ferruginous mine water in coal mining operations

NASA Astrophysics Data System (ADS)

Atkins, A. S.; Singh, R. N.

1982-06-01

The paper describes a bio-chemical investigation in the laboratory to identify various factors which promote the formation of acidic and ferruginous mine water. Biochemical reactions responsible for bacterial oxidation of Iron pyrites are described. The acidic and ferruginous mine water are not only responsible for the corrosion of mine plant and equipment and formation of scales in the delivery pipe range, but also pollution of the mine surface environment, thus affecting the surface ecology. Control measures to mitigate the adverse effects of acid mine discharge include the protection of mining equipment and prevention of formation of acid and ferruginous water. Various control measures discussed in the paper are blending with alkaline or spring water, use of neutralising agents and bactericides, and various types of seals for preventing water and air coming into contact with pyrites in caved mine workings.

Pyritic event beds and sulfidized Fe (oxyhydr)oxide aggregates in metalliferous black mudstones of the Paleoproterozoic Talvivaara formation, Finland

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.

Simulation of acid mine drainage generation around Küre VMS Deposits, Northern Turkey

NASA Astrophysics Data System (ADS)

Demirel, Cansu; Kurt, Mehmet Ali; Çelik Balci, Nurgül

2015-04-01

This study investigated comparative leaching characteristics of acidophilic bacterial strains under shifting environmental conditions at proposed two stages as formation stage or post acidic mine drainage (AMD) generation. At the first stage, initial reactions associated with AMD generation was simulated in shaking flasks containing massive pyritic chalcopyrite ore by using a pure strain Acidithiobacillus ferrooxidans and a mixed culture of Acidithiobacillus sp. mostly dominated by A. ferrooxidans and A. thiooxidans at 26oC. At the second stage, long term bioleaching experiments were carried out with the same strains at 26oC and 40oC to investigate the leaching characteristics of pyritic chalcopyrite ore under elevated heavy metal and temperature conditions. During the experiments, physicochemical characteristics (e.i. Eh, pH, EC) metal (Fe, Co, Cu, Zn) and sulfate concentration of the experimental solution were monitored during 180 days. Significant acid generation and sulfate release were determined during bioleaching of the ore by mixed acidophilic cultures containing both iron and sulfur oxidizers. In the early stage of the experiments, heavy metal release from the ore was caused by generation of acid due to accelerated bacterial oxidation of the ore. Generally high concentrations of Co and Cu were released into the solution from the experiments conducted by pure cultures of Acidithiobacillus ferrooxidans whereas high Zn and Fe was released into the solution from the mixed culture experiments. In the later stage of AMD generation and post AMD, chemical oxidation is accelerated causing excessive amounts of contamination, even exceeding the amounts resulted from bacterial oxidation by mixed cultures. Acidithibacillus ferrooxidans was found to be more effective in leaching Cu, Fe and Co at higher temperatures in contrary to mixed acidophiles that are more prone to operate at optimal moderate conditions. Moreover, decreasing Fe values are noted in bioleaching experiments with mixed acidophiles at higher temperatures. Further depleted Fe(III) values coinciding with decreasing pH may point to precipitation of secondary phases (i.e. jarosite). This study revealed that the metals (Fe, Cu, Co and Zn) released during short term leaching of the ore (34 days) are generally caused by acid produced by dissolution reactions rather than oxidation. In the long term experiments a more complex biogeochemical reactions (oxidation and dissolution) take place in conjunction. Key words: Bioleaching, AMD, heavy metal release, environment, acidophilic bacteria, Küre copper ore deposits, volcanogenic massive sulfide deposits

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

PubMed

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

Influence of the sulfur species reactivity on biofilm conformation during pyrite colonization by Acidithiobacillus thiooxidans.

PubMed

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.

Selective Adhesion of Thiobacillus ferrooxidans to Pyrite

PubMed Central

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

Surface chemical studies on selective separation of pyrite and galena in the presence of bacterial cells and metabolic products of Paenibacillus polymyxa.

PubMed

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.

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.

Final Technical Report. Reactivity of Iron-Bearing Minerals and CO 2 Sequestration and Surface Chemistry of Pyrite. An Interdisciplinary Approach

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

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

USGS Publications Warehouse

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.

Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

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.

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

Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

USGS Publications Warehouse

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.

Origin of stratiform sediment-hosted manganese carbonate ore deposits: Examples from Molango, Mexico, and TaoJiang, China

USGS Publications Warehouse

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.

Geochemistry of minor elements in the Monterey Formation, California; seawater chemistry of deposition

USGS Publications Warehouse

Piper, D.Z.; Isaacs, C.M.

1995-01-01

Approximately 24 samples of the Monterey Formation, Southern California, have been analyzed for their major-element oxide and minor-element content. These analyses allow identification of a detrital fraction, composed of terrigenous quartz, clay minerals, and other Al silicate minerals, and a marine fraction, composed of biogenic silica, calcite, dolomite, organic matter, apatite, and minor amounts of pyrite. The minor-element contents in the marine fraction alone are interpreted to have required, at the time of deposition, a high level of primary productivity in the photic zone and denitrifying bacterial respiration in the bottom water.

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

PubMed

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.

Different isotope and chemical patterns of pyrite oxidation related to lag and exponential growth phases of Acidithiobacillus ferrooxidans reveal a microbial growth strategy

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.

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

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.

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.

Geochemistry of arsenic in low sulfide-high carbonate coal waste rock, Elk Valley, British Columbia, Canada.

PubMed

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.

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

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.

Pyritized mudstone and associated facies in the Permian-Triassic boundary of the Çürük Daǧ section, Southern Turkey

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.

Microbially induced flotation and flocculation of pyrite and sphalerite.

PubMed

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.

Geologic and mineralogic controls on acid and metal-rich rock drainage in an alpine watershed, Handcart Gulch, Colorado

USGS Publications Warehouse

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.

Superparamagnetic Fe3O4 particles formed by oxidation of pyrite heated in an anoxic atmosphere

USGS Publications Warehouse

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.

Oxidative dissolution of pyrite surfaces by hexavalent chromium: Surface site saturation and surface renewal

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.

Fe(III):S(-II) concentration ratio controls the pathway and the kinetics of pyrite formation during sulfidation of ferric hydroxides

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.

Chemistry and phase evolution during roasting of toxic thallium-bearing pyrite.

PubMed

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.

Oxidation of pyrite in coal to magnetite

USGS Publications Warehouse

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.

Marine origin of pyritic sulfur in the Lower Bakerstown coal bed, Castleman coal field, Maryland (U.S.A.)

USGS Publications Warehouse

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.

Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

PubMed Central

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.

PubMed

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.

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.

Extraction of manganese from electrolytic manganese residue by bioleaching.

PubMed

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.

Sulfur Isotropic Studies of Archean Slate and Graywacke from Northern Minnesota: Evidence for the Existence of Sulfate Reducing Bacteria

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.

Enzyme-Linked Immunofiltration Assay To Estimate Attachment of Thiobacilli to Pyrite

PubMed Central

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

Pyrite oxidation and reduction - Molecular orbital theory considerations. [for geochemical redox processes

NASA Technical Reports Server (NTRS)

Luther, George W., III

1987-01-01

In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

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

PubMed Central

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.

PubMed

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.

Arsenic transformation and mobilization from minerals by the arsenite oxidizing strain WAO

USGS Publications Warehouse

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.

Variable infiltration and river flooding resulting in changing groundwater quality - A case study from Central Europe

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.

Bacterial community and groundwater quality changes in an anaerobic aquifer during groundwater recharge with aerobic recycled water.

PubMed

Ginige, Maneesha P; Kaksonen, Anna H; Morris, Christina; Shackelton, Mark; Patterson, Bradley M

2013-09-01

Managed aquifer recharge offers the opportunity to manage groundwater resources by storing water in aquifers when in surplus and thus increase the amount of groundwater available for abstraction during high demand. The Water Corporation of Western Australia (WA) is undertaking a Groundwater Replenishment Trial to evaluate the effects of recharging aerobic recycled water (secondary treated wastewater subjected to ultrafiltration, reverse osmosis, and ultraviolet disinfection) into the anaerobic Leederville aquifer in Perth, WA. Using culture-independent methods, this study showed the presence of Actinobacteria, Alphaproteobacteria, Bacilli, Betaproteobacteria, Cytophaga, Flavobacteria, Gammaproteobacteria, and Sphingobacteria, and a decrease in microbial diversity with an increase in depth of aquifer. Assessment of physico-chemical and microbiological properties of groundwater before and after recharge revealed that recharging the aquifer with aerobic recycled water resulted in elevated redox potentials in the aquifer and increased bacterial numbers, but reduced microbial diversity. The increase in bacterial numbers and reduced microbial diversity in groundwater could be a reflection of an increased denitrifier and sulfur-oxidizing populations in the aquifer, as a result of the increased availability of nitrate, oxygen, and residual organic matter. This is consistent with the geochemical data that showed pyrite oxidation and denitrification within the aquifer after recycled water recharge commenced. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

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

USGS Publications Warehouse

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.

Pyrite-enhanced degradation of chloramphenicol by low concentrations of H2O2.

PubMed

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.

Iron disulfide minerals and the genesis of roll-type uranium deposits.

USGS Publications Warehouse

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.

Formation of carbonate pipes in the northern Okinawa Trough linked to strong sulfate exhaustion and iron supply

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.

Biofilm formation, communication and interactions of leaching bacteria during colonization of pyrite and sulfur surfaces.

PubMed

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.

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

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.

Correlation of Surface Adsorption and Oxidation with a Floatability Difference of Galena and Pyrite in High-Alkaline Lime Systems.

PubMed

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.

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.

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

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.

Hydrochemical and stable isotope indicators of pyrite oxidation in carbonate-rich environment; the Hamersley Basin, Western Australia

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.

Treatment impacts on temporal microbial community dynamics during phytostabilization of acid-generating mine tailings in semiarid regions.

PubMed

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.

Effect of Surface Oxidation on Interfacial Water Structure at a Pyrite (100) Surface as Studied by Molecular Dynamics Simulation

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

Pyrite-Type Nanomaterials for Advanced Electrocatalysis.

PubMed

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.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

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.

Amphorous hydrated Fe(III) sulfate: metastable product and bio-geochemical marker of iron oxidizing thiobacilli

NASA Astrophysics Data System (ADS)

Lazaroff, Norman; Jollie, John; Dugan, Patrick R.

1998-07-01

Chemolithotrophic iron oxidation by Thiobacillus ferrooxidans and other iron oxidizing thiobacilli produce an Fe(III) sulfato complex that polymerizes as x-ray amorphous filaments approximately 40 nm in diameter. The precursor complex in solutionis seen by ATR-FTIR spectroscopy to have a sulfate spectrum resembling the v(subscript 3) and v(subscript 1) vibrational modes of the precipitated polymer. Chemically similar precipitates prepared by oxidation of acid ferrous sulfate with hydrogen peroxide have a different micromorphology, higher iron/sulfur ratio and acid solubility than the bacterial product. They possess coalescing globular microstructures composed of compacted micro-fibrils. Scanning electron microscopy and diffuse reflectance FTIR show the formation of iron polymer on the surface of immobilized cells of T. ferrooxidans, oxidizing iron during the corrosion of steel. Although spatially separated form the steel coupons by a membrane filter, the cell walls become covered with tufts of amorphous hydrated Fe(III) sulfate. The metastable polymer is converted to crystalline goethite, lepidocrocite, and magnetite in that order, as the pH rises due to proton reduction at cathodic sites on the steel. The instability of the iron polymer to changes in pH is also evidenced by the loss of sulfate when washed with lithium hydroxide solution at pH 8. Under those conditions there is little change in micromorphology, but restoration of sulfate with sulfuric acid at pH 2.5, fails to re-establish the original chemical structure. Adding sulfate salts of appropriate cations to solutions of the Fe(III) sulfato complex or suspensions of its precipitated polymer in dilute sulfuric acid, result in dissociation of the metastable complex followed by crystallization of ferric ions and sulfate in jarosites. Jarosites and other derivatives of iron precipitation by iron oxidizing thiobacilli, form conspicuous deposits in areas of natural pyrite leaching. The role of iron oxidizing thiobacilli in pyrite leaching, biohydrometallurgy, acid mine drainage, and the cycle of iron and sulfur in nature, has been studied for nearly 50 years. The manifestation of those activities, so widespread on Earth, can be a clue for seeking evidence of life elsewhere.

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

PubMed

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.

Uranium and plutonium in anoxic marine sediments of the Santiago River mouth (Eastern Pacific, Mexico).

PubMed

Almazán-Torres, María Guadalupe; Ordóñez-Regil, Eduardo; Ruiz-Fernández, Ana Carolina

2016-11-01

The uranium (U) and plutonium (Pu) content with depth in a sediment core collected in the continental shelf off the mouth of the Santiago River in the Mexican Pacific was studied to evaluate the contamination effects of the effluent of the Santiago-Lerma River as it moves into the sea. The large mass of terrestrial detritus delivered by the river influences the physicochemical and geochemical processes in the seafloor. Abnormal concentrations of U and Pu in sediments were examined as indicative of the effects of anoxic conditions. One of the indicators of pollution of seawater is the bacterial activity of the shallow seabed layer; and among the prevailing bacteria, the magnetotactic ones induce the formation of euhedral and framboidal shapes (pyrite). These pyrite entities are by-products of anoxic environments loaded with decomposing detrital material and are very abundant in the surface layers of the sediment core analyzed. The pyrite formation is the result of a biochemical reaction between iron and organic sulphur reduced by bacteria, and the pyrite entities precipitate to the seafloor. In the same upper zone of the profile, 238 U is readily immobilized, while 234 U is oxidized and dissolved in seawater by the effect of hot atom chemistry. This may cause the activity ratio (AR) 234 U/ 238 U disequilibrium (near 0.41). Furthermore, in the shallow layer of the sediment core, an abnormally high concentration of 239+240 Pu was detected. In this upper layer, the activity concentrations found were 3.19 Bq kg -1 for 238 U, 1.32 kg -1 for 234 U and 2.78 Bq kg -1 for 239+240 Pu. In the lower fractions of the sediment core, normal values of AR 234 U/ 238 U (≈1) were found, with traces of 239+240 Pu. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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.

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.

Heavy minerals and sedimentary organic matter in Pleistocene and Cretaceous sediments on Long Island, New York, with emphasis on pyrite and marcasite in the Magothy aquifer

USGS Publications Warehouse

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.

CHEMICAL MAPPING OF ELEMENTAL SULFUR ON PYRITE AND ARSENOPYRITE SURFACES USING NEAR-INFRARED RAMAN IMAGING MICROSCOPY. (R826189)

EPA Science Inventory

Abstract

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...

Chemistry and mineralogy of pyrite-enriched sediments at a passive margin sulfide brine seep: abyssal Gulf of Mexico

USGS Publications Warehouse

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.

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

A SIMS Study of Sulfur Isotopes of Accessory Pyrites Associated with Barites from Methane Cold Seeps in the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Morelli, E. C.; Aharon, P.

2017-12-01

Bacteria and archaea associated with seeps can fix methane from sublimating gas hydrates through coupled bacterial sulfate reduction/ anaerobic methane oxidation (BSR/AMO) and prevent outgassing to the atmosphere. The occurrence of such microbial processes has been established on the basis of the sulfur isotope compositions of microbial byproducts (pyrites; FeS2) that reflect the degree of fractionation between SO4 and FeS2 via the production of the H2S intermediate phase. BSR/AMO coupling has been discerned in accessory sulfides associated with carbonates from gas hydrate sites. Whether BSR/AMO coupling is also active in barites, another ubiquitous product of gas hydrate sublimation, has so far been overlooked. Here we present results of a new sulfur isotope study of accessory sulfides in barites associated with gas hydrates at the threshold of stability occurring on the Gulf of Mexico slope. Using a fractionation factor of 1.009 and a seawater δ34SSO4 value of 20.3‰ and assuming a Rayleigh distillation closed system model for marine sulfide precipitation, pyrites from barite gas seeps are predicted to exhibit a range of δ34S values (about -1‰ to 20‰ CDT) as the pool of sulfate is continuously depleted. Actual δ34S values could fall outside of the predicted range because the system in question is likely only partially closed and kinetic fractionations are likely. δ34S of accessory pyrites from three Garden Banks Lease Block 382 (510 - 640m water depth) and one Mississippi Canyon Lease Block 929 (590m) barite samples have been determined using an ims-1290 Secondary Ion Mass Spectrometer (SIMS). Two Garden Banks samples and one Mississippi Canyon sample reveal a spread of values from 5.30 ± 0.04 to 25.90 ± 0.09 (‰ CDT), which follow the predicted trend for gas seeps and indicate the source of fractionation is likely from the coupled BSR/AMO process. One Garden Banks sample yields a wide spread of values from -26.2 ± 0.05 to 20.5 ± 0.4 (‰ CDT). The negative values are unexpected because such values typically suggest a sole contribution by BSR. This sample was the youngest (12.8 ± 0.6 yrs versus 21.5 ± 1.9 to 44.23 ± 2.92 yrs) at time of collection, and thus some of the negative values could reflect kinetic effects governed by the BSR pathway or anaerobic bacterial disproportionation (BDS) of elemental sulfur.

Exploring Nested Reaction Fronts to Understand How Oxygen Cracks Rocks, Carbonic and Sulfuric Acids Dissolve Rocks, and Water Transports Rocks during Weathering

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.

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

PubMed

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.

Biogeochemical Cycling of Fe, S, C, N, and Mo in the 3.2 Ga ocean: Constraints from DXCL-DP Black Shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Naraoka, H.; Ikehara, M.; Ito, T.; Kiyokawa, S.

2014-12-01

Records of geochemical cycling of bio-essential, redox-sensitive elements have keys to decipher mysteries of the co-evolution of Earth and life. To obtain insight into biogeochemical cycling of those elements and early evolution of microbial biosphere from high-quality samples, we drilled through Mesoarchean strata in coastal Pilbara (Dixon Island-Cleaverville Drilling Project, see Yamaguchi et al., 2009; Kiyokawa et al., 2012), and obtained 3.2 Ga old drillcores (CL1, CL2, and DX) of sulfide-rich black shales in the Cleaverville Group, Pilbara Supergroup. We conducted a systematic geochemical study involving sequential extractions of Fe, S, C, and N for phase-dependent contents (e.g., pyrite-Fe, reactive-Fe, highly reactive-Fe, unreactive-Fe, pyrite-S, sulfate-S, organic-S, elemental-S, Corg, Ccarb, Norg, and Nclay) and their stable isotope compositions, micro FT-IR and laser Raman spectroscopy for extracted kerogen, in addition to major and trace (redox-sensitive; e.g., Mo) element analysis, for >100 samples. Here we integrate our recent multidisciplinary investigations into the redox state of ocean and nature of microbial biosphere in the ocean 3.2 Ga ago. All of the obtained data are very difficult to explain only by geochemical processes in strictly anoxic environments, where both atmosphere and oceans were completely anoxic, like an environment before the inferred "Great Oxidation Event" when pO2 was lower than 0.00001 PAL (e.g., Holland, 1994). Our extensive data set consistently suggests that oxygenic photosynthesis, bacterial sulfate reduction, and microbially mediated redox-cycling of nitrogen, possibly involving denitrification and N2-fixation, are very likely to have been operating, and may be used as a strong evidence for at least local and temporal existence of oxidized environment as far back as 3.2 Ga ago. Modern-style biogeochemical cycling of Fe, S, C, N, and Mo has been operating since then. The atmosphere-hydrosphere system 3.2 Ga ago would have been sufficiently oxidized to allow redox-cycling of elements during deposition of the sediments, ~800 Ma earlier than commonly thought. Our suggestions have far-reaching and astrobiological implications for earlier evolution of the surface environment, especially redox state, and marine microbial biosphere.

[Thermoacidophilic micirobial community oxidizing the gold-bearing flotation concentrate of a pyrite-arsenopyrite ore].

PubMed

Paniushkina, A E; Tsaplina, I A; Grigor'eva, N V; Kondrat'eva, T F

2014-01-01

An aboriginal community of thermophilic acidophilic chemolithotrophic microorganisms (ACM) was isolated from a sample of pyrite gold-bearing flotation concentrateat 45-47 degrees C and pH 1.8-2.0. Compared to an experimental thermoacidophilic microbial consortium formed in the course of cultivation in parallel bioreactors, it had lower rates of iron leaching and oxidation, while its rate of sulfur oxidation was higher. A new thermophilic acidophilic microbial community was obtained by mutual enrichment with the micioorganisms from thie experimental and aboriginal communities during oxidation of sulfide ore flotation concentrate at 47 degrees C. The dominant bacteria of this new ACM community were Acidithiobacillus caldus strains (the most active sulfur oxidizers) and Sulfobacillus thermotolerans strains (active oxidizers of both iron and sulfur), while iron-oxidizing archaea of the family Ferroplasmaceae and heterotrophic bacteria Alicyclobacillus tolerans were the minor components. The new ACM community showed promise for leaching/oxidation of sulfides from flotation concentrates at high pulp density (S:L = 1:4).

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

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.

Protein footprinting by pyrite shrink-wrap laminate.

PubMed

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.

Open system sulphate reduction in a diagenetic environment - Isotopic analysis of barite (δ34S and δ18O) and pyrite (δ34S) from the Tom and Jason Late Devonian Zn-Pb-Ba deposits, Selwyn Basin, Canada

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.

Oxidation of coal and coal pyrite mechanisms and influence on surface characteristics. Technical progress report, December 31, 1993

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

Evaluating the oxidation of shale during hydraulic fracturing using SEM-EDS and spectrocolorimetry

NASA Astrophysics Data System (ADS)

Tan, X. Y.; Nakashima, S.

2017-12-01

During hydraulic fracturing (fracking) for shale gas/oil extraction, oxygen is introduced into deep oxygen-poor environments, and Fe2+-bearing minerals in rocks can be oxidized thus leading to the degradation of rock quality. Akita diatomaceous shale is considered to be one of the source rocks for oil and gas fields in northwestern Japan. Outcrops of Akita shale often show presence of jarosite (Fe sulfate: yellow) and/or goethite (Fe hydroxide: brown to orange) as oxidation products of pyrite (FeS2). Several series of oxidation experiments of Akita shale under dry, humid, and wet conditions were conducted at temperatures of around 30 oC and 50oC for 30-40 days. Portable color spectro-colorimeters were used to monitor color changes of the rock surfaces every hour. SEM-EDS, UV-Vis, and Raman spectroscopic analyses were performed on the rock sample surface to examine the chemical and mineralogical compositions of Akita shale before and after the dry, humid, and wet experiments. In SEM-EDS analyses before the humid experiment, Fe and S containing phases show their atomic ratio close to 1:2 indicating that this is pyrite (FeS2). After the experiment, the ratio changed to around 1:1 suggesting a conversion from pyrite (FeS2) to mackinawite-like mineral (FeS). In addition, the formation of Ca sulfate (possibly gypsum: CaSO4.2H2O) and goethite-like Fe hydroxide were identified which were not present initially. Therefore, oxidation pathways of iron sulfide (pyrite: FeS2) via FeS to sulfate is confirmed by our humid experiments around 30oC on Akita shale. These oxidation processes might occur during the fracking of shale within relatively short time periods associated with precipitation of sulfates and hydroxides. Therefore, further studies are needed for their effects on rock properties and gas/oil production.

Redox processes in subducting oceanic crust recorded by sulfide-bearing high-pressure rocks and veins (SW Tianshan, China)

NASA Astrophysics Data System (ADS)

Li, Ji-Lei; Gao, Jun; Klemd, Reiner; John, Timm; Wang, Xin-Shui

2016-09-01

The oxidized nature of the sub-arc mantle and hence arc magmas is generally interpreted as a result of the migration of subduction-related oxidizing fluids or melts from the descending slab into the mantle wedge. This is of particular importance seeing that the oxidization state of sub-arc magmas seems to play a key role in the formations of arc-related ore deposits. However, direct constraints on the redox state of subducted oceanic crust are sparse. Here, we provide a detailed petrological investigation on sulfide- and oxide-bearing eclogites, blueschists, micaschists, eclogite-facies and retrograde veins from the Akeyazi high-pressure (HP) terrane (NW China) in order to gain insight into the redox processes recorded in a subducting oceanic slab. Sulfides in these rocks are mainly pyrite and minor pyrrhotite, chalcopyrite, bornite, molybdenite, sphalerite and chalcocite, including exsolution textures of bornite-chalcopyrite intergrowth. Magnetite, ilmenite and pyrite occur as inclusions in garnet, whereas sulfides are dominant in the matrix. Large pyrite grains in the matrix contain inclusions of garnet, omphacite and other HP index minerals. However, magnetite replacing pyrite textures are commonly observed in the retrograded samples. The eclogite-facies and retrograde veins display two fluid events, which are characterized by an early sulfide-bearing and a later magnetite-bearing mineral assemblage, respectively. Textural and petrological evidences show that the sulfides were mainly formed during HP metamorphism. Mineral assemblage transitions reveal that the relative oxygen fugacity of subducted oceanic crust decreases slightly with increasing depths. However, according to oxygen mass balance calculations, based on the oxygen molar quantities ( nO2), the redox conditions remain constant during HP metamorphism. At shallow levels (<60 km) in the subduction channel, interaction with oxidized fluid seems to have caused an increase of the oxygen fugacity and the oxidation state of exhuming HP rocks. This study suggests that oxygen components are not released in significant amounts during HP metamorphism of subducted oceanic crust and, thus, cannot be responsible for oxidizing the mantle wedge and increasing the oxidation state of sub-arc mantle melts.

Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2015-12-01

The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at <10-5 present atmospheric O2).2 As a result, it is difficult to quantify O2 concentrations implied by observed trace metal variations. As a first step toward providing more quantitative constraints on late Archean pO2, we conducted laboratory studies of pyrite and molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our results provide new empirical data that should allow for more precise quantitative constraints on atmospheric pO2 based on the sedimentary rock record. 1Anbar, A.D. et al., 2007. Science, 317, i. 5846: 1903-1906. 2Williamson & Rimstidt, 1994. Geochim. et Cosmochim. Acta, 58, n. 24: 5443-5454. 3Lehner et al., 2015. PLoS ONE, 10, n. 6: 1-15.

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

DOE PAGES

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.

Multidisciplinary integrated field campaign to an acidic Martian Earth analogue with astrobiological interest: Rio Tinto

NASA Astrophysics Data System (ADS)

Gómez, F.; Walter, N.; Amils, R.; Rull, F.; Klingelhöfer, A. K.; Kviderova, J.; Sarrazin, P.; Foing, B.; Behar, A.; Fleischer, I.; Parro, V.; Garcia-Villadangos, M.; Blake, D.; Martin Ramos, J. D.; Direito, S.; Mahapatra, P.; Stam, C.; Venkateswaran, K.; Voytek, M.

2011-07-01

Recently reported results from latest Mars Orbiters and Rovers missions are transforming our opinion about the red planet. That dry and inhospitable planet reported in the past is becoming a wetter planet with high probabilities of water existence in the past. Nowadays, some results seem to indicate the presence of water beneath the Mars surface. But also mineralogy studies by NASA Opportunity Rover report iron oxides and hydroxides precipitates on Endurance Crater. Sedimentary deposits have been identified at Meridiani Planum. These deposits must have generated in a dune aqueous acidic and oxidizing environment. Similarities appear when we study Rio Tinto, and acidic river under the control of iron. The discovery of extremophiles on Earth widened the window of possibilities for life to develop in the Universe, and as a consequence on Mars and other planetary bodies with astrobiological interest. The compilation of data produced by the ongoing missions offers an interested view for life possibilities to exist: signs of an early wet Mars and rather recent volcanic activity as well as ground morphological characteristics that seem to be promoted by liquid water. The discovery of important accumulations of sulfates and the existence of iron minerals such as jarosite in rocks of sedimentary origin has allowed specific terrestrial models to come into focus. Río Tinto (Southwestern Spain, Iberian Pyritic Belt) is an extreme acidic environment, product of the chemolithotrophic activity of micro-organisms that thrive in the massive pyrite-rich deposits of the Iberian Pyritic Belt. Some particular protective environments should house the organic molecules and bacterial life forms in harsh environments such as Mars surface supporting microniches inside precipitated minerals or inside rocks. Terrestrial analogues could help us to afford the comprehension of habitability (on other planetary bodies). We are reporting here the multidisciplinary study of some endolithic niches inside salt deposits used by phototrophs for taking advantage of sheltering particular light wavelengths. These acidic salts deposits located in Río Tinto shelter life forms that are difficult to visualize by eye. This interdisciplinary field analogue campaign was conducted in the framework of the CAREX FP7 EC programme.

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.

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

PubMed

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

2015-07-07

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

Selective geochemistry of iron in mangrove soils in a semiarid tropical climate: effects of the burrowing activity of the crabs Ucides cordatus and Uca maracoani

NASA Astrophysics Data System (ADS)

Araújo, J. M. C.; Otero, X. L.; Marques, A. G. B.; Nóbrega, G. N.; Silva, J. R. F.; Ferreira, T. O.

2012-08-01

Bioturbation by crabs may affect processes associated with organic matter decomposition in mangrove soils. This study examines how two crabs ( Uca maracoani and Ucides cordatus), which are of substantial ecological and economic importance in semiarid coastal areas of Brazil, affect biogeochemical processes in mangrove soils. For this purpose, the physicochemical and geochemical parameters of the soils at different sites were analyzed. The redox potential was always positive at bioturbated sites (+12 to +218 mV), indicating more oxidizing conditions conducive to the oxidation of pyrite and precipitation of oxyhydroxides. In contrast, anoxic conditions prevailed at the control site (Eh < 0 mV), and the most abundant form of iron was Fe-pyrite. The highest degree of iron pyritization (DOP) was observed in soils from the control site (˜48%) and the lowest in the bioturbated soils (5-16%), indicating that crabs have an oxidative effect on iron sulfides. The results also suggest that U. cordatus has a higher oxidizing capacity than U. maracoani, probably because it constructs larger and deeper burrows. The results demonstrate that both crabs must be considered as important bioturbators in Brazilian semiarid mangrove soils, being capable of enhancing organic matter decomposition and also shifting the dominant pathway of organic matter degradation.

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.

Environmental Geochemistry and Acid Mine Drainage Evaluation of an Abandoned Coal Waste Pile at the Alborz-Sharghi Coal Washing Plant, NE Iran

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

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

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.

Release of Particulate Iron Sulfide during Shale-Fluid Interaction.

PubMed

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.

Synergistic effect of biogenic Fe3+ coupled to S° oxidation on simultaneous bioleaching of Cu, Co, Zn and As from hazardous Pyrite Ash Waste.

PubMed

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.

Minor element distribution in iron disulfides in coal: a geochemical review

USGS Publications Warehouse

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.

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.

Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S-I and Octahedral FeII Sites: Evidence from EXAFS-DFT Analysis.

PubMed

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.

Textures and trace element composition of pyrite from the Bukit Botol volcanic-hosted massive sulphide deposit, Peninsular Malaysia

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.

Pyrite oxidation under simulated acid rain weathering conditions.

PubMed

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.

Thermal Stability of FeS2 Cathode Material in "Thermal" Batteries: Effect of Dissolved Oxides in Molten Salt Electrolytes

NASA Astrophysics Data System (ADS)

Masset, Patrick J.

2008-09-01

The thermal stability of FeS2 cathode material for thermal batteries is investigated in the LiCl-KCl eutectic containing up to 10 wt% Li2O (used as anti-peak). The results show that the decomposition of pyrite shifts to higher temperatures in the presence of molten salts as the S2 gas is repressed by the liquid phase. For high lithium oxide contents the decomposition temperature of pyrite decreases by 100 °C. In addition Li2FeS2 as reaction product is evidenced whereas Li3Fe2S4 is expected from literature data.

A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation

NASA Technical Reports Server (NTRS)

Raiswell, R.; Canfield, D. E.; Berner, R. A.

1994-01-01

Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

Multiple sulfur isotope constraints on sulfate-driven anaerobic oxidation of methane: Evidence from authigenic pyrite in seepage areas of the South China Sea

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.

Solution-based Syntheses of Iron Pyrite Thin Films for Photovoltaic and Protein Foot-printing Applications

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.

Habitability: Where to look for life? Halophilic habitats: Earth analogs to study Mars habitability

NASA Astrophysics Data System (ADS)

Gómez, F.; Rodríguez-Manfredi, J. A.; Rodríguez, N.; Fernández-Sampedro, M.; Caballero-Castrejón, F. J.; Amils, R.

2012-08-01

Oxidative stress, high radiation doses, low temperature and pressure are parameters which made Mars's surface adverse for life. Those conditions found on Mars surface are harsh conditions for life to deal with. Life, as we know it on Earth, needs several requirements for its establishment but, the only "sine qua nom" element is water. Extremophilic microorganisms widened the window of possibilities for life to develop in the universe, and as a consequence on Mars. Recently reported results in extreme environments indicate the possibility of presence of "oasys" for life in microniches due to water deliquescence in salts deposits. The compilation of data produced by the ongoing missions (Mars Global Surveyor, Mars Odyssey, Mars Express and Mars Exploration Rover Opportunity) offers a completely different view from that reported by Viking missions: signs of an early wet Mars and rather recent volcanic activity. The discovery of important accumulations of sulfates, and the existence of iron minerals like jarosite, goethite and hematite in rocks of sedimentary origin has allowed specific terrestrial models related with this type of mineralogy to come into focus. Río Tinto (Southwestern Spain, Iberian Pyritic Belt) is an extreme acidic environment, product of the chemolithotrophic activity of microorganisms that thrive in the massive pyrite-rich deposits of the Iberian Pyritic Belt. The high concentration of ferric iron and sulfates, products of the metabolism of pyrite, generate a collection of minerals, mainly gypsum, jarosite, goethite and hematites, all of which have been detected in different regions of Mars. Some particular protective environments or elements could house organic molecules or the first bacterial life forms on Mars surface. Terrestrial analogs could help us to afford its comprehension. We are reporting here some preliminary studies about endolithic niches inside salt deposits used by phototrophs for taking advantage of sheltering particular light wavelengths. These acidic salts deposits located in Río Tinto shelter life forms which are difficult to localize by eye. Techniques for its localization and study during space missions are needed to develop. Extreme environments are good scenarios where to test and train those techniques and where hypothetical astrobiological space missions could be simulated for increasing possibilities of micro niches identification.

Inhibition of bacterial activity in acid mine drainage

NASA Astrophysics Data System (ADS)

Singh, Gurdeep; Bhatnagar, Miss Mridula

1988-12-01

Acid mine drainage water give rise to rapid growth and activity of an iron- and sulphur- oxidizing bacterium Thiobacillus ferrooxidians which greatly accelerate acid producing reactions by oxidation of pyrite material associated with coal and adjoining strata. The role of this bacterium in production of acid mine drainage is described. This study presents the data which demonstrate the inhibitory effect of certain organic acids, sodium benzoate, sodium lauryl sulphate, quarternary ammonium compounds on the growth of the acidophilic aerobic autotroph Thiobacillus ferrooxidians. In each experiment, 10 milli-litres of laboratory developed culture of Thiobacillus ferrooxidians was added to 250 milli-litres Erlenmeyer flask containing 90 milli-litres of 9-k media supplemented with FeSO4 7H2O and organic compounds at various concentrations. Control experiments were also carried out. The treated and untreated (control) samples analysed at various time intervals for Ferrous Iron and pH levels. Results from this investigation showed that some organic acids, sodium benzoate, sodium lauryl sulphate and quarternary ammonium compounds at low concentration (10-2 M, 10-50 ppm concentration levels) are effective bactericides and able to inhibit and reduce the Ferrous Iron oxidation and acidity formation by inhibiting the growth of Thiobacillus ferrooxidians is also discussed and presented

Micro-Scale Sulfur and Carbon Isotope Analysis of a Neoarchean Stromatolite: Evidence for a Profound Redox Transition in Shelf Margins prior to the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Ilhardt, P.; House, C. H.; Altermann, W.

2016-12-01

Neoarchean shelf margin environments such as the Campbellrand-Malmani platform are believed to have been sites of substantial O2 accumulation and nutrient cycling prior to the Great Oxidation Event (GOE). Stromatolites in particular serve as biogeochemical "hotspots" where evidence of various metabolic pathways and bacterial lineages can be traced through geochemical fingerprints. We identified morphologically-unique, organic-rimmed pyrite grains embedded in the dolomitic lamina of a Campbellrand Subgroup stromatolite (2.6 Ga). Carbon and sulfur isotopes measured in situ revealed a multi-layered microbial community employing photoautotrophic carbon fixation, organic matter respiration, sulfate reduction, and potentially assimilation of methane. In particular, unusually high kerogen δ13Corg and pyrite δ34S compositions are consistent with a semi-aerobic ecosystem recycling photosynthetic biomass and sulfate reduction in sulfate-limited porewaters, respectively. In addition, an array of positive Δ33S values suggests incorporation of atmospherically-derived sulfur formed from volcanic SO2 photochemistry and isolated in particulate form. We argue the Δ33S-δ34S trend is best explained by mixing between a δ34S-enriched coastal marine sulfate reservoir and stratospheric Δ33S-positive sulfate or elemental sulfur aerosols. The hypothesized buildup of sulfur gases at higher altitudes agrees with prior arguments for increased subaerial felsic volcanism and intense plume activity coinciding with oxidation of the upper mantle. We suggest explosive subaerial eruptions sustained a stratospheric SO2 reservoir that underwent photochemistry via long-wavelength (250-330 nm) UV radiation to produce positive MIF-carrying aerosol particles (sulfate or sulfur) in the Neoarchean. This contrasts with Paleoarchean sulfur chemistry dominated by SO2 photolysis in the 190-220 nm excitation band and points to an evolving Archean atmosphere, culminating in a coupled biogeochemical-tectonic redox transformation that fundamentally changed the atmospheric sulfur cycle and ultimately prompted the GOE.

Oxidative Degradation of Chlorophenolic Compounds with Modified-Fenton Process Using Pyrite as the Catalyst

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.

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

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.

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.

Coupled Fe and multiple-S isotope systematics of pyrite and evidence of increasing atmospheric oxygen in 2.5 Ga sediments of the Kaapvaal Craton

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.

Iron and sulfur geochemistry in semi-arid mangrove soils (Ceará, Brazil) in relation to seasonal changes and shrimp farming effluents.

PubMed

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.

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Grangeon, S.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Guerrot, C.; Widory, D.; Fléhoc, C.; Wille, G.; Ramboz, C.; Vinsot, A.; Buschaert, S.

2011-05-01

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (-38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (-38‰ to -22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (-14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ 18O values (˜+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.

Enhanced Reactant-Contaminant Contact through the Use of Persulfate In Situ Chemical Oxidation (ISCO)

DTIC Science & Technology

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

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

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.

(S, C, O, Sr) isotopic constraints on the diagenetic evolution of the COX clay formations at the Bure URL site, Paris Basin)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Widory, D.; Guerrot, C.; Buschaert, S.

2009-04-01

The Underground Research Laboratory of Bure, located in the Eastern part of the Paris Basin, was selected by ANDRA (French Agency for Nuclear Management) in order to study the feasibility of a nuclear waste disposal in the Callovian-Oxfordian thick clayey formation at 400 meters depth. Since 1994's, numerous investigations have been initiated to understand and predict the behaviour of the clay formation in time and in space, by constraining its stability, the chemical evolution of the porewaters, and solution transfers between the clayey formation and its adjacent limestone sequences during geological times (ANDRA, 2005). In that way, this study presents combined new mineralogical and isotopic data of the diagenetic mineral sequence to constrain the porewater chemistry of the rock at different stages of the sedimentary then burial history of the clayey formation. The petrological study of Callovian-Oxfordian claystones provided evidence of the following diagenetic mineral sequence: 1) Framboïdal pyrite ± micritic calcite in replacement of carbonate bioclasts and in bioturbations, 2) Iron-rich euhedral carbonates (ankerite, sideroplesite), Glauconite, 3) Sparry dolomite, celestite in residual porosity, 4) Chalcedony 5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (-38 to +74 permil/CDT), providing evidence of bacterial sulphate reduction processes. The lowest negative values (-38 to -22 permil) indicate precipitation of pyrite in a marine environment with a permanent recharge in sulphate, whereas the higher pyrite δ34S values (-14 up to +74 permil) show that pyrite precipitated in a system that closed for sulphate. Consequently the variations of pyrite δ34S in bioturbations along the lithostratigraphic profil indicate a change of sedimentation conditions from a deep marine environment to an environment with alternative recharge of marine sulphates; that is consistent with the transgression/regression cycle observed in the middle sequence of the formation. The δ34S values of celestite (+ 22 to +31 permil /CDT) reflect the last evolution stage of the system at which the bacterial activity ends, the celestite corresponding to the deposition of the residual dissolved sulphate anions in the diagenetic porewaters. The 87Sr/86Sr ratio of celestite (0.706872-0.707040) is consistent with a deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates (δ13C= +0.2 to +2.3 permil/PDB, δ18O= +27.7 to +28.7 permil/SMOW) whereas late diagenetic siderite is slightly 13C- depleted. The 13C-depletion could be attributed to a partial contribution in diagenetic porewaters of carbonate ions derived partially from the degradation of organic matter issue of the bacterial sulphate reduction. The δ18O values of late diagenetic chalcedony range between +27 and +31 permil(/SMOW), suggesting precipitation from marine-derived porewaters at temperatures of maximum burial (~40-50°C). Late calcite in veinlet reworking with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ18O values (~+19 permil/SMOW), suggesting they precipitated from meteoric fluids (δ18O ~ -6 permil), whose signature is close to present-day porewaters of the formation. To conclude, combined mineralogical and isotopic data show that pyrite, sulfates, calcite cement, euhedral iron-bearing carbonates and probably chalcedony are diagenetic phases precipitated from marine-derived porewaters in conditions controlled by bacterial sulphate reduction. A calcite veinlet reworking chalcedony and celestite (in the middle sequence of the formation) and euhedral quartz encrusting a vug in a limestone from the top of the clayey formation are the only mineral records of the introduction of meteoric fluid in the clay formation, and the only phases at isotopic equilibrium with present-day porewaters.

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

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H 2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

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

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Oxygen transport and pyrite oxidation in unsaturated coal-mine spoil

USGS Publications Warehouse

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.

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.

Draft genome sequence of Bosea sp. WAO an arsenite and sulfide oxidizer isolated from a pyrite rock outcrop in New Jersey.

PubMed

Walczak, Alexandra B; Yee, Nathan; Young, Lily Y

2018-01-01

This genome report describes the draft genome and physiological characteristics of Bosea sp. WAO (=DSM 102914), a novel strain of the genus Bosea in the family Bradyrhizobiaceae . Bosea sp. WAO was isolated from pulverized pyritic shale containing elevated levels of arsenic. This aerobic, gram negative microorganism is capable of facultative chemolithoautotrophic growth under aerobic conditions by oxidizing the electron donors arsenite, elemental sulfur, thiosulfate, polysulfide, and amorphous sulfur. The draft genome is of a single circular chromosome 6,125,776 bp long consisting of 21 scaffolds with a G + C content of 66.84%. A total 5727 genes were predicted of which 5665 or 98.92% are protein-coding genes and 62 RNA genes. We identified the genes aioA and aioB , which encode the large and small subunits of the arsenic oxidase respectively. We also identified the genes for the complete sulfur oxidation pathway sox which is used to oxidize thiosulfate to sulfate.

Mineral sources and transport pathways for arsenic release in a coastal watershed, USA

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

2008-01-01

Metasedimentary bedrock of coastal Maine contains a diverse suite of As-bearing minerals that act as significant sources of elements found in ground and surface waters in the region. Arsenic sources in the Penobscot Formation include, in order of decreasing As content by weight: löllingite and realgar (c.70%), arsenopyrite, cobaltite, glaucodot, and gersdorffite (in the range of 34–45%), arsenian pyrite (<4%), and pyrrhotite (<0.15%). In the Penobscot Formation, the relative stability of primary As-bearing minerals follows a pattern where the most commonly observed highly altered minerals are pyrrhotite, realgar, niccolite, löllingite > glaucodot, arsenopyrite-cobaltian > arsenopyrite, cobaltite, gersdorffite, fine-grained pyrite, Ni-pyrite > coarse-grained pyrite. Reactions illustrate that oxidation of Fe-As disulphide group and As-sulphide minerals is the primary release process for As. Liberation of As by carbonation of realgar and orpiment in contact with high-pH groundwaters may contribute locally to elevated contents of As in groundwater, especially where As is decoupled from Fe. Released metals are sequestered in secondary minerals by sorption or by incorporation in crystal structures. Secondary minerals acting as intermediate As reservoirs include claudetite (c.75%), orpiment (61%), scorodite (c. 45%), secondary arsenopyrite (c. 46%), goethite (<4490 ppm), natrojarosite (<42 ppm), rosenite, melanterite, ferrihydrite, and Mn-hydroxide coatings. Some soils also contain Fe-Co-Ni-arsenate, Ca-arsenate, and carbonate minerals. Reductive dissolution of Fe-oxide minerals may govern the ultimate release of iron and arsenic – especially As(V) – to groundwater; however, dissolution of claudetite (arsenic trioxide) may directly contribute As(III). Processes thought to explain the release of As from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulphides, and most models based on these generally rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of As-bearing Fe-cobalt-nickel-sulphide minerals, dissolution (by reduction) of As-bearing secondary As and Fe hydroxide and sulphate minerals, carbonation and/or oxidation of As-sulphide minerals, and desorption of As from Fe-hydroxide mineral surfaces are all thought to be involved. All of these processes contribute to the occurrence of As in groundwaters in coastal Maine, as a result of variability in composition and in stability of the As source minerals. Arsenic contents of soils and groundwater thus reflect the predominant influence and integration of a spectrum of primary mineral reservoirs (instead of single or unique mineral reservoirs). Cycling of As through metasedimentary bedrock aquifers may therefore depend on consecutive stages of carbonation, oxidation and reductive dissolution of primary and secondary As host minerals.

Kinetic studies of sulfide mineral oxidation and xanthate adsorption

NASA Astrophysics Data System (ADS)

Mendiratta, Neeraj K.

2000-10-01

Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel studies have been used to elucidate the depressing action of DETA and SO2. It was observed that DETA and SO2 complement each other in maintaining lower pulp potentials and removing polysulfides. DETA also helps in deactivating pyrrhotite. Therefore, the combined use of DETA and SO2 leads to the inhibition of both the collectorless flotation and the adsorption of xanthate. The adsorption of xanthate on sulfide minerals is a mixed-potential mechanism, i.e., the anodic oxidation of xanthate requires a cathodic counterpart. Normally, the cathodic reaction is provided by the reduction of oxygen. However, oxygen can be replaced by other oxidants. Ferric ions are normally present in the flotation pulp. Their source could be either iron from the grinding circuit or the ore itself. The galvanic studies were carried out to test the possibility of using ferric ions as oxidants and positive results were obtained. Tafel studies were carried out to measure the activation energies for the adsorption of ethylxanthate on several sulfide minerals. Pyrite, pyrrhotite (pure and nickel activated), chalcocite and covellite were studied in 10 -4 M ethylxanthate solution at pH 6.8 at temperatures in the range of 22--30°C. The Tafel studies showed that xanthate adsorbs as dixanthogen (X2) on pyrite and pyrrhotite, nickel dixanthate (NiX2) on nickel-activated pyrrhotite and cuprous xanthate (CuX) on both chalcocite and covellite. However, the mechanism for xanthate adsorption on each mineral is different. The free energy of reaction estimated from the activation energies are in good agreement with thermodynamically calculated ones.

[Optimization of bioleaching and oxidation of gold-bearing pyrite-arsnopyrite ore concentrate in batch mode].

PubMed

Grigor'eva, N V; Tsaplina, I A; Paniushkina, A E; Kondrat'eva, T F

2014-01-01

Biooxidation of refractory gold-bearing pyrite-arsenopyrite flotation concentrate was optimized and aburidance of predominant groups in the community ofthermophilic acidophilic chemolithotrophic microorganisms at various stages ofbioleaching was determined. The optimal parameters for growth and leaching/oxidation of the mineral components of the concentrate were pSH 1.4, 1.6-1.8; 47.5 degrees C; and the following salt concentrations in the liquid phase (g/L): K2HPO4.3H2O, 0.53; (NH4)2SO4, 1.6 and MgSO4.7H2O, 2.5 (or (NH4)2SO4, 1.23; ammophos, 0.41; KOH, 0.1) with 0.03% yeast extract. The optimal conditions resulted in high growth rate, high levels of iron andarsenic leaching, of Fe2+ and S(2-)/S0 oxidation, and predominance of Acidithiobacillus caldus, Sulfobacillus spp., and Ferroplasma spp. in the community.

A geochemical transport model for redox-controlled movement of mineral fronts in groundwater flow systems: A case of nitrate removal by oxidation of pyrite

USGS Publications Warehouse

Engesgaard, Peter; Kipp, Kenneth L.

1992-01-01

A one-dimensional prototype geochemical transport model was developed in order to handle simultaneous precipitation-dissolution and oxidation-reduction reactions governed by chemical equilibria. Total aqueous component concentrations are the primary dependent variables, and a sequential iterative approach is used for the calculation. The model was verified by analytical and numerical comparisons and is able to simulate sharp mineral fronts. At a site in Denmark, denitrification has been observed by oxidation of pyrite. Simulation of nitrate movement at this site showed a redox front movement rate of 0.58 m yr−1, which agreed with calculations of others. It appears that the sequential iterative approach is the most practical for extension to multidimensional simulation and for handling large numbers of components and reactions. However, slow convergence may limit the size of redox systems that can be handled.

Bacterial sulfur disproportionation constrains timing of neoproterozoic oxygenation

USGS Publications Warehouse

Kunzmann, Marcus; Bui, Thi Hao; Crockford, Peter W.; Halverson, Galen P.; Scott, Clinton T.; Lyons, Timothy W.; Wing, Boswell A.

2017-01-01

Various geochemical records suggest that atmospheric O2 increased in the Ediacaran (635–541 Ma), broadly coincident with the emergence and diversification of large animals and increasing marine ecosystem complexity. Furthermore, geochemical proxies indicate that seawater sulfate levels rose at this time too, which has been hypothesized to reflect increased sulfide oxidation in marine sediments caused by sediment mixing of the newly evolved macrofauna. However, the exact timing of oxygenation is not yet understood, and there are claims for significant oxygenation prior to the Ediacaran. Furthermore, recent evidence suggests that physical mixing of sediments did not become important until the late Silurian. Here we report a multiple sulfur isotope record from a ca. 835–630 Ma succession from Svalbard, further supported by data from Proterozoic strata in Canada, Australia, Russia, and the United States, in order to investigate the timing of oxygenation. We present isotopic evidence for onset of globally significant bacterial sulfur disproportionation and reoxidative sulfur cycling following the 635 Ma Marinoan glaciation. Widespread sulfide oxidation helps to explain the observed first-order increase in seawater sulfate concentration from the earliest Ediacaran to the Precambrian-Cambrian boundary by reducing the amount of sulfur buried as pyrite. Expansion of reoxidative sulfur cycling to a global scale also indicates increasing environmental O2 levels. Thus, our data suggest that increasing atmospheric O2 levels may have played a role in the emergence of the Ediacaran macrofauna and increasing marine ecosystem complexity.

Thermal activated ("thermal") battery technology. Part IIIb. Sulfur and oxide-based cathode materials

NASA Astrophysics Data System (ADS)

Masset, Patrick J.; Guidotti, Ronald A.

This article presents an overview of cathode materials (except the pyrite FeS 2) used or envisaged in thermally activated ("thermal") batteries. The physicochemical properties and electrochemical performance of different cathode families (oxides, sulfides) are reviewed, including discharge mechanisms, when known.

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.

High-resolution (SIMS) versus bulk sulfur isotope patterns of pyrite in Proterozoic microbialites with diverse mat textures

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.

Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst.

PubMed

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.

Habitability: where lo look for life? Habitability Index Earth analogs to study Mars and Europa`s habitability

NASA Astrophysics Data System (ADS)

Gomez, F.; Amils, R.; Gomez-Elvira, J.

2010-12-01

The first astrobiological mission specially designed to detect life on Mars, the Viking missions, thought life unlikely, considering the amount of UV radiation bathing the surface of the planet, the resulting oxidative conditions, and the lack of adequate atmospheric protection. The necessity of the Europa surface exploration comes from the idea of a water ocean existence in its interior. Life needs several requirements for its establishment but, the only sine qua nom elements is the water, taking into account our experience on Earth extreme ecosystems The discovery of extremophiles on Earth widened the window of possibilities for life to develop in the universe, and as a consequence on Mars. The compilation of data produced by the ongoing missions (Mars Global Surveyor, Mars Odyssey, Mars Express and Mars Exploration Rover Opportunity) offers a completely different view: signs of an early wet Mars and rather recent volcanic activity. The discovery of important accumulations of sulfates, and the existence of iron minerals like jarosite, goethite and hematite in rocks of sedimentary origin has allowed specific terrestrial models related with this type of mineralogy to come into focus. Río Tinto (Southwestern Spain, Iberian Pyritic Belt) is an extreme acidic environment, product of the chemolithotrophic activity of microorganisms that thrive in the massive pyrite-rich deposits of the Iberian Pyritic Belt. The high concentrations of ferric iron and sulfates, products of the metabolism of pyrite, generate a collection of minerals, mainly gypsum, jarosite, goethite and hematites, all of which have been detected in different regions of Mars (Fernández-Remolar et al., 2004). But, where to look for life in other planetary bodies? Planet`s or Icy Moon`s surface are adverse for life. Some particular protective environments or elements should house the organic molecules and the first bacterial life forms (Gómez F. et al., 2007). Terrestrial analogues work could help us to afford its comprehension (Gómez F. et al., 2010). We are reporting here some preliminary studies about endolithic niches inside salt deposits used by phototrophs for taking advantage of sheltering particular light wavelengths. These acidic salts deposits located in Río Tinto shelter life forms which are difficult to localize by eye. Molecular ecology techniques are needed for its localization and study. We also are reporting here some results about bacterial survivability in Mars simulation conditions (Gómez F. et al., 2010). Final objective of this work is the development of the Habitability Index. Bibliography Fernández-Remolar, D. et al., Planetary and Space Science 52 (2004) 239 - 248 Gómez, F. et al., Icarus 191 (2007) 352-359. Gómez, F. et al. Icarus (2010), doi:10.1016/j.icarus.2010.05.027 Acknowledgments This study was funded by the project ESP2006-06640 from Spanish Ministry of Education and Science and FEDER funds from European Community.

The Transfiguration continental red-bed Cu-Pb-Zn-Ag deposit, Quebec Appalachians, Canada

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Beaudoin, Georges; Taylor, Bruce E.

2009-04-01

The Transfiguration Cu-Pb-Zn-Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from -7.5‰ to -1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from -19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from -21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe3+/Fe2+ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.

Comparison of methods for the removal of organic carbon and extraction of chromium, iron and manganese from an estuarine sediment standard and sediment from the Calcasieu River estuary, Louisiana, U.S.A.

USGS Publications Warehouse

Simon, N.S.; Hatcher, S.A.; Demas, C.

1992-01-01

U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments. ?? 1992.

Chemical and surface analysis during evolution of arsenopyrite oxidation by Acidithiobacillus thiooxidans in the presence and absence of supplementary arsenic.

PubMed

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.

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposits at Rio Tinto, Spain: Implications for Extant Life on Mars

NASA Technical Reports Server (NTRS)

Stoker, C. R.; Stevens, T.; Amils, R.; Gomez-Elvira, J.; Rodriquez, N.; Gomez, F.; Gonzalez-Toril, E.; Aguilera, A.; Fernandez-Remolar, D.; Dunagan, S.

2005-01-01

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth s largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposit At Rio Tinto, Spain: Implications For Extant Life On Mars

NASA Technical Reports Server (NTRS)

Stoker, C. R.; Stevens, T.; Amils, R.; Gomez-Elvira, J.; Rodriguez, N.; Gomez, F.; Gonzalez-Toril, E.; Aguilera, A.; Fernandez-Remolar, D.; Dunagan, S.

2005-01-01

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth's largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Sedimentary phosphate and associated fossil bacteria in a Paleoproterozoic tidal flat in the 1.85 Ga Michigamme Formation, Michigan, USA

NASA Astrophysics Data System (ADS)

Hiatt, Eric E.; Pufahl, Peir K.; Edwards, Cole T.

2015-04-01

Phosphorus is a nutrient fundamental to life and when it precipitates in modern environments bacteria are intimately involved in its release, concentration, and mineralization. Preserved fossil bacteria in phosphate crusts and grains from the ca. 1850 million-year-old Bijiki Iron Formation Member of the Michigamme Formation, Michigan provide insight into the longevity and nature of this relationship. The Michigamme Formation accumulated near the end of the Earth's initial phosphogenic episode (ca. 2.2 and 1.8 Ga) to produce one of the first granular phosphorites. Phosphatic lithofacies consist of fine- to medium-sand-sized francolite peloids concentrated on bedding surfaces in peritidal facies. Granular beds are up to 2 cm thick and peloids are often partially to completely replaced by dolomite and chert. The grains contain organic matter and pyrite framboids that suggest bacterial breakdown of organic matter and bacterial sulfate reduction. The peritidal nature of phosphorite in the Michigamme Formation is in sharp contrast to Phanerozoic phosphogenic environments in deeper coastal upwelling settings. Peritidal settings were well suited for phosphogenesis under the very low oxygen and low dissolved sulfate levels of the Paleoproterozoic as cyanobacteria produced oxygen in shallow water and evaporation led to increased sulfate concentrations. Such concomitant processes helped establish focused redox interfaces in the sediment that chemosynthetic bacterial communities (sulfur oxidizers, reducers, forms that concentrate P, and possibly iron oxidizers) could exploit. Phosphate released from organic matter by heterotrophic bacteria and Fe-redox pumping was further concentrated by these chemotrophs; a process that forms late Neoproterozoic to Phanerozoic phosphorites but on a much larger scale. This early example of a granular phosphorite demonstrates that, like their Phanerozoic counterparts, Paleoproterozoic phosphorites are the concentrated indirectly biomineralized products of bacterial communities. But unlike younger analogs, which accumulated across subtidal shelves and shelf margins, these ancient deposits formed only in tidal flat settings where phosphogenic redox processes could be established in the sediment. From this early beginning, the zone of phosphogenesis likely migrated into deeper water settings as oxygen and sulfate levels rose, expanding the zone of chemosynthetic bacterial and associated phosphogenesis across the shelf.

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

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.

Iron catalyzed coal liquefaction process

DOEpatents

Garg, Diwakar; Givens, Edwin N.

1983-01-01

A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

Beneficiation of Turkish lignites by thermal treatment and magnetic separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Onal, G.; Renda, D.; Mustafaev, I.

1999-07-01

In this paper, the improvement of Turkish lignites by semi-coking and REMS magnetic separation, in two stages, is discussed. The oxidation and decomposition of pyrite through the thermal treatment result in the formation of iron oxide and pyrrhotite on the surface. In addition to pyrite, part of the organic sulfur is also removed. After thermal treatment of lignites at temperatures ranging from 370 to 650 C, the application of REMS magnetic separator produces a product higher in calorific value and lower in sulfur content. The product can be utilized after briquetting. The volatile gases can also be used after sulfurmore » removal. This process appears to be feasible as a clean coal manufacture from the point of energy efficiency. A short economic analysis is also presented.« less

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation.

PubMed

Claff, Salirian R; Sullivan, Leigh A; Burton, Edward D; Bush, Richard T; Johnston, Scott G

2011-11-01

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite. Copyright © 2011 Elsevier Ltd. All rights reserved.

Geochemical characterisation of pyrite oxidation and environmental problems related to release and transport of metals from a coal washing low-grade waste dump, Shahrood, northeast Iran.

PubMed

Doulati Ardejani, Faramarz; Jodieri Shokri, Behshad; Moradzadeh, Ali; Shafaei, Seyed Ziadin; Kakaei, Reza

2011-12-01

Pyrite oxidation and release of the oxidation products from a low-grade coal waste dump to stream, groundwater and soil was investigated by geochemical and hydrogeochemical techniques at Alborz Sharghi coal washing plant, Shahrood, northeast Iran. Hydrogeochemical analysis of water samples indicates that the metal concentrations in the stream waters were low. Moreover, the pH of the water showed no considerable change. The analysis of the stream water samples shows that except the physical changes, pyrite oxidation process within the coal washing waste dump has not affected the quality of the stream water. Water type was determined to be calcium sulphate. The results of the analysis of groundwater samples indicate that the pH varies from 7.41 to 7.51. The concentrations of the toxic metals were low. The concentration of SO4 is slightly above than its standard concentration in potable water. It seems that the groundwater less affected by the coal washing operation in the study area. Geochemical analysis of the sediment samples shows that Fe concentration decreases gradually downstream the waste dump with pH rising. SO(4) decreases rapidly downstream direction. Copper, Zn and Co concentrations decrease with distance from the waste dump due to a dilution effect by the mixing of uncontaminated sediments. These elements, in particular, Zn are considerably elevated in sediment sample collected at the nearest distance to the waste dump. There is no doubt that such investigations can help to develop an appropriate water remediation plan.

Mode of occurrence of arsenic in feed coal and its derivative fly ash, Black Warrior Basin, Alabama

USGS Publications Warehouse

Zielinski, R.A.; Foster, A.L.; Meeker, G.P.; Brownfield, I.K.

2007-01-01

An arsenic-rich (As = 55 ppm) bituminous feed coal from the Black Warrior Basin, Alabama and its derivative fly ash (As = 230 ppm) were selected for detailed investigation of arsenic residence and chemical forms. Analytical techniques included microbeam analysis, selective extraction, and As K-edge X-ray absorption fine-structure (XAFS) spectroscopy. Most As in the coal is contained in a generation of As-bearing pyrite (FeS2) that formed in response to epigenetic introduction of hydrothermal fluids. XAFS results indicate that approximately 50% of the As in the coal sample occurs as the oxidized As(V) species, possibly the result of incipient oxidation of coal and pyrite prior to our analysis. Combustion of pyrite and host coal produced fly ash in which 95% of As is present as As(V). Selective extraction of the fly ash with a carbonate buffer solution (pH = 10) removed 49% of the As. A different extraction with an HCl-NH2OH mixture, which targets amorphous and poorly crystalline iron oxides, dissolved 79% of the As. XAFS spectroscopy of this highly acidic (pH = 3.0) fly ash indicated that As is associated with some combination of iron oxide, oxyhydroxide, or sulfate. In contrast, a highly alkaline (pH = 12.7) fly ash from Turkey shows most As associated with a phase similar to calcium orthoarsenate (Ca3(AsO4)2). The combined XAFS results indicate that fly ash acidity, which is determined by coal composition and combustion conditions, may serve to predict arsenic speciation in fly ash.

Origin of minerals in joint and cleat systems of the Pottsville Formation, Black Warrior basin, Alabama: Implications for coalbed methane generation and production

USGS Publications Warehouse

Pitman, Janet K.; Pashin, J.C.; Hatch, J.R.; Goldhaber, M.B.

2003-01-01

Coalbed methane is produced from naturally fractured strata in the lower Pennsylvanian Pottsville Formation in the eastern part of the Black Warrior basin, Alabama. Major fracture systems include orthogonal fractures, which consist of systematic joints in siliciclastic strata and face cleats in coal that strike northeast throughout the basin. Calcite and minor amounts of pyrite commonly fill joints in sandstone and shale and, less commonly, cleats in coal. Joint-fill calcite postdates most pyrite and is a weakly ferroan, coarse-crystalline variety that formed during a period of uplift and erosion late in the burial history. Pyrite forms fine to coarse euhedral crystals that line jointwalls or are complexly intergrown with calcite. Stable-isotope data reveal large variations in the carbon isotope composition of joint- and cleat-fill calcite (-10.3 to +24.3 per mil Peedee belemnite [PDB]) but only a relatively narrow range in the oxygen-isotope composition of this calcite (-16.2 to -4.1 per mil PDB). Negative carbon values can be attributed to (super 13) C-depleted CO (sub 2) derived from the oxidation of organic matter, and moderately to highly positive carbon values can be attributed to bacterial methanogenesis. Assuming crystallization temperatures of 20-50 degrees C, most joint- and cleat-fill calcite precipitated from fluids with delta (super 18) O ratios ranging from about -11 to +2 per mil standard mean ocean water (SMOW). Uplift and unroofing since the Mesozoic led to meteoric recharge of Pottsville strata and development of freshwater plumes that were fed by meteoric recharge along the structurally upturned, southeastern margin of the basin. Influxes of fresh water into the basin via faults and coalbeds facilitated late-stage bacterial methanogenesis, which accounts for the high gas content in coal and the carbonate cementation of joints and cleats. Diagenetic and epigenetic minerals can affect the transmissivity and storage capacity of joints and cleats, and they appear to contribute significantly to interwell heterogeneity in the Pottsville Formation. In highly productive coalbed methane fields, joint- and cleat-fill calcite have strongly positive delta (super 13) C values, whereas calcite fill has lower delta (super 13) C values in fields that are shut in or abandoned. Petrographic analysis and stable-isotope geochemistry of joint- and cleat-fill cements provide insight into coalbed methane reservoir quality and the nature and extent of reservoir compartmentalization, which are important factors governing methane production.

Specification and prediction of nickel mobilization using artificial intelligence methods

NASA Astrophysics Data System (ADS)

Gholami, Raoof; Ziaii, Mansour; Ardejani, Faramarz Doulati; Maleki, Shahoo

2011-12-01

Groundwater and soil pollution from pyrite oxidation, acid mine drainage generation, and release and transport of toxic metals are common environmental problems associated with the mining industry. Nickel is one toxic metal considered to be a key pollutant in some mining setting; to date, its formation mechanism has not yet been fully evaluated. The goals of this study are 1) to describe the process of nickel mobilization in waste dumps by introducing a novel conceptual model, and 2) to predict nickel concentration using two algorithms, namely the support vector machine (SVM) and the general regression neural network (GRNN). The results obtained from this study have shown that considerable amount of nickel concentration can be arrived into the water flow system during the oxidation of pyrite and subsequent Acid Drainage (AMD) generation. It was concluded that pyrite, water, and oxygen are the most important factors for nickel pollution generation while pH condition, SO4, HCO3, TDS, EC, Mg, Fe, Zn, and Cu are measured quantities playing significant role in nickel mobilization. SVM and GRNN have predicted nickel concentration with a high degree of accuracy. Hence, SVM and GRNN can be considered as appropriate tools for environmental risk assessment.

Geology and recognition criteria for sandstone uranium deposits in mixed fluvial-shallow marine sedimentary sequences, South Texas. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, S.S.; Smith, R.B.

1981-01-01

Uranium deposits in the South Texas Uranium Region are classical roll-type deposits that formed at the margin of tongues of altered sandstone by the encroachment of oxidizing, uraniferous solutions into reduced aquifers containing pyrite and, in a few cases, carbonaceous plant material. Many of the uranium deposits in South Texas are dissimilar from the roll fronts of the Wyoming basins. The host sands for many of the deposits contain essentially no carbonaceous plant material, only abundant disseminated pyrite. Many of the deposits do not occur at the margin of altered (ferric oxide-bearing) sandstone tongues but rather occur entirely within reduced,more » pyurite-bearing sandstone. The abundance of pyrite within the sands probably reflects the introduction of H/sub 2/S up along faults from hydrocarbon accumulations at depth. Such introductions before ore formation prepared the sands for roll-front development, whereas post-ore introductions produced re-reduction of portions of the altered tongue, leaving the deposit suspended in reduced sandstone. Evidence from three deposits suggests that ore formation was not accompanied by the introduction of significant amounts of H/sub 2/S.« less

Reconciling "Whiffs" of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments

NASA Astrophysics Data System (ADS)

Johnson, A.; Reinhard, C. T.; Romaniello, S. J.; Greaney, A. T.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2016-12-01

The Archean-Proterozoic transition is marked by the first appreciable accumulation of O2 in Earth's oceans and atmosphere at 2.4 billion years ago (Ga). However, this Great Oxidation Event (GOE) is not the first evidence for O2 in Earth's surface environment. Paleoredox proxies preserved in ancient marine shales (Mo, Cr, Re, U) suggest transient episodes of oxidative weathering before the GOE, perhaps as early as 3.0 Ga. One marine shale in particular, the 2.5 Ga Mount McRae Shale of Western Australia, contains a euxinic interval with Mo enrichments up to 50 ppm. This enrichment is classically interpreted as the result of oxidative weathering of sulfides on the continental surface. However, prior weathering models based on experiments suggested that sulfides require large amounts of O2 [>10-4 present atmospheric level (PAL) pO2] to produce this weathering signature, in conflict with estimates of Archean pO2 from non-mass-dependent (NMD) sulfur isotope anomalies (<10-5 PAL pO2). To reconcile these datasets, we conducted aqueous oxidation experiments of pyrite and molybdenite from 3 - 700 nM O2 (equivalent at equilibrium to 10-5 - 10-3 PAL) to measure oxidation kinetics as a function of the concentration of dissolved O2. We measured rates by injecting oxygenated water at a steady flow rate and monitoring dissolved O2 concentrations with LUMOS sensors. Our data extend the O2 range explored in pyrite oxidation experiments by three orders of magnitude and provide the first rates for molybdenite oxidation at O2 concentrations potentially analogous to those characteristic of the Archean atmosphere. Our results show that pyrite and molybdenite oxidize significantly more rapidly at lower O2 levels than previously thought. As a result, our revised weathering model demonstrates that the Mo enrichments observed in late Archean marine shales are potentially attainable at extremely low atmospheric pO2 values (e.g., <10-5 PAL), reconciling large sedimentary Mo enrichments with co-occurring NMD sulfur isotope anomalies.

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.

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.

Expanding lipid proxies to the next dimension: Developing methods for determination of oxygen isotope ratios in plant waxes

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.

Nanominerals and nanoparticles in feed coal and bottom ash: implications for human health effects.

PubMed

Silva, Luis F O; da Boit, Kátia M

2011-03-01

Environmental and human health risk assessments of nanoparticle effects from coal and bottom ash require thorough characterisation of nanoparticles and their aggregates. In this manuscript, we expand the study of human exposure to nanosized particles from coal combustion sources (typically <100 nm in size), characterising the complex micromineralogy of these airborne combustion-derived nanomaterials. Our study focuses on bottom ash generated in the Santa Catarina power station (Brazil) which uses coal enriched in ashes, many potential elements (e.g. Cr and Ni) and pyrite. Transmission electron microscope data reveal nanoscale C deposits juxtaposed with and overgrown by slightly larger aluminosilicate (Al-Si) glassy spheres, oxides, silicates, carbonated, phosphates and sulphates. Iron oxides (mainly hematite and magnetite) are the main bottom ash products of the oxidation of pyrite, sometimes via intermediate pyrrhotite formation. The presence of iron oxide nanocrystals mixed with silicate glass particles emphasises the complexity of coal and bottom ash micromineralogy. Given the potentially bioreactive nature of such transition metal-bearing materials, there is likely to be an increased health risk associated with their inhalation.

Distribution of trace elements in selected pulverized coals as a function of particle size and density

USGS Publications Warehouse

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.

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

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.

Lower Carboniferous Siderites: A Product of Bottom Seeps and Bacterial Metanogenesis (Subpolar Urals)

NASA Astrophysics Data System (ADS)

Antoshkina, A. I.; Ryabinkina, N. N.

2018-02-01

Complex modern micro- and spectroscopic methods for study of siderite concretions in the Lower Carboniferous terrigenous strata on the Kozhym River (Subpolar Urals) have shown that its formation was caused by destruction of clay minerals due to the activity of bacterial communities. The abundance of these bacteria was caused by gas-fluid seeps and bacterial methanogenesis processes in bottom deposits. In basins with normal marine fauna, this led to local desalination, hydrogen sulfide contamination, mass collapse of primary organisms, and the development of element-specific bacteria. The occurrence of these bacteria caused the formation of specific authigenic mineralization in the concretion of sideritic bacteriolites: the framboidal pyrite, sphalerite, galenite, barite, sulfoselenides, and tellurides.

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.

Metal dispersion and mobility in soils from the Lik Zn-Pb-Ag massive sulphide deposit, NW Alaska: Environmental and exploration implications

USGS Publications Warehouse

Kelley, K.D.; Kelley, D.L.

2003-01-01

The Lik deposit in northern Alaska is a largely unexposed shale-hosted Zn-Pb-Ag massive sulphide deposit that is underlain by continuous permafrost. Residual soils overlying the mineralized zone have element enrichments that are two to six times greater than baseline values. The most prominent elements are Ag, Mo, P, Se, Sr, V by total 4-acid digestion and Tl by a weak partial digestion (Enzyme Leach or EL) because they show multi-point anomalies that extend across the entire mineralized zone, concentration ranges are 0.5-2.6 ppm Ag, 4-26 ppm Mo, 0.1-0.3% P, 3-22 ppm Se, 90-230 ppm Sr, 170-406 ppm V, and 1.6-30 ppb Tl. Lead, Sb, and Hg are also anomalous (up to 178 ppm, 30 ppm, and 1.9 ppm, respectively), but all are characterized by single point anomalies directly over the mineralized zone, with only slightly elevated concentrations over the lower mineralized section. Zinc (total) has a consistent baseline response of 200 ppm, but it is not elevated in soils overlying the mineralized zone. However, Zn by EL shows a distinct single-point anomaly over the ore zone that suggests it was highly mobile and partly adsorbed on oxides or other secondary phases during weathering. In situ analyses (by laser ablation ICP-MS) of pyrite and sphalerite from drill core suggest that sphalerite is the primary residence for Ag, Cd, and Hg in addition to Zn, and pyrite contains As, Fe, Sb, and Tl. The level and degree of oxidation, and the proportion of reacting pyrite and carbonate minerals are two factors that affected the mobility and transport of metals. In oxidizing conditions, Zn is highly mobile relative to Hg and Ag, perhaps explaining the decoupling of Zn from the other sphalerite-hosted elements in the soils. Soils are acidic (to 3.9 pH) directly over the deposit due to the presence of acid-producing pyrite, but acid-neutralizing carbonate away from the mineralized zone yield soils that are near neutral. The soils therefore formed in a complex system involving oxidation and weathering (mechanical and chemical) of sulphide minerals, dissolution of carbonate minerals, and precipitation of iron and manganese oxide minerals.

Geochemistry of pyrite from diamictites of the Hamersley Basin, Western Australia with implications for the GOE and Paleoproterozoic ice ages.

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.

Use of variations in unit cell length, reflectance and hardness for determining the origin of Fe disulphides in sedimentary rocks

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.

The Russell gold deposit, Carolina Slate Belt, North Carolina

USGS Publications Warehouse

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.

Geochemistry and microbial community composition across a range of acid mine drainage impact and implications for the Neoarchean-Paleoproterozoic transition

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.

Classification scheme for acid rock drainage detection - the Hamersley Basin, Western Australia

NASA Astrophysics Data System (ADS)

Skrzypek, Grzegorz; Dogramaci, Shawan; McLean, Laura

2017-04-01

In arid environment where precipitation and surface water are very limited, groundwater is the most important freshwater resource. For this reasons it is intensively exploited and needs to be managed wisely and protected from pollutants. Acid rock drainage often constitutes a serious risk to groundwater quality, particularly in catchments that are subject to mining, large scale groundwater injection or abstraction. However, assessment of the potential acid rock drainage risk can be challenging, especially in carbonate rich environment, where the decreasing pH that usually accompanies pyrite oxidation, can be masked by the high pH-neutralisation capacity of carbonate minerals. In this study, we analysed 73 surface and groundwater samples from different water bodies and aquifers located in the Hamersley Basin, Western Australia. Although the majority of samples had a neutral pH, there was a large spatial variability in the dissolved sulphate concentrations that ranged from 1 mg/L to 15,000 mg/L. Waters with high dissolved sulphate concentration were found in areas with a high percentage of sulphide minerals (e.g. pyrite) located within the aquifer matrix and were characterised by low δ34SSO4 values (+1.2‰ to +4.6) consistent with signatures of 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. Based on the results from this study, a classification scheme has been developed for identification of waters impacted by acid rock drainage that also encompasses numerous concomitant geochemical processes that often occur in aqueous systems. The classification uses five proxies: SO4, SO4/Cl, SI of calcite, δ34SSO4 and δ18OSO4 to improve assessment of the contribution that oxidation of sulphide minerals has to overall sulphate ion concentrations, regardless of acidity levels of the aqueous system. This classification scheme enables a more direct monitoring regime for early detection of acid rock drainage processes and better groundwater quality management. References Dogramaci S., McLean L., Skrzypek G., 2017. Hydrochemical and stable isotope indicators of pyrite oxidation in carbonate-rich environment; the Hamersley Basin, Western Australia. Journal of Hydrology 545, 288-298.

Sulfur cycling in an iron oxide-dominated, dynamic marine depositional system: The Argentine continental margin

NASA Astrophysics Data System (ADS)

Riedinger, Natascha; Brunner, Benjamin; Krastel, Sebastian; Arnold, Gail L.; Wehrmann, Laura M.; Formolo, Michael J.; Beck, Antje; Bates, Steven M.; Henkel, Susann; Kasten, Sabine; Lyons, Timothy W.

2017-05-01

The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Sulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles.

PubMed

Dold, Bernhard; Spangenberg, Jorge E

2005-08-01

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments--Piuquenes, Cauquenes, and Salvador No. 1--formed from the exploitation of the Rio Blanco/La Andina, El Teniente, and El Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(III) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes, the delta34S(SO4)values ranged from +0.5 per thousand to +2.0 per thousand and from -0.4 per thousand to +1.4 per thousand Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (delta34S(pyrite) = -1.1 per thousand and -0.9 per thousand). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8 per thousand to +0.3 per thousand and from +2.2 per thousand to +3.9 per thousand, respectively. At Cauquenes the 34S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (approximately +10.9 per thousand). At El Salvador No. 1, the delta34S(SO4) average value is -0.9 per thousand, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a delta34S approximately -0.7 per thousand as the most probable sulfate source. The gradual decrease of delta18O(SO4) values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5 per thousand to -8.6 per thousand Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3 per thousand to -3.5 per thousand) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different delta18O(SO4) values between the tailings impoundments studied here reflect the local climates.

Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit, West Qinling orogen, central China: An in situ SIMS study with implications for the source of sulfur

USGS Publications Warehouse

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.

Concentration-Discharge Relationships, Nested Reaction Fronts, and the Balance of Oxidative and Acid-Base Weathering Fluxes in an Alpine Catchment, East River, Colorado

NASA Astrophysics Data System (ADS)

Winnick, M.; Carroll, R. W. H.; Williams, K. H.; Maxwell, R. M.; Maher, K.

2016-12-01

Although important for solute production and transport, the varied interactions between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the headwaters of the East River, CO, a high-elevation shale-dominated catchment system in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with well-defined clockwise hysteresis, indicating the mobilization and depletion of DOC in the upper soil horizons and highlighting the importance of shallow flowpaths through the snowmelt period. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both carbonic acid and sulfuric acid derived from oxidation of pyrite in the shale bedrock. Sulfuric acid weathering in the deep subsurface dominates during base flow conditions when waters have infiltrated below the hypothesized pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during the snowmelt period as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This increase in CO2(aq) at the expense of HCO3- results in outgassing of CO2 when waters equilibrate to surface conditions, and reduces the export of carbon and alkalinity from the East River by roughly 33% annually. Future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering therefore have the capacity to substantially alter the cycling of carbon in the East River catchment. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.

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

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.

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

PubMed

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.

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

NASA Astrophysics Data System (ADS)

Lengke, Maggy F.; Tempel, Regina N.

2005-01-01

Arsenic sulfide (AsS (am), As 2S 3 (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH˜2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As 2S 3 (am), orpiment, AsS (am), and realgar, respectively. Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ˜1.14 to 13 times and that pH values decrease by ˜0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase. Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As 2S 3 (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH˜8 and temperature 25 to 40°C, and pyrite activation energies are ˜52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As 2S 3 (am). Low activation energies of As 2S 3 (am) indicate that diffusion may be rate controlling. Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO 3) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.

Gold deposition by sulfidation of ferrous Fe in the lacustrine sediments of the Pueblo Viejo district (Dominican Republic): The effect of Fe-C-S diagenesis on later hydrothermal mineralization in a Maar-Diatreme complex

USGS Publications Warehouse

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.

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.

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

USGS Publications Warehouse

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Preliminary Mineralogic and Stable Isotope Studies of Altered Summit and Flank Rocks and Osceola Mudflow Deposits on Mount Rainier, Washington

USGS Publications Warehouse

Rye, Robert O.; Breit, George N.; Zimbelman, David R.

2003-01-01

About 5600 years ago part of Mount Rainier?s edifice collapsed with the resultant Osceola Mudflow traveling more than 120 km and covering an area of at least 505 km2. Mineralogic and stable isotope studies were conducted on altered rocks from outcrops near the summit and east flank of the volcano and samples of clasts and matrix from the Osceola Mudflow. Results of these analyses are used to constrain processes responsible for pre-collapse alteration and provide insight into the role of alteration in edifice instability prior to the Osceola collapse event. Jarosite, pyrite, alunite, and kaolinite occur in hydrothermally altered rock exposed in summit scarps formed by edifice collapse events and in altered rock within the east-west structural zone (EWSZ) of the volcano?s east flank. Deposits of the Osceola Mudflow contain clasts of variably altered and unaltered andesite within a clay-rich matrix. Minerals detected in samples from the edifice are also present in many of the clasts. The matrix includes abundant smectite, kaolinite and variably abundant jarosite. Hydrothermal fluid compositions calculated from hydrogen and oxygen isotope data of alunite, and smectite on Mount Rainier reflect mixing of magmatic and meteoric waters. The range in the dD values of modern meteoric water on the volcano (-85 to 155?) reflect the influence of elevation on the dD of precipitation. The d34S and d18OSO4 values of alunite, gypsum and jarosite are distinct but together range from 1.7 to 17.6? and -12.3 to 15.0?, respectively; both parameters increase from jarosite to gypsum to alunite. The variations in sulfur isotope composition are attributed to the varying contributions of disproportionation of magmatic SO2, the supergene oxidation of hydrothermal pyrite and possible oxidation of H2S to the parent aqueous sulfate. The 18OSO4 values of jarosite are the lowest recorded for the mineral, consistent with a supergene origin. The mineralogy and isotope composition of alteration minerals define two and possibly three environments of alteration. At deeper levels magmatic vapor, H2S, SO2 and other gases from venting magmas migrated upward and condensed into the meteoric water. Disproportionation of SO2 into aqueous sulfate and H2S resulted in acid-sulfate (alunite + kaolinite + pyrite) and related argillic and propylitic alteration envelopes in a magmatic hydrothermal environment. At shallow levels H2S reacted with andesite to form pyrite that is associated with smectite along fractures on both the flanks and upper edifice. It is not clear to what extent H2S was oxidized by atmospheric O2 to form aqueous sulfate in a steam-heated environment. Near the ground surface, pyrite is oxidized by atmospheric oxygen resulting in soluble iron-and aluminum-hydroxysulfates. These supergene hydroxysulfates, which may also form around fumaroles from the oxidation of H2S, are subject to continuous solution and redeposition.

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.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

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.

Modeling low-temperature geochemical processes: Chapter 2

USGS Publications Warehouse

Nordstrom, D. Kirk; Campbell, Kate M.

2014-01-01

This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.

Deep aquifer as driver for mineral authigenesis in Gulf of Alaska sediments (IODP Expedition 341, Site U1417)

NASA Astrophysics Data System (ADS)

Zindorf, Mark; März, Christian; Wagner, Thomas; Strauss, Harald; Gulick, Sean P. S.; Jaeger, John M.; LeVay, Leah J.

2016-04-01

Bacterial sulphate reduction plays a key role in authigenic mineral formation in marine sediments. Usually, decomposition of organic matter follows a sequence of microbial metabolic pathways, where microbial sulphate reduction leads to sulphate depletion deeper in the sediment. When sulphate is consumed completely from the pore waters, methanogenesis commences. The contact of sulphate- and methane-containing pore waters is a well-defined biogeochemical boundary (the sulphate-methane transition zone, SMTZ). Here authigenic pyrite, barite and carbonates form. Pyrite formation is directly driven by bacterial sulphate reduction since pyrite precipitates from produced hydrogen sulphide. Barite and carbonate formation are secondary effects resulting from changes of the chemical milieu due to microbial activity. However, this mineral authigenesis is ultimately linked to abiotic processes that determine the living conditions for microorganisms. At IODP Site U1417 in the Gulf of Alaska, a remarkable diagenetic pattern has been observed: Between sulphate depletion and methane enrichment, a ~250 m wide gap exists. Consequently, no SMTZ can be found under present conditions, but enrichments of pyrite indicate that such zones have existed in the past. Solid layers consisting of authigenic carbonate-cemented sand were partly recovered right above the methane production zone, likely preventing continued upward methane diffusion. At the bottom of the sediment succession, the lower boundary of the methanogenic zone is constrained by sulphate-rich pore waters that appear to originate from a deeper source. Here, a well-established SMTZ exists, but in reversed order (sulphate diffusing up, methane diffusing down). Sulphur isotopes of pyrite reveal that sulphate reduction here does not occur under closed system conditions. This indicates that a deep aquifer is actively recharging the deep sulphate pool. Similar deep SMTZs have been found at other sites, yet mostly in geologically active environments such as ridge flanks or above subduction zones. Therefore Site U1417, in a relatively inactive intraplate environment, represents a so far under-sampled geochemical setting. Calculated accumulation times for authigenic minerals in the deep SMTZ are on the same order of magnitude as the onset of subduction-related bending of the Pacific Plate, suggesting that both processes are linked. Plate bending could create fractures in the overlying sediments allowing seawater to penetrate and recharge a deep aquifer. Our study provides insights into a newly discovered geological process suitable for delivering sulphate-rich water deep into the sediments and installing diagenetically active environments where microbial activity would otherwise be very limited.

Mixing of sulfur between pyritic and organic phases during coal conversion processes: Annual final report, March 1, 1986-February 28, 1987

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

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

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

USGS Publications Warehouse

Asta, Maria P.; Nordstrom, D. Kirk; McCleskey, R. Blaine

2012-01-01

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H2SO4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl− concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.

Composition and risk assessment of roasted pyrite ash from fertiliser production.

PubMed

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.

Separate zones of sulfate and sulfide release from subducted mafic oceanic crust

NASA Astrophysics Data System (ADS)

Tomkins, Andrew G.; Evans, Katy A.

2015-10-01

Liberation of fluids during subduction of oceanic crust is thought to transfer sulfur into the overlying sub-arc mantle. However, despite the importance of sulfur cycling through magmatic arcs to climate change, magma oxidation and ore formation, there has been little investigation of the metamorphic reactions responsible for sulfur release from subducting slabs. Here, we investigate the relative stability of anhydrite (CaSO4) and pyrite (FeS2) in subducted basaltic oceanic crust, the largest contributor to the subducted sulfur budget, to place constraints on the processes controlling sulfur release. Our analysis of anhydrite stability at high pressures suggests that this mineral should dominantly dissolve into metamorphic fluids released across the transition from blueschist to eclogite facies (∼450-650 °C), disappearing at lower temperatures on colder geothermal trajectories. In contrast, we suggest that sulfur release via conversion of pyrite to pyrrhotite occurs at temperatures above 750 °C. This higher temperature stability is indicated by the preservation of pyrite-bornite inclusions in coesite-bearing eclogites from the Sulu Belt in China, which reached temperatures of at least 750 °C. Thus, sulfur may be released from subducting slabs in two separate pulses; (1) varying proportions of SO2, HSO4- and H2S are released via anhydrite breakdown at the blueschist-eclogite transition, promoting oxidation of remaining silicates in some domains, and (2) H2S is released via pyrite breakdown well into the eclogite facies, which may in some circumstances coincide with slab melting or supercritical liquid generation driven by influx of serpentinite-derived fluids. These results imply that the metallogenic potential in the sub-arc mantle above the subducting slab varies as a function of subduction depth, having the greatest potential above the blueschist-eclogite transition given the association between oxidised magmas and porphyry Cu(-Au-Mo) deposits. We speculate that this zoned sulfur liberation might be one of the factors that lead to the apparently redox-influenced zoned distribution of ore deposit types in the Andean arc. Furthermore, given the lack of sulfate-associated sea floor oxidation prior to the second great oxidation event, the pattern of sulfur transfer from the slab to the sub-arc mantle likely changed over time, becoming shallower and more oxidised from the Neoproterozoic onwards.

Early-diagenetic processes in marine mangrove sediments from Guadeloupe, French West Indies

NASA Astrophysics Data System (ADS)

Crémière, Antoine; Sebilo, Mathieu; Strauss, Harald; Gros, Olivier; Laverman, Anniet M.

2014-05-01

Sediment and pore-water geochemistry were investigated in two short sediment cores from the Manche-à-eau lagoon (Guadeloupe, French Caribbean island) surrounded by mangroves trees. These sediments present high total organic carbon content, ranging between 10 to 18 % wt, mainly originating from mangrove litter fall. Oxygen is depleted in the first few millimetres of the sediment indicating active organic carbon degradation. Seawater sulphate is entirely consumed within the first 20 cm of the sediments and total organic carbon content decreases with depth pointing out that early-diagenetic degradation of organic matter occurs with sulphate reduction. Sulphide produced as the results of sulphate reduction partly reacts with detrital iron-bearing minerals and precipitates as pyrite which is consistent with high amounts of sulphur in the sediments (4-5 % wt). The sulphur isotopic composition (δ34S) of both dissolved sulphate and sulphide in pore-water increases with depth displaying a large apparent isotopic fractionation (Δ34S) between both species of 65-80o as a result of bacterial sulphate reduction. Scanning electron microscopy investigation reveals that a part of the carbonate alkalinity produced either by organic matter oxidation or anaerobic methane oxidation leads to authigenic carbonates precipitation. These results provide straightforward evidence that carbon and sulphur biogeochemical cycles are intimately governed by sedimentary microbial activity.

Supergene oxidation of epithermal gold-silver mineralization in the Deseado massif, Patagonia, Argentina: response to subduction of the Chile Ridge

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.

Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese

PubMed Central

Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm

1993-01-01

A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835

Ore microscopy of the Paoli silver-copper deposit, Oklahoma

USGS Publications Warehouse

Thomas, C.A.; Hagni, R.D.; Berendsen, P.

1991-01-01

The Paoli silver-copper deposit is located in south-central Oklahoma, 56 km south-southeast from Norman, Oklahoma. It was mined for high-grade silver-copper near the beginning of this century, and intensive exploratory drilling during the early 1970's delineated unmined portions of the deposit. A collaborative study between the U.S.G.S., the Kansas Geological Survey, and the University of Missouri-Rolla was undertaken to provide new information on the character of red bed copper deposits of the Midcontinent region. The Paoli deposit has been interpreted to occur as a roll-front type of deposit. The silver and copper mineralization occurs within paleochannels in the Permian Wellington Formation. The silver-copper interfaces appear to be controlled by oxidation-reduction interfaces that are marked by grey to red color changes in the host sandstone. Ore microscopic examinations of polished thin sections show that unoxidized ore consists of chalcocite, digenite, chalcopyrite, covellite and pyrite; and oxidized ores are characterized by covellite, bornite, hematite and goethite. In sandstone-hosted ores, chalcocite and digenite replace dolomite and border clastic quartz grains. In siltstone-hosted ores, the copper sulfide grains have varied shapes; most are irregular in shape and 5-25 ??m across, others have euhedral shapes suggestive of pyrite crystal replacements, and some are crudely spherical and are 120-200 ??m across. Chalcopyrite is the predominant copper sulfide at depth. Covellite and malachite replace chalcocite and digenite near the surface. Silver only occurs as native silver; most as irregularly shaped grains 40-80 ??m across, but some as cruciform crystals that are up to 3.5 mm across. The native silver has been deposited after copper sulfides, and locally replaces chalcocite. Surficial nodules of pyrite, malachite and hematite locally are present in outcrops at the oxidation-reduction fronts. Polished sections of the nodules show that malachite forms a cement around quartz sand grains, and brecciated pyrite grains are surrounded by rims of hematite and goethite. Dolomite is the principal sandstone cement. Cathodoluminescence microscopic study of the mineral has shown that it was deposited during seven periods before the copper sulfide mineralization. ?? 1991.

Thermodynamic Cconstraints on Coupled Carbonate-Pyrite Weathering Dynamics and Carbon Fluxes

NASA Astrophysics Data System (ADS)

Winnick, M.; Maher, K.

2017-12-01

Chemical weathering within the critical zone regulates global biogeochemical cycles, atmospheric composition, and the supply of key nutrients to terrestrial and aquatic ecosystems. Recent studies suggest that thermodynamic limits on solute production act as a first-order control on global chemical weathering rates; however, few studies have addressed the factors that set these thermodynamic limits in natural systems. In this presentation, we investigate the effects of soil CO2 concentrations and pyrite oxidation rates on carbonate dissolution and associated carbon fluxes in the East River watershed in Colorado, using concentration-discharge relationships and thermodynamic constraints. Within the shallow subsurface, soil respiration rates and moisture content determine the extent of carbonic acid-promoted carbonate dissolution through their modulation of soil pCO2 and the balance of open- v. closed-system weathering processes. At greater depths, pyrite oxidation generates sulfuric acid, which alters the approach to equilibrium of infiltrating waters. Through comparisons of concentration-discharge data and reactive transport model simulations, we explore the conditions that determine whether sulfuric acid reacts to dissolve additional carbonate mineral or instead reacts with alkalinity already in solution - the balance of which determines watershed carbon flux budgets. Our study highlights the importance of interactions between the chemical structure of the critical zone and the hydrologic regulation of flowpaths in determining concentration-discharge relationships and overall carbon fluxes.

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

NASA Astrophysics Data System (ADS)

Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

2017-08-01

Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

NASA Astrophysics Data System (ADS)

Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

2012-04-01

Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7 ± 0.3‰) when sulfate concentrations rose above 0.5 mM and sulfide concentrations had became negligible.

Geochemical and biological characterisation of supergene efflorescences in pollymetallic mining wastes from Portman Bay (SE, Spain)

NASA Astrophysics Data System (ADS)

García-Lorenzo, Maria Luz; Herrero, Maria Jose; Martinez-Sanchez, Maria Jose; Molina-Ruiz, Jose; Hernandez, Carmen; Bech, Jaume; Perez-Sirvent, Carmen

2017-04-01

In freshly deposited sulphidic mine tailings, the pH is neutral or slightly alkaline. Due to pyrite oxidation, the pH decreases to values lower than 3 at which acidophilic iron- and sulphur-oxidizing prokaryotes prevail and accelerate the oxidation processes. Portman Bay is heavily polluted as a result of historical mining and processing activities, during which time great amounts of wastes were produced, characterised by a high potentially toxic elements (PTE) content, acidic pH and minerals resulting from supergene alteration. Three soil samples were collected from the most recent exploitation stage, stored in containers for a year and moistened simulating rainfall events. The percolates obtained were collected and naturally evaporated, obtaining three efflorescence samples. The existence of bacterial activity was evaluated by scanning electron microscopy (SEM). C15 sample is characterised by copiapite small crystals generating an homogeneous, porous mass. Inside the mass of copiapite crystals, both pyrite and gypsum were also found. In this sample, a laminae of material fills the pore space. The high carbon content shown in the spectrum of this material permits to characterise it as a biofilm. In the cross section sample of C15, a noticeable lamination of copiapite crystals has been observed, probably originated by dissolution processes. A clear limit between the lamination zone and the upper zone of the efflorescence was noticed, and here arborescent forms are developed. C17 and C18 also presented copiapite crystals, but, unlike C15, they do not present lamination and are characterized by an irregular shape and massive fabric. In C17, small crystals growing in the surface of this material were observed, generating small crusts. According to the spectrum analysis, these crusts are formed by alunogen. In C18, crystals of acicular morphology are present, and appear grouped at certain points. Therefore, out of the three natural efflorescences, biotic activity was only found in C15. This efflorescence differs significantly in morphology and fabric from samples C17 and C18. Besides the morphology, the PTEs content is also different, suggesting that chemical properties of this soil favoured the organic activity. An important factor could be related to a high iron content, since, as demonstrated in similar materials, iron performs a fundamental factor for bioinducted nucleation.

Bibliography for acid-rock drainage and selected acid-mine drainage issues related to acid-rock drainage from transportation activities

USGS Publications Warehouse

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.

The Ancient Wood of the Acqualadrone Rostrum: A Materials History Through GC-MS and Sulfur X-ray Absorption Spectroscopy

PubMed Central

Frank, Patrick; Caruso, Francesco; Caponetti, Eugenio

2012-01-01

In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge x-ray absorption spectroscopy (XAS) and GC-MS. GC-MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic dimethylsulfonio-propionate. High valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality. PMID:22545724

Exploration for uranium deposits in the Spring Creek Mesa area, Montrose County, Colorado

USGS Publications Warehouse

Roach, Carl Houston

1954-01-01

4. The “ore-bearing sandstone” in the vicinity of relatively unoxidized ore deposits commonly contains sparse to abundant disseminated pyrite. In the vicinity of oxidized deposits it commonly contains abundant limonite spots and widespread limonite staining.

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".

Early diagenetic processes of saline meromictic Lake Kai-ike, southwest Japan: III. Sulfur speciation and isotopes

NASA Astrophysics Data System (ADS)

Sakai, N.; Yamaguchi, K. E.; Oguri, K.

2014-12-01

Lake Kai-ike is a saline meromictic lake located along the coast of Kami-Koshiki Island. The lake is isolated from ocean by a gravel bar, through which seawater infiltrates by tidal pumping. The lake is permanently redox (density)-stratified with a mid-depth development of photic zone anoxia and a dense community of photosynthetic bacteria pinkish "bacterial plate". The early diagenesis of sulfur in sediments overlain by an anoxic water body was investigated using a sediment core (KAI4) from the lake. We determined abundance of various S-bearing species (i.e., Cr-reducible sulfide (= pyrite S: Spy), acid-volatile sulfide (AVS), sulfate sulfur (SSO4), elemental sulfur (S0), and organic sulfur) by an improved sequential extraction method. Here we focus on drastic and rapid changes on sulfur biogeochemistry found in the uppermost 5cm layer. With increasing depth, abundance of Spy increased but that of SSO4 and δ34S value of Spy (δ34Spy) decreased. These results suggest progressive formation of bacteriogenic pyrite. The δ34S values of SSO4 (δ34SSO4) ranged from 25.1 ‰ (at sediment surface) to 3.8 ‰ in the uppermost 5 cm layer. This δ34SSO4 decrease in the top 5 cm sediment suggests that SSO4 in the surface sediment inherits SO42- with elevated δ34S values (higher than typical seawater δ34S value of 21‰) in the water column, which is due to extensive bacterial sulfate reduction with preferential removal of low-δ34S sulfur as sulfide. In the lower part of the uppermost 5 cm layer, SO42- formed by oxidation of S0, AVS, and/or Spy with low-δ34S values by SO42--bearing seawater introduced by infiltration through the gravel bar. Increasing δ34Spy values with increasing depth suggest near complete consumption of SO42- by active bacterial sulfate reduction, and this process could be explained by Rayleigh distillation model. Early diagenesis of sulfur does occur in whole section of 25cm-long KAI4 core that accumulated for the last ~60 years (Yamaguchi et al., 2010; Palaeo3). Geochemical characteristics of sulfur in the uppermost part of Lake Kai-ike sediment were significantly modified during early diagenesis. Such diagenetic modification for sulfur isotopes should be fully taken into account to better reconstruct past anoxic environment such as Cretaceous OAEs and Archean oceans.

Integrated experimental and modeling assessment of potential effects of gas leakages on groundwater composition

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.

Terminal oxidase diversity and function in "Metallosphaera yellowstonensis": gene expression and protein modeling suggest mechanisms of Fe(II) oxidation in the sulfolobales.

PubMed

Kozubal, M A; Dlakic, M; Macur, R E; Inskeep, W P

2011-03-01

"Metallosphaera yellowstonensis" is a thermoacidophilic archaeon isolated from Yellowstone National Park that is capable of autotrophic growth using Fe(II), elemental S, or pyrite as electron donors. Analysis of the draft genome sequence from M. yellowstonensis strain MK1 revealed seven different copies of heme copper oxidases (subunit I) in a total of five different terminal oxidase complexes, including doxBCEF, foxABCDEFGHIJ, soxABC, and the soxM supercomplex, as well as a novel hypothetical two-protein doxB-like polyferredoxin complex. Other genes found in M. yellowstonensis with possible roles in S and or Fe cycling include a thiosulfate oxidase (tqoAB), a sulfite oxidase (som), a cbsA cytochrome b(558/566), several small blue copper proteins, and a novel gene sequence coding for a putative multicopper oxidase (Mco). Results from gene expression studies, including reverse transcriptase (RT) quantitative PCR (qPCR) of cultures grown autotrophically on either Fe(II), pyrite, or elemental S showed that the fox gene cluster and mco are highly expressed under conditions where Fe(II) is an electron donor. Metagenome sequence and gene expression studies of Fe-oxide mats confirmed the importance of fox genes (e.g., foxA and foxC) and mco under Fe(II)-oxidizing conditions. Protein modeling of FoxC suggests a novel lysine-lysine or lysine-arginine heme B binding domain, indicating that it is likely the cytochrome component of a heterodimer complex with foxG as a ferredoxin subunit. Analysis of mco shows that it encodes a novel multicopper blue protein with two plastocyanin type I copper domains that may play a role in the transfer of electrons within the Fox protein complex. An understanding of metabolic pathways involved in aerobic iron and sulfur oxidation in Sulfolobales has broad implications for understanding the evolution and niche diversification of these thermophiles as well as practical applications in fields such as bioleaching of trace metals from pyritic ores.

Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

NASA Astrophysics Data System (ADS)

Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

2012-04-01

Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to 13 mg L-1 and reduced Cu and Mn from 8 and 3 mg L-1 to below the detection limits, respectively. The experimental results suggested that the amendment of surface coating agents can be a promising alternative for inhibition of sulfide oxidation at AMD sites.

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

USGS Publications Warehouse

Zimbelman, D.R.; Rye, R.O.; Breit, G.N.

2005-01-01

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

PASSIVE TREATMENT OF ACID ROCK DRAINAGE FROM A SUBSURFACE MINE

EPA Science Inventory

Acidic, metal-contaminated drainages are a critical problem facing many areas of the world. Acid rock drainage results when metal sulfide minerals, particularly pyrite, are oxidized by exposure to oxygen and water. The deleterious effects of these drainages on receiving streams a...

Understanding Cu release into environment from Kure massive sulfide ore deposits, Kastamonu, NW Turkey

NASA Astrophysics Data System (ADS)

Demirel, Cansu; Sonmez, Seref; Balci, Nurgul

2014-05-01

Covering a wide range on the earth's crust, oxidation of metal sulfide minerals have vital environmental impacts on the aquatic environment, causing one of the major environmental problems known as acid mine drainage (AMD). Located in the Kastamonu province of the Western Black Sea region, Kure district is one of the major copper mining sites in Turkey. Mining activities in the area heads back to ancient times, such that operation is thought to be started with the Roman Empire. Currently, only the underground mining tunnels of Bakibaba and Asikoy are being operated. Thus, mining heaps and ores of those pyritic deposits have been exposed to the oxidative conditions for so long. As a result of weathering processes of past and recent heaps of the Kure volcanic massive sulfide deposits in addition to the main ore mineral (chalcopyrite), significant amount of metals, especially Cu, are being released into the environment creating undesirable environmental conditions. In order to elucidate Cu release mechanisms from Kure pyritic ore deposits and mining wastes, field and laboratory approaches were used. Surface water and sediment samples from the streams around the mining and waste sites were collected. Groundwater samples from the active underground mining site were also collected. Physical parameters (pH, Eh, T°C, and EC) of water samples were determined in situ and in the laboratory using probes (WTW pH 3110, WTW Multi 9310 and CRISON CM 35). Metal and ion concentrations of the water samples were analysed using ICP-MS and DR 2800 spectrophotometer, respectively. High Cu, Co, Zn and Fe concentrations were determined in the water samples with pH values ranging from 2.9- 4. Cu concentrions ranges from 345 ppm to 36 ppm in the water samples. Consistent with the water samples, high Cu, Fe, Zn and Co were also determined in the sediment samples. Laboratory chalcopyrite oxidation experiments under the conditions representing the field site were set up as biological and abiotic in order to elucidate Cu release from ore and wastes. Greater Cu release were measured from the biological experiments carried out with S and Fe oxidizers compared to those from the chemical experiments. Fe-oxide precipitation experiments carried out in the laboratory showed high Cu absorbtion into Fe-oxides produced by biological reactions carried out with Fe oxidizers. Overall, these preliminary experimental results showed that Cu release and migration from the source can be controlled by various microorganims which regulate S and Fe cycles in the field. Key words: Metal sulfide oxidation, Kure pyritic copper mines, AMD, Bioleaching, Secondary Fe-oxide precipitation

Enriching acid rock drainage related microbial communities from surface-deposited oil sands tailings.

PubMed

Dean, Courtney; Xiao, Yeyuan; Roberts, Deborah J

2016-10-01

Little is known about the microbial communities native to surface-deposited pyritic oil sands tailings, an environment where acid rock drainage (ARD) could occur. The goal of this study was to enrich sulfur-oxidizing organisms from these tailings and determine whether different populations exist at pH levels 7, 4.5, and 2.5. Using growth-based methods provides model organisms for use in the future to predict potential activities and limitations of these organisms and to develop possible control methods. Thiosulfate-fed enrichment cultures were monitored for approximately 1 year. The results showed that the enrichments at pH 4.5 and 7 were established quicker than at pH 2.5. Different microbial community structures were found among the 3 pH environments. The sulfur-oxidizing microorganisms identified were most closely related to Halothiobacillus neapolitanus, Achromobacter spp., and Curtobacterium spp. While microorganisms related to Chitinophagaceae and Acidocella spp. were identified as the only possible iron-oxidizing and -reducing microbes. These results contribute to the general knowledge of the relatively understudied microbial communities that exist in pyritic oil sands tailings and indicate these communities may have a potential role in ARD generation, which may have implications for future tailings management.

Oxidative degradation of benzene rings using iron sulfide activated by hydrogen peroxide/ozone.

PubMed

Hara, Junko

2017-12-01

Mineral pyrites-metal sulfides abundant in the earth's crust-exhibit oxidative ability when exposed to water. This oxidizing ability makes mineral pyrites suitable for the natural and enhanced remediation of environmentally hazardous materials. Herein, we evaluate the benzene ring degradation ability of iron bisulfide activated by H 2 O 2 and O 3 and elucidate the corresponding reaction pathways. A set of control experiments was conducted to optimize the reaction conditions, i.e., the FeS 2 /H 2 O ratio under aerobic conditions and the H 2 O 2 and/or O 3 dosages. Benzene ring was successfully decomposed to CO 2 via organic acids even by the simplest FeS 2 /H 2 O combination. This process was accelerated by the addition of both O 3 and H 2 O 2 . The extent of degradation to CO 2 increased in the presence of O 3 , while oxalic acid generation increased in the presence of H 2 O 2 . The reaction proceeded via the radicals generated on FeS 2 /H 2 O, which is enhanced by O 3 , and a Fenton-like reaction using the iron obtained from FeS 2 dissolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Impact of Aeolian Dry Deposition of Reactive Iron Minerals on Sulfur Cycling in Sediments of the Gulf of Aqaba

PubMed Central

Blonder, Barak; Boyko, Valeria; Turchyn, Alexandra V.; Antler, Gilad; Sinichkin, Uriel; Knossow, Nadav; Klein, Rotem; Kamyshny, Alexey

2017-01-01

The Gulf of Aqaba is an oligotrophic marine system with oxygen-rich water column and organic carbon-poor sediments (≤0.6% at sites that are not influenced by anthropogenic impact). Aeolian dust deposition from the Arabian, Sinai, and Sahara Deserts is an important source of sediment, especially at the deep-water sites of the Gulf, which are less affected by sediment transport from the Arava Desert during seasonal flash floods. Microbial sulfate reduction in sediments is inferred from the presence of pyrite (although at relatively low concentrations), the presence of sulfide oxidation intermediates, and by the sulfur isotopic composition of sulfate and solid-phase sulfides. Saharan dust is characterized by high amounts of iron minerals such as hematite and goethite. We demonstrated, that the resulting high sedimentary content of reactive iron(III) (hydr)oxides, originating from this aeolian dry deposition of desert dust, leads to fast re-oxidation of hydrogen sulfide produced during microbial sulfate reduction and limits preservation of reduced sulfur in the form of pyrite. We conclude that at these sites the sedimentary sulfur cycle may be defined as cryptic. PMID:28676799

Element mobilization from Bakken shales as a function of water chemistry.

PubMed

Wang, Lin; Burns, Scott; Giammar, Daniel E; Fortner, John D

2016-04-01

Waters that return to the surface after injection of a hydraulic fracturing fluid for gas and oil production contain elements, including regulated metals and metalloids, which are mobilized through interactions between the fracturing fluid and the shale formation. The rate and extent of mobilization depends on the geochemistry of the formation and the chemical characteristics of the fracturing fluid. In this work, laboratory scale experiments investigated the influence of water chemistry on element mobilization from core samples taken from the Bakken formation, one of the most productive shale oil plays in the US. Fluid properties were systematically varied and evaluated with regard to pH, oxidant level, solid:water ratio, temperature, and chemical additives. Element mobilization strongly depended on solution pH and redox conditions and to a lesser extent on the temperature and solid:water ratio. The presence of oxygen and addition of hydrogen peroxide or ammonium persulfate led to pyrite oxidation, resulting in elevated sulfate concentrations. Further, depending on the mineral carbonates available to buffer the system pH, pyrite oxidation could lower the system pH and enhance the mobility of several metals and metalloids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

USGS Publications Warehouse

Molins, S.; Mayer, K.U.

2007-01-01

The two‐way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate‐rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

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

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

USGS Publications Warehouse

Yaofa, Jiang; Elswick, E.R.; Mastalerz, Maria

2008-01-01

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur ( 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the ??34S values for fly-ash samples from the low-sulfur Danville coal average 10.2???, only slightly enriched in 34S relative to those from the parent coal (average 7.5???). The ??34S values for bulk S determined directly from the fly-ash samples show close correspondence with the ??34S values for SO4- 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion. ?? 2007 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Heterogeneous arsenic enrichment in meta-sedimentary rocks in central Maine, United States.

PubMed

O'Shea, Beth; Stransky, Megan; Leitheiser, Sara; Brock, Patrick; Marvinney, Robert G; Zheng, Yan

2015-02-01

Arsenic is enriched up to 28 times the average crustal abundance of 4.8 mg kg(-1) for meta-sedimentary rocks of two adjacent formations in central Maine, USA where groundwater in the bedrock aquifer frequently contains elevated As levels. The Waterville Formation contains higher arsenic concentrations (mean As 32.9 mg kg(-1), median 12.1 mg kg(-1), n=38) than the neighboring Vassalboro Group (mean As 19.1 mg kg(-1), median 6.0 mg kg(-1), n=38). The Waterville Formation is a pelitic meta-sedimentary unit with abundant pyrite either visible or observed by scanning electron microprobe. Concentrations of As and S are strongly correlated (r=0.88, p<0.05) in the low grade phyllite rocks, and arsenic is detected up to 1944 mg kg(-1) in pyrite measured by electron microprobe. In contrast, statistically significant (p<0.05) correlations between concentrations of As and S are absent in the calcareous meta-sediments of the Vassalboro Group, consistent with the absence of arsenic-rich pyrite in the protolith. Metamorphism converts the arsenic-rich pyrite to arsenic-poor pyrrhotite (mean As 1 mg kg(-1), n=15) during de-sulfidation reactions: the resulting metamorphic rocks contain arsenic but little or no sulfur indicating that the arsenic is now in new mineral hosts. Secondary weathering products such as iron oxides may host As, yet the geochemical methods employed (oxidative and reductive leaching) do not conclusively indicate that arsenic is associated only with these. Instead, silicate minerals such as biotite and garnet are present in metamorphic zones where arsenic is enriched (up to 130.8 mg kg(-1) As) where S is 0%. Redistribution of already variable As in the protolith during metamorphism and contemporary water-rock interaction in the aquifers, all combine to contribute to a spatially heterogeneous groundwater arsenic distribution in bedrock aquifers. Copyright © 2014 Elsevier B.V. All rights reserved.

Heterogeneous arsenic enrichment in meta-sedimentary rocks in central Maine, United States

PubMed Central

O’Shea, Beth; Stransky, Megan; Leitheiser, Sara; Brock, Patrick; Marvinney, Robert G.; Zheng, Yan

2014-01-01

Arsenic is enriched up to 28 times the average crustal abundance of 4.8 mg kg−1 for meta-sedimentary rocks of two adjacent formations in central Maine, USA where groundwater in the bedrock aquifer frequently contains elevated As levels. The Waterville Formation contains higher arsenic concentrations (mean As 32.9 mg kg−1, median 12.1 mg kg−1, n=36) than the neighboring Vassalboro Group (mean As 19.1 mg kg−1, median 6.0 mg kg−1, n=36). The Waterville Formation is a pelitic meta-sedimentary unit with abundant pyrite either visible or observed by scanning electron microprobe. Concentrations of As and S are strongly correlated (r=0.88, p<0.05) in the low grade phyllite rocks, and arsenic is detected up to 1,944 mg kg−1 in pyrite measured by electron microprobe. In contrast, statistically significant (p<0.05) correlations between concentrations of As and S are absent in the calcareous meta-sediments of the Vassalboro Group, consistent with the absence of arsenic-rich pyrite in the protolith. Metamorphism converts the arsenic-rich pyrite to arsenic-poor pyrrhotite (mean As 1 mg kg−1, n=15) during de-sulfidation reactions: the resulting metamorphic rocks contain arsenic but little or no sulfur indicating that the arsenic is now in new mineral hosts. Secondary weathering products such as iron oxides may host As, yet the geochemical methods employed (oxidative and reductive leaching) do not conclusively indicate that arsenic is associated only with these. Instead, silicate minerals such as biotite and garnet are present in metamorphic zones where arsenic is enriched (up to 130.8 mg kg−1 As) where S is 0%. Redistribution of already variable As in the protolith during metamorphism and contemporary water-rock interaction in the aquifers, all combine to contribute to a spatially heterogeneous groundwater arsenic distribution in bedrock aquifers. PMID:24861530

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

KUBILIUS, WALTER

The origin of elevated radium-226 in groundwater beneath a sanitary landfill at the Savannah River Site (SRS) was investigated. Nearly one hundred monitoring wells are developed in the Steed Pond Aquifer (SPA), which consists of 100-150 ft of Coastal Plain sand, iron oxides, and minor clay. Wells screened in the upper and middle portions of the aquifer have average Ra-226 between 0.5 and 2.5 pCi/L, and average pHs above 4.7. However, wells screened near the base of the aquifer exhibit higher average Ra-226 concentrations of 2.5 to 4.6 pCi/L, with some measurements exceeding the MCL of 5 pCi/L, and showmore » average pHs of 4.1 to 4.7. These wells are not downgradient of the landfill, and are not impacted by landfill leachate. The Crouch Branch Confining Unit (CBCU) underlies the aquifer, and is composed partly of reduced gray/brown clay with lignite and authigenic pyrite. Gamma ray logs show that the SPA has low gamma counts, but the CBCU is consistently elevated. Groundwater with high radium/low pH also contains elevated sulfate concentrations. pH calculations indicate that sulfate is in the form of sulfuric acid. A model for the origin of elevated Ra-226 levels in deeper SPA wells envisions infiltration of oxygenated SPA groundwater into reduced pyritic CBCU sediments, with consequent oxidative pyrite dissolution, and acidification of groundwater. Then, naturally occurring CBCU radium dissolves, and mixes into the Steed Pond Aquifer.« less

Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

USGS Publications Warehouse

Palandri, J.L.; Rosenbauer, R.J.; Kharaka, Y.K.

2005-01-01

Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

ENVIRONMENTAL CONDITIONS, MICROBIAL POPULATIONS, AND THE ROLE OF ATTACHMENT IN OXIDATIVE DISSOLUTION OF PYRITE AT IRON MT. (R826189)

EPA Science Inventory

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...

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

PubMed

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.

Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Formolo, Michael J.; Lyons, Timothy W.

2013-10-01

Cold seeps in the Gulf of Mexico provide a natural laboratory to study biogeochemical cycling of sulfur, carbon, and oxygen at hydrate- and hydrocarbon-rich deep marine settings with obvious additional relevance to studies of diverse modern and ancient seeps. Of particular interest are the sulfur isotope signatures of microbial sulfate reduction coupled to anaerobic oxidation of methane and other non-methane liquid and gaseous hydrocarbons. Whereas most of the published sulfur isotope data from cold seep systems pertain to pore-water species, our study integrates both solid and dissolved sulfur: acid-volatile sulfides (SAVS), pyrite (Spy), elemental sulfur (S°), dissolved sulfate and ΣH2S. Modeled and 35SO42- reduction rates and δ13C and δ18O data for authigenic carbonates are integrated within this sulfur framework. Our results indicate extreme variability over narrow spatial and temporal scales within short distances (meters) from active seeps. High rates of microbial sulfate reduction can lead to complete consumption of the sulfate within the upper few centimeters of burial, while meters away the sulfate profile shows little depletion. Such small-scale variability must reflect the structure and temporal dynamics of hydrocarbon migration in the presence of low amounts of background organic matter. Our past work demonstrated that electron donors other than methane drive significant levels of microbial activity at these seeps, and very recent work has demonstrated that oxidation of higher chain volatile hydrocarbons can contribute to the high levels of microbial activity. These findings are consistent with our new results. Elevated concentrations of pyrite and diagenetic carbonate relative to background sediments are diagnostic of active seepage, yet the S isotopes tell more complex stories. Low levels of the transient, 'instantaneous' products of S cycling-AVS and S°-show high δ34S values that increase with depth. Most of the pyrite formation, however, seems to be very early as limited by the availability of reactive Fe phases. As such, δ34S values for pyrite at ancient seeps can show consistently low δ34S values that undersell the full intensity of microbial sulfate reduction. Low sedimentation rates, and the resulting low detrital iron fluxes, may in fact limit our ability to recognize seeps in the geologic record using only δ34S compositions for pyrite.

Cryptic oxygen oases: Hypolithic photosynthesis in hydrothermal areas and implications for Archean surface oxidation

NASA Astrophysics Data System (ADS)

Havig, J. R.; Hamilton, T. L.

2017-12-01

Mounting geochemical evidence suggests microorganisms capable of oxygenic photosynthesis (e.g., Cyanobacteria) colonized Archean continental surfaces, driving oxidative weathering of detrital pyrites prior to the 2.5 Ga great oxidation event. Modern terrestrial environments dominated by single-celled phototrophs include hydrothermal systems (e.g., Yellowstone National Park) and hypolithic communities found in arid to hyper-arid deserts (e.g., McMurdo Dry Valleys of Antarctica, Atacama Desert of Chile). Recent work indicates terrestrial hydrothermal systems date back at least as far as 3.5 Ga. Here, we explore phototrophic communities in both hypolithic (sub-sinter) and hydrothermal (subaqueous and subaerial) environments in Yellowstone National Park as potential analogs to Archean continental surfaces. Hydrothermal sub-sinter environments provide ideal conditions for phototrophic microbial communities, including blocking of harmful UV radiation, trapping and retention of moisture, and protection from erosion by rain and surface runoff. Hypolithic communities in geothermal settings were similar in both composition and carbon uptake rates to nearby hot spring communities. We hypothesize that hydrothermal area hypolithic communities represent modern analogs of phototrophic microbial communities that colonized Archean continental surfaces, producing oxygen locally and facilitating microbially-mediated pyrite oxidation prior to the presence of free oxygen in the global atmosphere. These results have implications for oxidation of the early Earth surface, the search for biosignatures in the rock record, as well as for potential harbors of past life on Mars and the search for life on Exoplanets.

Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

NASA Astrophysics Data System (ADS)

Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn

2015-04-01

Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope composition of the host sediment differs significantly from the siderite concretions. The δ13C values of the Gosau host sediment reflect marine conditions, whereas the oxygen isotope values are best explained by meteoric overprint. Lipid biomarkers have been extracted before and after dissolution of the concretions in order to assess their authenticity and to exclude recent surface contamination. In the following, only the biomarkers extracted after dissolution are discussed, since they are thought to be related to concretion formation. The calcite concretions comprise abundant plant wax derived long-chain n-alkanes, reflecting high terrestrial input. Bacterial, terminally-branched fatty acids were found, but in overall low abundance. The siderite concretions did not yield biomarkers due to their high maturity. No archaeal biomarkers were found in any of the concretions. Considering the presence of framboidal pyrite, the moderately low δ13C values, and the biomarker inventory, bacterial sulfate reduction apparently contributed to the formation of the calcite concretions in a brackish environment. In contrast, ongoing sulfate reduction and resultant hydrogen sulfide production inhibit siderite precipitation. Therefore, the low δ13C values of the siderite concretions are best explained by bacterial iron reduction.

Chemical and mineralogical changes of waste and tailings from the Murgul Cu deposit (Artvin, NE Turkey): implications for occurrence of acid mine drainage.

PubMed

Sağlam, Emine Selva; Akçay, Miğraç

2016-04-01

Being one of the largest copper-producing resources in Turkey, the Murgul deposit has been a source of environmental pollution for very long time. Operated through four open pits with an annual production of about 3 million tons of ore at an average grade of about 0.5% Cu, the deposit to date has produced an enormous pile of waste (exceeding 100 million tons) with tailings composed of 36 % SiO2, 39% Fe2O3 and 32% S, mainly in the form of pyrite and quartz. Waters in the vicinity of the deposit vary from high acid-acid (2.71-3.85) and high-extremely metal rich (34.48-348.12 mg/l in total) in the open pits to near neutral (6.51-7.83) and low metal (14.39-973.52 μg/l in total) in downstream environments. Despite low metal contents and near neutral pH levels of the latter, their suspended particle loads are extremely high and composed mainly of quartz and clay minerals with highly elevated levels of Fe (3.5 to 24.5% Fe2O3; 11% on average) and S (0.5 to 20.6% S; 7% on average), showing that Fe is mainly in the form of pyrite and lesser hematite. They also contain high concentrations of As, Au, Ba, Cu, Pb, and Zn. Waters collected along the course of polluted drainages are supersaturated with respect to Fe phases such as goethite, hematite, maghemite, magnetite, schwertmannite and ferrihydrite. Secondary phases such as Fe-sulphates are only found near the pits, but not along the streams due to neutral pH conditions, where pebbles are covered and cemented by Fe-oxides and hydroxides indicating that oxidation of pyrite has taken place especially at times of low water load. It follows, then, that the pyrite-rich sediment load of streams fed by the waste of the Murgul deposit is currently a big threat to the aquatic life and environment and will continue to be so even after the closure of the deposit. In fact, the oxidation will be enhanced and acidity increased due to natural conditions, which necessitates strong remedial actions to be taken.

Solution-processable pyrite FeS(2) nanocrystals for the fabrication of heterojunction photodiodes with visible to NIR photodetection.

PubMed

Wang, Di-Yan; Jiang, You-Ting; Lin, Chih-Cheng; Li, Shao-Sian; Wang, Yaw-Tyng; Chen, Chia-Chun; Chen, Chun-Wei

2012-07-03

A heterojunction photodiode with NIR photoresponse using solution processable pyrite FeS(2) nanocrystal ink is demonstrated which has the advantages of earth-abundance and non-toxicity. The device consists of a FeS(2) nanocrystal (NC) thin film sandwiched with semiconducting metal oxides with a structure of ITO/ZnO/FeS(2) NC/MoO(3) /Au, which exhibits an excellent photoresponse with a spectral response extended to NIR wavelengths of up to 1150 nm and a high photocurrent/dark current ratio of up to 8000 at -1 V under AM1.5 illumination (100 mW cm(-2) ). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probabilistic, sediment-geochemical parameterisation of the groundwater compartment of the Netherlands for spatially distributed, reactive transport modelling

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.

Formation and resulfidization of a South Texas roll-type uranium deposit

USGS Publications Warehouse

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.

Water characterization and seasonal heavy metal distribution in the Odiel River (Huelva, Spain) by means of principal component analysis.

PubMed

Montes-Botella, C; Tenorio, M D

2003-11-01

The Iberian Pyrite Belt is the largest mass of sulfide and manganese ores in Western Europe. Its sulfide oxidation is the origin of a heavily acidic drainage that affects the Odiel River in southwestern Huelva (Spain). To assess physicochemical, contamination parameters, heavy metal distribution and its seasonal variation in the upper Odiel River and in El Lomero mines, three water samplings were undertaken and analyzed between July 1998 and November 1999. Water from the Odiel River in the polluted zone showed low pH values (2.76-3.51), high heavy metal content, and high values of conductivity (1410-3648 microS/cm) and dissolved solids (1484-5602 mg/L). Principal Component Analysis (PCA) showed that variables related with the products of the pyrite oxidation and the salts that are solubilized by the high acidity generated in the oxidation of sulfides, grouped in the first component, accounted for 40.88% of total variance, and were the main influential factor in physicochemical water sample properties. The second influential factor was minority metals (nickel, cobalt, cadmium). Heavy metals showed three different seasonal patterns, closely related with saline efflorescences formed next to the river bed: majority metals (iron, copper, manganese, zinc); minority metals (lead, nickel, cobalt, cadmium); and chromium, which had a distinctive behavior.

Linking leach chemistry and microbiology of low-grade copper ore bioleaching at different temperatures

NASA Astrophysics Data System (ADS)

Jia, Yan; Sun, He-yun; Tan, Qiao-yi; Gao, Hong-shan; Feng, Xing-liang; Ruan, Ren-man

2018-03-01

The effects of temperature on chalcocite/pyrite oxidation and the microbial population in the bioleaching columns of a low-grade chalcocite ore were investigated in this study. Raffinate from the industrial bioleaching heap was used as an irrigation solution for columns operated at 20, 30, 45, and 60°C. The dissolution of copper and iron were investigated during the bioleaching processes, and the microbial community was revealed by using a high-throughput sequencing method. The genera of Ferroplasma, Acidithiobacillus, Leptospirillum, Acidiplasma, and Sulfobacillus dominated the microbial community, and the column at a higher temperature favored the growth of moderate thermophiles. Even though microbial abundance and activity were highest at 30°C, the column at a higher temperature achieved a much higher Cu leaching efficiency and recovery, which suggested that the promotion of chemical oxidation by elevated temperature dominated the dissolution of Cu. The highest pyrite oxidation percentage was detected at 45°C. Higher temperature resulted in precipitation of jarosite in columns, especially at 60°C. The results gave implications to the optimization of heap bioleaching of secondary copper sulfide in both enhanced chalcocite leaching and acid/iron balance, from the perspective of leaching temperature and affected microbial community and activity.

ACID-BASE ACCOUNT EFFECTIVENESS FOR DETERMINATION OF MINE WASTE POTENTIAL ACIDITY. (R825549C048)

EPA Science Inventory

The oxidation of sulfide minerals in mine waste is a widespread source of resource degradation, often resulting in the generation of acidic water and mobilization of heavy metals. The quantity of acid forming minerals present in mine waste, dominantly as pyrite (FeS₂

Application of Reactive Transport Modeling to Heap Bioleaching of Copper

NASA Astrophysics Data System (ADS)

Liu, W.

2017-12-01

Copper heap bioleaching is a complex industrial process that utilizes oxidative chemical leaching and microbial activities to extract copper from packed ore beds. Mathematical modelling is an effective tool for identifying key factors that determine the leaching performance. HeapSim is a modelling tool that incorporates all fundamental processes that occur in a heap under leach, such as the movement of leaching solution, chemical reaction kinetics, heat transfer, and microbial activities, to predict the leaching behavior of a heap. In this study, the HeapSim model was applied to simulate chalcocite heap bioleaching at Quebrada Blanca mine located in the Northern Chile. The main findings were that the model could be satisfactorily calibrated and validated to simulate chalcocite leaching. Heap temperature was sensitive to the changes in the raffinate temperature, raffinate flow rate, and the extent of pyrite oxidation. At high flow rates, heap temperature was controlled by the raffinate temperature. In contrast, heat removal by the raffinate solution flow was insignificant at low flow rates, leading to the accumulation of heat generated by pyrite reaction and therefore an increase in heap temperature.

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area, USA

USGS Publications Warehouse

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

Sedimentary Carbon, Sulfur, and Iron Relationships in Modern and Ancient Diagenetic Environments of the Eel River Basin (U.S.A.)

USGS Publications Warehouse

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.

Significance of Microbial Communities and Interactions in Safeguarding Reactive Mine Tailings by Ecological Engineering▿†

PubMed Central

N̆ancucheo, Ivan; Johnson, D. Barrie

2011-01-01

Pyritic mine tailings (mineral waste generated by metal mining) pose significant risk to the environment as point sources of acidic, metal-rich effluents (acid mine drainage [AMD]). While the accelerated oxidative dissolution of pyrite and other sulfide minerals in tailings by acidophilic chemolithotrophic prokaryotes has been widely reported, other acidophiles (heterotrophic bacteria that catalyze the dissimilatory reduction of iron and sulfur) can reverse the reactions involved in AMD genesis, and these have been implicated in the “natural attenuation” of mine waters. We have investigated whether by manipulating microbial communities in tailings (inoculating with iron- and sulfur-reducing acidophilic bacteria and phototrophic acidophilic microalgae) it is possible to mitigate the impact of the acid-generating and metal-mobilizing chemolithotrophic prokaryotes that are indigenous to tailing deposits. Sixty tailings mesocosms were set up, using five different microbial inoculation variants, and analyzed at regular intervals for changes in physicochemical and microbiological parameters for up to 1 year. Differences between treatment protocols were most apparent between tailings that had been inoculated with acidophilic algae in addition to aerobic and anaerobic heterotrophic bacteria and those that had been inoculated with only pyrite-oxidizing chemolithotrophs; these differences included higher pH values, lower redox potentials, and smaller concentrations of soluble copper and zinc. The results suggest that empirical ecological engineering of tailing lagoons to promote the growth and activities of iron- and sulfate-reducing bacteria could minimize their risk of AMD production and that the heterotrophic populations could be sustained by facilitating the growth of microalgae to provide continuous inputs of organic carbon. PMID:21965397

Sulphur cycling in a Neoarchaean microbial mat.

PubMed

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.

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.

Distribution of arsenic, selenium, and other trace elements in high pyrite Appalachian coals: evidence for multiple episodes of pyrite formation

USGS Publications Warehouse

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.

Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

NASA Astrophysics Data System (ADS)

Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

2016-09-01

With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

Bacterial community composition in the water column of a lake formed by a former uranium open pit mine.

PubMed

Edberg, Frida; Andersson, Anders F; Holmström, Sara J M

2012-11-01

Mining of pyrite minerals is a major environmental issue involving both biological and geochemical processes. Here we present a study of an artificial lake of a former uranium open pit mine with the aim to connect the chemistry and bacterial community composition (454-pyrosequencing of 16S rRNA genes) in the stratified water column. A shift in the water chemistry from oxic conditions in the epilimnion to anoxic, alkaline, and metal and sulfide-rich conditions in the hypolimnion was corresponded by a strong shift in the bacterial community, with few shared operational taxonomic units (OTU) between the water layers. The epilimnetic bacterial community of the lake (~20 years old) showed similarities to other temperate freshwater lakes, while the hypolimnetic bacterial community showed similarity to extreme chemical environments. The epilimnetic bacterial community had dominance of Actinobacteria and Betaproteobacteria. The hypolimnion displayed a higher bacterial diversity and was dominated by the phototrophic green sulphur bacterium of the genus Chlorobium (ca. 40 % of the total community). Deltaproteobacteria were only represented in the hypolimnion and the most abundant OTUs were affiliated with ferric iron and sulfate reducers of the genus Geobacter and Desulfobulbus, respectively. The chemistry is clearly controlling, especially the hypolimnetic, bacterial community but the community composition also indicates that the bacteria are involved in metal cycling in the lake.

RECONSTRUCTING PALEO-SMT POSITIONS ON THE CASCADIA MARGIN USING MAGNETIC SUSCEPTIBILITY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Joel; Phillips, Stephen

2014-09-30

Magnetic susceptibility (κ) is a mixed signal in marine sediments, representing primary depositional and secondary diagenetic processes. Production of hydrogen sulfide via anaerobic oxidation of methane (AOM) at the sulfate-methane transition (SMT) and organoclastic sulfate reduction above the SMT can result in the dissolution of iron oxides, altering κ in sediments in methane gas and gas hydrate bearing regions. We investigated records of κ on the Cascadia margin (ODP Sites 1249 and 1252; IODP Site 1325) using a Zr/Rb heavy mineral proxy from XRF core scanning to identify intervals of primary detrital magnetic susceptibility and intervals and predict intervals affectedmore » by magnetite dissolutions. We also measured total sulfur content, grain size distributions, total organic carbon (TOC) content, and magnetic mineral assemblage. The upper 100 m of Site 1252 contains a short interval of κ driven by primary magnetite, with multiple intervals (> 90 m total) of decreased κ correlated with elevated sulfur content, consistent with dissolution of magnetite and re-precipitation of pyrite. In the upper 90 m of Site 1249, κ is almost entirely altered by diagenetic processes, with much of the low κ explained by a high degree of pyritization, and some intervals affected by the precipitation of magnetic iron sulfides. At Site 1325, κ between 0-20 and 51-73 mbsf represents primary mineralogy, and in the interval 24-51 mbsf, κ may be reduced due to pyritization. This integrated approach allows for a prediction of primary κ and the amount of κ loss at each site when compared to actual κ measurements. In the case of magnetite dissolution and full pyritization, these drawdowns in κ are supported by sulfur measurements, and the exposure times of magnetite to hydrogen sulfide can be modeled. The presence of methane and methane hydrates at these sites, as well as large variations in TOC content, suggest that the past migration rates of the SMT and variation in sulfate reduction rates may influence κ alteration along the Cascadia margin.« less

A proposed origin for fossilized Pennsylvanian plant cuticles by pyrite oxidation (Sydney Coalfield, Nova Scotia, Canada)

USGS Publications Warehouse

Zodrow, E.L.; Mastalerz, Maria

2009-01-01

Fossilized cuticles, though rare in the roof rocks of coal seam in the younger part of the Pennsylvanian Sydney Coalfield, Nova Scotia, represent nearly all of the major plant groups. Selected for investigation, by methods of Fourier transform infrared spectroscopy (FTIR) and elemental analysis, are fossilized cuticles (FCs) and cuticles extracted from compressions by Schulze's process (CCs) of Alethopteris ambigua. These investigations are supplemented by FTIR analysis of FCs and CCs of Cordaites principalis, and a cuticle-fossilized medullosalean(?) axis. The purpose of this study is threefold: (1) to try to determine biochemical discriminators between FCs and CCs of the same species using semi-quantitative FTIR techniques; (2) to assess the effects chemical treatments have, particularly Schulze's process, on functional groups; and most importantly (3) to study the primary origin of FCs. Results are equivocal in respect to (1); (2) after Schulze's treatment aliphatic moieties tend to be reduced relative to oxygenated groups, and some aliphatic chains may be shortened; and (3) a primary chemical model is proposed. The model is based on a variety of geological observations, including stratal distribution, clay and pyrite mineralogies associated with FCs and compressions, and regional geological structure. The model presupposes compression-cuticle fossilization under anoxic conditions for late authigenic deposition of sub-micron-sized pyrite on the compressions. Rock joints subsequently provided conduits for oxygen-enriched ground-water circulation to initiate in situ pyritic oxidation that produced sulfuric acid for macerating compressions, with resultant loss of vitrinite, but with preservation of cuticles as FCs. The timing of the process remains undetermined, though it is assumed to be late to post-diagenetic. Although FCs represent a pathway of organic matter transformation (pomd) distinct from other plant-fossilization processes, global applicability of the chemical models remains to be tested. CCs and FCs are inferred endpoints on a spectrum of pomd which complicates assessing origin of in-between transformations (partially macerated cuticles). FCs index highly acidic levels that existed locally in the roof rocks.

Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions

USGS Publications Warehouse

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.

Interpreting the History of Lake Anoxia Using Iron and Sulfur Geochemistry

NASA Astrophysics Data System (ADS)

Ku, T.; Lozewski, J.; Ekdahl, E.; Teranes, J.

2004-05-01

Over the last thousand years, anthropogenic activities, such as land cultivation and atmospheric pollution, have increased the flux of growth-limiting nutrients to several North American lakes. The most common effect of this enhanced nutrient supply is a dramatic increase in the abundance of aquatic plants and algae. When these organisms die, the organic carbon in their remains falls through the water column and is oxidized by dissolved oxygen. Thus, eutrophic lakes are characterized by seasonally or permanently anoxic bottom waters because the rate of organic carbon oxidation exceeds the rate at which oxygen is replenished. The depletion of water column oxygen adversely affects lake ecosystems by decreasing water quality and by altering the community structure of fish and algae populations. In this study we examine the history of lake anoxia in two North American lakes, Half-Moon Lake in Michigan and Crawford Lake in Ontario. Sediment freeze cores and water column samples were taken from each site and both lakes contained well-preserved varved sediments. The sediments were analyzed for FeH (HCl-extractable iron), AVS (acid-volatile sulfur), CRS (chromium-reducible sulfur), d34S(CRS), CaCO3, CH2O, C/N, and d13C (CaCO3). Water samples were analyzed for pH, O2, cations, anions, and d34S(SO4). Today, Half-Moon Lake is seasonal anoxic while Crawford Lake has not overturned in the past ~15 years. Geochemical and biological data indicate that both lakes have experienced cultural eutrophication events in the 1800-1900s related to European-style agricultural practices. In addition, Crawford Lake experienced an earlier eutrophication episode around 1325 A.D. related to Iroquoian settlement of the area. Each eutrophication event showed an increase in the mass accumulation rate of pyritic sulfur, suggesting that sediments were exposed to longer durations of low-O2, H2S-rich waters during periods of cultural eutrophication. The geochemical parameter DOP (degree of pyritization) is defined as pyrite Fe/(pyrite Fe + FeH) and quantifies the fraction of iron that is converted into pyrite. DOP values from Half-Moon Lake are low (~0.1) prior to European settlement and increase to high values (>0.7) after European settlement. In Crawford Lake, our preliminary data indicate that the Iroquoian horizon has lower DOP values than the European horizon. This indicates that the water column was less sulfidic (more oxygen-rich) during the 1300s than in the 1800-1900s. These results show that Fe and S geochemistry can be used to document the history of lake anoxia.

Control of pyrite addition in coal liquefaction process

DOEpatents

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.

Natural Arsenic in the Miocene Hawthorn Group, Florida: Wide Ranging Implications for ASR, Phosphate Mining, Private Well

NASA Astrophysics Data System (ADS)

Lazareva, O. V.; Pichler, T.

2004-12-01

In order to understand the mineralogical association and distribution of arsenic (As) in the Hawthorn Group we examined in detail the chemical and mineralogical composition of 370 samples that were collected from 16 cores in central Florida. In our study area the Hawthorn group consists primarily of a basal carbonate unit (the Arcadia Formation) and an upper siliciclastic unit (The Peace River Formation). The Peace River Formation contains appreciable amounts of phosphate and is currently being exploited for phosphate ore. Samples were taken for each Formation at intervals of 25ft. In addition to the interval samples we also took samples that contained visible pyrite crystals, iron oxides, green clays, phosphatic and organic material. These additional samples were collected because of their potential of high As concentrations. Arsenic concentrations were determined by hydride generation - atomic fluorescence spectrometry (HG-AFS) after digestion with aqua regia (3:1 HCl and HNO3). The elements Fe, Na, Al, Si, Mg, Ca, S, P, and K were measured on the same solutions by inductively coupled plasma optical emission spectrometry (ICP-OES). The identification of discrete minerals was aided by scanning electron microscopy (SEM) and chemical compositions were obtained by electron-probe microanalyses (EMPA). Our study indicates that the average As concentrations significantly change from 9.0 ppm in the Peace River Formation to 3.0 ppm in the Tampa Member of the Arcadia Formation. As concentrations for all Hawthorn samples vary from 0.07 to 68.98 ppm ( μ = 5.6, σ = 7.1). Our detailed mineralogical and geochemical study demonstrates that: (1) The As in the Hawthorn group varies from the formation to formation and is mostly concentrated in trace minerals, such as pyrite; (2) Concentrations of the As in pyrite crystals can vary drastically from a minimum of 0 ppm to a maximum of 8260 ppm; (3) Pyrite is an unevenly distributed throughout the Hawthorn Group; (4) Phosphate and organic material, clays, and iron oxides contain lower As concentrations contrasted to pyrite; (5) Pyrite occurs in framboidal and euhedral forms. Because phosphorous, arsenic and sulfur are chemically closely related, they often occur together in nature, thus posing a potential problem for the phosphate industry. There have been several occurrences of swine fatalities due to arsenic poisoning as a result of phosphate feed supplements. Information about the concentration, distribution and mineralogical association of naturally occurring As is important, because this is a first step to forecast its behavior during anthropogenic induced physico-chemical changes in the aquifer. Recently, aquifer storage and recovery (ASR) facilities in central Florida reported As concentrations in excess of 100 μ g/L in recovered water. The ASR storage zone is the Suwannee Limestone, which directly underlies the Hawthorn sediments. It is crucial to the future of ASR in this area to understand the source and distribution of arsenic in the overlying Hawthorn Group and the cycling of arsenic in the Florida platform.

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

PubMed

Tao, Huang; Dongwei, Li

2014-12-01

This review outlines classic and current research, scientific documents and research achievements in bioleaching, particularly in respect of the bioleaching of chalcopyrite and pyrite. The diversity and commonality of the microbial leaching process can be easily studied through comparing the bioleaching mechanism and the application of these two metal sulfides. The crystal, electronic and surface structures of chalcopyrite and pyrite are summarized in detail in this paper. It determines the specific and complicated interaction pathways, kinetics of the atmospheric/aqueous oxidation, and the control process of bioleaching of the minerals as the precondition. Bioleaching of metal sulfides is performed by a diverse group of microorganisms and microbial communities. The species of the bacteria which have a significant effect on leaching ores are miraculously diverse. The newly identified acidophilic microorganisms with unique characteristics for efficient bioleaching of sulfidic minerals are increasing sharply. The cell-to-cell communication mechanisms, which are still implicit, elusive and intangible at present day, have gradually become a research hotspot. The different mineralogy characteristics and the acid solubility of the metal sulfides (e.g., chalcopyrite and pyrite) cause two different dissolution pathways, the thiosulfate and the polysulfide pathways. The bioleaching mechanisms are categorized by contact (an electrostatic attachment) and noncontact (planktonic) process, with emphasis on the produce of extracellular polymeric substances and formation of biofilm on the surface of the metal sulfides in this paper. The division of the direct and indirect effect are not adopted due to the redox chain, the reduction of the ferric iron and oxidation of the ferrous iron. The molecular oxygen is reduced by the electrons extracted from the specific metal sulfide, via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner membrane. The passivation of the mineral surface can obviously hinder the dissolution of metal sulfides during the bioleaching process, which is significantly affected by the kinetic model, microenvironment on the surface of ore and the leach conditions, such as temperature, pH and E h . The new development of mechanism research, enhanced and intensified technologies on the bioleaching of chalcopyrite and pyrite, are conducted and summarized from the different branches of natural science. Some are depicted and explained based on molecular level in this paper. Catalyst and catalytic mechanisms in bioleaching and biooxidation for this two sulfide minerals have been concluded and applied for several decades, the continuous emergence of the new material and technology are also gradually applied into the biohydrometallurgy. The industrial applications of the bioleaching on chalcopyrite and pyrite are totally based on the understanding of the interaction mechanism between microbes and minerals, the optimization of ore leaching conditions and the development of new material and the leaching equipment. It is not incredible and unimaginable to take a different bioleaching process and diagram to deal with the two sulfuric metals, which is vital to succeed in elevating the leaching rate of copper.

Microbial sulfate reduction and the sulfur budget for a complete section of altered oceanic basalts, IODP Hole 1256D (eastern Pacific)

USGS Publications Warehouse

Alt, Jeffrey C.; Shanks, Wayne C.

2011-01-01

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155ppm sulfur and are more oxidized, have high SO4/ΣS ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative δ34Ssulfide-S values (down to -30 °) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940ppm S, and with δ34S shifted to -6.0‰) from the mantle value (0 ‰). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 X1010molSyr-1, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 X 10-8molcm-2yr-1 over 15m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 X 1011moly-1, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Fundamental aspects related to batch and fixed-bed sulfate sorption by the macroporous type 1 strong base ion exchange resin Purolite A500.

PubMed

Guimarães, Damaris; Leão, Versiane A

2014-12-01

Acid mine drainage is a natural process occurring when sulfide minerals such as pyrite are exposed to water and oxygen. The bacterially catalyzed oxidation of pyrite is particularly common in coal mining operations and usually results in a low-pH water polluted with toxic metals and sulfate. Although high sulfate concentrations can be reduced by gypsum precipitation, removing lower concentrations (below 1200 mg/L) remains a challenge. Therefore, this work sought to investigate the application of ion exchange resins for sulfate sorption. The macroporous type 1 strong base IX resin Purolite A500 was selected for bath and fixed-bed sorption experiments using synthetic sulfate solutions. Equilibrium experiments showed that sulfate loading on the resin can be described by the Langmuir isotherm with a maximum uptake of 59 mg mL-resin(-1). The enthalpy of sorption was determined as +2.83 kJ mol(-1), implying an endothermic physisorption process that occurred with decreasing entropy (-15.5 J mol(-1).K(-1)). Fixed-bed experiments were performed at different bed depths, flow rates, and initial sulfate concentrations. The Miura and Hashimoto model predicted a maximum bed loading of 25-30 g L-bed(-1) and indicated that both film diffusion (3.2 × 10(-3) cm s(-1) to 22.6 × 10(-3) cm s(-1)) and surface diffusion (1.46 × 10(-7) cm(2) s(-1) to 5.64 × 10(-7) cm(2) s(-1)) resistances control the sorption process. It was shown that IX resins are an alternative for the removal of sulfate from mine waters; they ensure very low residual concentrations, particularly in effluents where the sulfate concentration is below the gypsum solubility threshold. Copyright © 2014 Elsevier Ltd. All rights reserved.

Compositions, ages, and diagenetic histories of the carbonate, sulfide, oxide, and phosphatic concretions at Gay Head, Massachusetts

USGS Publications Warehouse

Poppe, L.J.; Commeau, R.F.; O'Leary, Dennis W.

1988-01-01

The calcite/ankerite concretions were formed in a hot, seasonally arid, caliche-prone environment of early Raritan age; the pyrite, marcasite, and siderite concretions precipitated in sediments deposited in low-energy, marshy, estuarine environments of late Raritan age. The phosphate concretions formed in a middle to inner shelf environment. The goethite and lepidocrocite concretions are secondary oxidation or alteration products of the prexistent Cretaceous concretions that were excavated during the Pleistocene and incorporated into the glacial drift. -from Authors

Genesis of the Doğankuzu and Mortaş Bauxite deposits, Taurides, Turkey: separation of Al, Fe, and Mn and implications for passive margin metallogeny

USGS Publications Warehouse

Öztürk, Hüseyin; Hein, James R.; Hanilçi, Nurullah

2002-01-01

The Taurides region of Turkey is host to a number of important bauxite, Al-rich laterite, and Mn deposits. The most important bauxite deposits, Doğankuzu and Mortaş, are karst-related, unconformity-type deposits in Upper Cretaceous limestone. The bottom contact of the bauxite ore is undulatory, and bauxite fills depressions and sinkholes in the footwall limestone, whereas its top surface is concordant with the hanging-wall limestone. The thickness of the bauxite varies from 1 to 40 m and consists of böhmite, hematite, pyrite, marcasite, anatase, diaspore, gypsum, kaolinite, and smectite. The strata-bound, sulfide- and sulfate-bearing, low-grade lower part of the bauxite ore bed contains pyrite pseudomorphs after hematite and is deep red in outcrop owing to supergene oxidation. The lower part of the bauxite body contains local intercalations of calcareous conglomerate that formed in fault-controlled depressions and sinkholes. Bauxite ore is overlain by fine-grained Fe sulfide-bearing and calcareous claystone and argillaceous limestone, which are in turn overlain by massive, compact limestone of Santonian age. That 50-m-thick limestone is in turn overlain by well-bedded bioclastic limestone of Campanian or Maastrichtian age, rich with rudist fossils. Fracture fillings in the bauxite orebody are up to 1 m thick and consist of bluish-gray-green pyrite and marcasite (20%) with böhmite, diaspore, and anatase. These sulfide veins crosscut and offset the strata-bound sulfide zones. Sulfur for the sulfides was derived from the bacterial reduction of seawater sulfate, and Fe was derived from alteration of oxides in the bauxite. Iron sulfides do not occur within either the immediately underlying or overlying limestone. The platform limestone and shale that host the bauxite deposits formed at a passive margin of the Tethys Ocean. Extensive vegetation developed on land as the result of a humid climate, thereby creating thick and acidic soils and enhancing the transport of large amounts of organic matter to the ocean. Alteration of the organic matter provided CO2 that contributed to formation of a relatively 12C-rich marine footwall limestone. Relative sea-level fall resulted from strike-slip faulting associated with closure of the ocean and local uplift of the passive margin. That uplift resulted in karstification and bauxite formation in topographic lows, as represented by the Doğankuzu and Mortaş deposits. During stage 1 of bauxite formation, Al, Fe, Mn, and Ti were mobilized from deeply weathered aluminosilicate parent rock under acidic conditions and accumulated as hydroxides at the limestone surface owing to an increase in pH. During stage 2, Al, Fe, and Ti oxides and clays from the incipient bauxite (bauxitic soil) were transported as detrital phases and accumulated in the fault-controlled depressions and sinkholes. During stage 3, the bauxitic material was concentrated by repeated desilicification, which resulted in the transport of Si and Mn to the ocean through a well-developed karst drainage system. The transported Mn was deposited in offshore muds as Mn carbonates. The sulfides also formed in stage 3 during early diagenesis. Transgression into the foreland basin resulted from shortening of the ocean basin and nappe emplacement during the latest Cretaceous. During that time bioclastic limestone was deposited on the nappe ramp, which overlapped bauxite accumulation.

Trace-metal sources and their release from mine wastes: examples from humidity cell tests of hardrock mine waste and from Warrior Basin coal

USGS Publications Warehouse

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.

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.

Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

USGS Publications Warehouse

Seal, R.R.; Hammarstrom, J.M.; Johnson, A.N.; Piatak, N.M.; Wandless, G.A.

2008-01-01

The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

Comparison of three preservation techniques for slowing dissolution of calcareous nannofossils in organic rich sediments

USGS Publications Warehouse

Seefelt, Ellen L.; Self-Trail, Jean; Schultz, Arthur P.

2015-01-01

In an attempt to halt or reduce dissolution of calcareous nannofossils in organic and/or pyrite-rich sediments, three different methods of short-term storage preservation were tested for efficacy: vacuum packing, argon gas replacement, and buffered water. Abundance counts of calcareous nannofossil assemblages over a six month period showed that none of the three preservation methods were consistently effective in reducing assemblage loss due to dissolution. In most cases, the control slides made at the drill site had more abundant calcareous nannofossil assemblages than those slides made from sediments stored via vacuum packing, argon gas replacement, or buffered water. Thin section and XRD analyses showed that in most cases, <1% pyrite was needed to drive the oxidation-reduction reaction that resulted in dissolution, even in carbonate-rich sediments.

Environmental geochemistry at Red Mountain, an unmined volcanogenic massive sulphide deposit in the Bonnifield district, Alaska Range, east-central Alaska

USGS Publications Warehouse

Eppinger, R.G.; Briggs, P.H.; Dusel-Bacon, C.; Giles, S.A.; Gough, L.P.; Hammarstrom, J.M.; Hubbard, B.E.

2007-01-01

The unmined, pyrite-rich Red Mountain (Dry Creek) deposit displays a remarkable environmental footprint of natural acid generation, high metal and exceedingly high rate earth element (REE) concentrations in surface waters. The volcanogenic massive sulphide deposit exhibits well-constrained examples of acid-generating, metal-leaching, metal-precipitation and self-mitigation (via co-precipitation, dilution and neutralization) processes that occur in an undisturbed natural setting, a rare occurrence in North America. Oxidative dissolution of pyrite and associated secondary reactions under near-surface oxidizing conditions are the primary causes for the acid generation and metal leaching. The deposit is hosted in Devonian to Mississippian felsic metavolcanic rocks of the Mystic Creek Member of the Totatlanika Schist. Water samples with the lowest pH (many below 3.5), highest specific conductance (commonly >2500 ??S/cm) and highest major- and trace-element concentrations are from springs and streams within the quartz-sericite-pyrite alteration zone. Aluminum, Cd, Co, Cu, Fe, Mn, Ni, Pb, Y, Zn and, particularly, the REEs are found in high concentrations, ranging across four orders of magnitude. Waters collected upstream from the alteration zone have near-neutral pH, lower specific conductance (370 to 830 ??S/cm), lower metal concentrations and measurable alkalinities. Water samples collected downstream of the alteration zone have pH and metal concentrations intermediate between these two extremes. Stream sediments are anomalous in Zn, Pb, S, Fe, Cu, As, Co, Sb and Cd relative to local and regional background abundances. Red Mountain Creek and its tributaries do not, and probably never have, supported significant aquatic life. ?? 2007 AAG/ Geological Society of London.

Age of Sulfate Methane Transition Zone Determined by Modelling Barium Sulfate Growth

NASA Astrophysics Data System (ADS)

Lin, S.; Wang, W. C.; Lien, K. L.; Liu, C. C.; Fan, L. F.

2017-12-01

Methane seep to the sediment/water interface could initiate anaerobic methane oxidation (AOM) with subsequent build up of chemosynthetic community, carbonate, pyrite and a number of other authigenic mineral formation. Determination the duration, sequence and time of methane seeps are keys to understand how methane seep to the environment and degree of alteration to the vicinity area. However, limited method existed in defining time of methane seep since there are some known problems involving typical dating methods, i.e. old carbon on C14 of fossil test or authigenic carbonate, thorium from surrounding matrix on U/Th authigenic carbonate dating. In this study, we have employed barium determination method (Dickens, 2001) to model timing of methane seep at two locations in the South China Sea. Our objective is to compare timing of the barium accumulation near the sulfate methane transition zone (SMTZ) on these two different locations and to seek if a similar mechanism driving the methane seep at two locations far apart. Dissolved barium, total sediment barium and aluminum were measured as well as pore water sulfate, and sediment pyrite concentrations. Time for the barium sulfate accumulation is calculated by: T = C/F, C= ∫ I x p x (1-Ø) Our results show that SMTZ is stabilized at each site for a duration of about 4000-5000 years. AOM process have been active at both sites at about the same time. In conjunction, pyrite also accumulated at a depth near the SMTZ as a result of methane oxidation. This result show that AOM could stay at the SMTZ for a relatively long period of time, on a scale of thousands of years.

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Snyder, D.M.; McCleskey, R. Blaine; Amils, R.; Poulson, S.R.

2008-01-01

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Ri??o Tinto, Ri??o Odiel, and Ri??o Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66????M at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3??nmol L- 1 s- 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3??nmol L- 1 s- 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Ri??o Tinto in about 30??days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research. ?? 2008 Elsevier B.V. All rights reserved.

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

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

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

DOE PAGES

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

Hydrothermal oxidation in the Biwabik Iron Formation, MN, USA

NASA Astrophysics Data System (ADS)

Losh, Steven; Rague, Ryan

2018-02-01

Precambrian iron formations throughout the world, notably in Australia, Brazil, and South Africa, show evidence of hypogene (≥ 110 °C, mostly > 250 °C) oxidation, alteration, and silica dissolution as a result of tectonic or magmatic activity. Although hydrothermal oxidation has been proposed for the prototype Lake Superior-type iron formation, the Biwabik Iron Formation in Minnesota (USA), it has not been documented there. By examining oxidized and unoxidized Biwabik Iron Formation in three mines, including material from high-angle faults that are associated with oxidation, we document an early hypogene oxidation event ( 175 °C) involving medium-salinity aqueous fluids (8.4 ± 4.9 wt% NaCl equiv) that infiltrated iron formation along high-angle faults. At the Hibbing Taconite Mine, hydrothermal fluids oxidized iron carbonates and silicates near faults, producing goethite ± quartz. In contrast with much of the oxidized iron ores on the Mesabi Range, silica was not removed but rather recrystallized during this event, perhaps lying in a rock-dominated system at low cumulative fluid flux. During the hydrothermal oxidation event in the Hibbing Taconite deposit, quartz-filled microfractures and irregular inclusions commonly formed in coarse variably oxidized magnetite, currently the ore mineral: these inclusions degrade the ore by introducing excess silica in magnetic concentrate. Hydrothermal oxidation at Hibbing Taconite Mine is overprinted by later, relatively minor supergene oxidation both along faults and near the surface, which locally dissolved quartz. At the Fayal Reserve Mine, widespread silicate and carbonate gangue dissolution and iron oxidation was followed by precipitation of pyrite, Mn-siderite, apatite, and other minerals in void spaces, which prevented post-oxidation compaction and significant volume loss in the sampled rocks. Although definitive temperature data for this assemblage are needed, the weight of evidence indicates that this mineralization is hypogene. The association of oxidation with epithermal conditions constrains the oxidation and subsequent mineralization to have taken place during the Precambrian, the only time when these rocks would have experienced the necessary temperatures. The mineralization at Fayal Reserve shows little supergene overprint: pyrite is largely unoxidized. Hydrothermal oxidation in both mines was likely produced by basinal fluids that were expelled during the 1.83-1.87 Ga Penokean Orogeny, and mixing with meteoric fluids along faults, although a 1.1 Ga rift-related fluid flow event is also possible. Later supergene overprinting of the iron formation was minor.

Factors affecting the transformation of a pyritic tailing: scaled-up column tests.

PubMed

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.

Marine sulfur cycle constrained from isotope analysis of different forms of sulfur in the 3.2 Ga black shale (DXCL-DP) from Pilbara, Australia

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.

Soil amendments promote vegetation establishment and control acidity in coal combustion waste

Treesearch

R.M. Danker; D.C. Adriano; Bon-Jun Koo; C.D. Barton

2003-01-01

The effects of adding various soil amendments and a pyrite oxidation inhibitor to aid in the establishment of vegetation and to reduce acid drainage (AD) from coal fly ash and coal reject (FA + CR*) were assessed in an outdoor mesocosm study. Preliminary greenhouse experiments and field observations at the U.S. Department of Energy's Savannah River Site (SRS)...

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

DOE PAGES

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.; ...

2017-03-01

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

Size and maceral association of pyrite in Illinois coals and their float-sink fractions

USGS Publications Warehouse

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.

AHL signaling molecules with a large acyl chain enhance biofilm formation on sulfur and metal sulfides by the bioleaching bacterium Acidithiobacillus ferrooxidans.

PubMed

González, Alex; Bellenberg, Sören; Mamani, Sigde; Ruiz, Lina; Echeverría, Alex; Soulère, Laurent; Doutheau, Alain; Demergasso, Cecilia; Sand, Wolfgang; Queneau, Yves; Vera, Mario; Guiliani, Nicolas

2013-04-01

Biofilm formation plays a pivotal role in bioleaching activities of bacteria in both industrial and natural environments. Here, by visualizing attached bacterial cells on energetic substrates with different microscopy techniques, we obtained the first direct evidence that it is possible to positively modulate biofilm formation of the extremophilic bacterium Acidithiobacillus ferrooxidans on sulfur and pyrite surfaces by using Quorum Sensing molecules of the N-acylhomoserine lactone type (AHLs). Our results revealed that AHL-signaling molecules with a long acyl chain (12 or 14 carbons) increased the adhesion of A. ferrooxidans cells to these substrates. In addition, Card-Fish experiments demonstrated that C14-AHL improved the adhesion of indigenous A. ferrooxidans cells from a mixed bioleaching community to pyrite. Finally, we demonstrated that this improvement of cell adhesion is correlated with an increased production of extracellular polymeric substances. Our results open up a promising means to develop new strategies for the improvement of bioleaching efficiency and metal recovery, which could also be used to control environmental damage caused by acid mine/rock drainage.

Bacterial leaching of waste uranium materials.

PubMed

Barbic, F F; Bracilović, D M; Krajincanić, B V; Lucić, J L

1976-01-01

The effect of ferrobacteria and thiobacteria on the leaching of waste uranium materials from which 70-80% of uranium was previously leached by classical chemical hydrometallurgical procedure has been investigated. The bacteria used are found in the ore and the mine water of Zletovska River locality, Yugoslavia. Parameters of biological leaching were examined in the laboratory. Leaching conditions were changed with the aim of increasing the amount of uranium leached. The effect of pyrite added to the waste materials before the beginning of leaching has also been examined. Uranium leaching is directly proportional to the composition and number of ferrobacteria and thiobacteria, and increased by almost twice the value obtained from the same starting materials without using bacteria. Increased sulphuric acid concentrations stimulate considerably the rate of leaching. Uranium leaching is increased up to 20% while sulphuric acid consumption is simultaneously decreased by the addition of pyrite. Uranium concentrations in starting waste materials used for leaching were extremely low (0.0278 and 0.372% U) but about 60% recovery of uranium was obtained, with relatively low consumption of sulphuric acid.

Arsenic contamination of the environment: a new perspective from central-east India.

PubMed

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.

Novel electrochemical process for coal conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farooque, M.

1989-07-01

The feasibility of two distinctly different routes to coal conversion at low severity conditions was investigated. An electrochemical approach utilizing both the electro-oxidation and electro-reduction routes was employed. The electro-oxidation route consists of an electrochemical reaction involving H{sub 2}O and coal, leading to the breakup of coal molecules. The observed reaction rate has been explained as a combination of the coal and pyrite electro-oxidation currents. Organic sulfur has been identified as the contributing factor for the observation of more than 100% H{sub 2} production current efficiency with several coal samples. Also, an attractive coal pre-treatment process has been identified whichmore » results in production of useful products and simultaneous upgrading of the coal. Electrochemical oxidation of coal with H{sub 2}O leads to the production of hydrogen, CO{sub 2}, simultaneous removal of pyritic sulfur, and significant reduction of ash content. There is also indirect evidence that the organic sulfur may be removed in the process. A preliminary economic evaluation of this process has projected a cost advantage of > $8 per ton of Illinois {number sign}2 coal. A lab-scale cell has been successfully employed in this study for generating process data useful for future design calculations. This study also explored the electro-reduction route of coal conversion and has successfully demonstrated production of liquid products from different coal types at low severity conditions. A variety of aliphatic and aromatic compounds have been identified in the products. Coal type appeared to be the most important parameter affecting the product spectrum. 32 refs., 26 figs., 19 tabs.« less

An unusual occurrence of arsenic-bearing pyrite in the Upper Freeport coal bed, West-Central Pennsylvania

USGS Publications Warehouse

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.

Bacterial oxidation of dibromomethane and methyl bromide in natural waters and enrichment cultures

USGS Publications Warehouse

Goodwin, K.D.; Schaefer, J.K.; Oremland, R.S.

1998-01-01

Bacterial oxidation of 14CH2Br2 and 14CH3Br was measured in freshwater, estuarine, seawater, and hypersaline-alkaline samples. In general, bacteria from the various sites oxidized similar amounts of 14CH2Br2 and comparatively less 14CH3Br. Bacterial oxidation of 14CH3Br was rapid in freshwater samples compared to bacterial oxidation of 14CH3Br in more saline waters. Freshwater was also the only site in which methyl fluoride-sensitive bacteria (e.g., methanotrophs or nitrifiers) governed brominated methane oxidation. Half-life calculations indicated that bacterial oxidation of CH2Br2 was potentially significant in all of the waters tested. In contrast, only in freshwater was bacterial oxidation of CH3Br as fast as chemical removal. The values calculated for more saline sites suggested that bacterial oxidation of CH3Br was relatively slow compared to chemical and physical loss mechanisms. However, enrichment cultures demonstrated that bacteria in seawater can rapidly oxidize brominated methanes. Two distinct cultures of nonmethanotrophic methylotrophs were recovered; one of these cultures was able to utilize CH2Br2 as a sole carbon source, and the other was able to utilize CH3Br as a sole carbon source.

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

USGS Publications Warehouse

Ayuso, Robert A.; Foley, Nora K.

2008-01-01

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry (n=53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206Pb/204Pb from 18.186 to 18.391, 207Pb/204Pb from 15.617 to 15.657, 208Pb/204Pb from 38.052 to 38.210, 206Pb/207Pb from c. 1.1625 to 1.1760 and 208Pb/207Pb from c. 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206Pb/204Pb from 18.495 to 19.747 (one sample at 21.495), 207Pb/204Pb from 15.595 to 15.722 (one sample at 15.839), 208Pb/204Pb from 38.186 to 39.162,206Pb/207Pb from c.1.1860 to 1.2575 (one sample at 1.3855) and 208Pb/207Pb from c. 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more radiogenic than the pyrite-rich sulphidic schists. Sulphides from other regional bedrock units also have heterogeneous isotope values. Lead isotopic compositions of the sulphides from the sulphidic schists and coexisting Fe-oxides and Fe-sulphates produced by weathering and alteration overlap, but the secondary minerals extend toward more radiogenic values that broadly indicate the addition of Pb from anthropogenic origin. As a component of Pb from extensively used arsenical pesticides may also be present in the secondary minerals, the range in Pb isotope values is consistent with multiple sources: natural Pb from the schists and anthropogenic Pb (industrial and possibly from agricultural activities). Contributions from past mining activities or from other bedrock sources are not implicated.

Application of Mössbauer spectroscopy for: (1) characterization of Egyptian Maghara coal; (2) evaluating the efficiency of different methods for coal desulphurization

NASA Astrophysics Data System (ADS)

Eissa, N. A.; Sheta, N. H.; Ahmed, M. A.

1992-04-01

Coal has been recently discovered in Maghara mine at Northern Sinai, Egypt. Coal samples have been collected from different depths and were measured by XRD, XRF, and MS, in order to characterize this type of coal. It has been found that the iron bearing minerals are mainly pyrite and different sulphates depending on the depth of the sample. The second part contains the application of desulphurization techniques to Egyptian coal which are: floatation (one step and two steps) chemical [(HCl+HNO3), and Fe2(SO4)3] and bacterial methods (Chromatium and Chlorobium species). The efficiency of each technique was calculated. A comparative discussion is given of each desulphurization method, from which the bacterial method has proved to be the most efficient one.

Expression of Genes Involved in Iron and Sulfur Respiration in a Novel Thermophilic Crenarchaeon Isolated from Acid-Sulfate-Chloride Geothermal Systems

NASA Astrophysics Data System (ADS)

Kozubal, M.; Macur, R.; Inskeep, W. P.

2007-12-01

Acidic geothermal springs within Yellowstone National Park (YNP) provide an excellent opportunity to study microbial populations and their relationship with geochemical processes such as redox cycling and biomineralization of iron. Fourteen acid-sulfate-chloride (ASC) and acid-sulfate (AS) geothermal springs located in (YNP) have been extensively characterized for aqueous chemistry, solid phase mineral deposition and microbial diversity and distribution. The oxidation of Fe(II) with oxygen as an electron acceptor is exergonic under these conditions, consequently, Fe(II) may be an important electron donor driving primary production in ASC and AS habitats, and products of biomineralization (e.g. Fe[III]-oxides of varying crystallinity and structure, as well as jarosite in some cases) are common in the outflow channels of these environments. Recently, we isolated a novel Metallosphaera-like microorganism (Metallosphaera strain MK1) from an ASC spring in Norris Geyser Basin, YNP. Clone libraries (16S rRNA gene) from multiple sites suggest that microorganisms closely related to strain MK1 (between 98-100 percent similarity) dominate many spring locations between 55-80 C. The in situ abiotic oxidation rate of Fe(II) has been shown to be very slow in these systems and Metallosphaera strain MK1 has been directly implicated in biotic Fe(II) oxidation. Metallosphaera strain MK1 has been submitted for full genome sequencing and is yielding gene sequences related to the terminal oxidases SOXABC and SOXM super-complex. In addition, sequences from a recently characterized terminal oxidase FOX complex involved in Fe(II) and pyrite oxidation from Sulfolobus metallicus have been found in Metallosphaera strain MK1. A protein complex analogous to Metallosphaera sedula has been identified in strain MK1 and this complex has also been expressed in cells grown on pyrite and Fe(II). Other sequences identified in Metallosphaera strain MK1 that are involved in respiration are the TQO complex (thiosulfate:quinone oxidoreductase) related to the Acidianus ambivalens DOXAD complex and a sulfur reductase (SRE) complex related to one found in Sulfolobus solfataricus and Acidianus ambivalens. Here we report on the RNA expression of seven gene sequences from each of the above mentioned complexes for Metallosphaera strain MK1 grown aerobically on pyrite, sulfur, Fe(II)-ferrihydrite, and anaerobically with yeast extract and sulfur. In addition, expression studies are also compared to in situ samples collected from the geothermal Fe-mats.

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

PubMed Central

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

Cysteine and cystine adsorption on FeS2(100)

NASA Astrophysics Data System (ADS)

Suzuki, Teppei; Yano, Taka-aki; Hara, Masahiko; Ebisuzaki, Toshikazu

2018-08-01

Iron pyrite (FeS2) is the most abundant metal sulfide on Earth. Owing to its reactivity and catalytic activity, pyrite has been studied in various research fields such as surface science, geochemistry, and prebiotic chemistry. Importantly, native iron-sulfur clusters are typically coordinated by cysteinyl ligands of iron-sulfur proteins. In the present paper, we study the adsorption of L-cysteine and its oxidized dimer, L-cystine, on the FeS2 surface, using electronic structure calculations based density functional theory and Raman spectroscopy measurements. Our calculations suggest that sulfur-deficient surfaces play an important role in the adsorption of cysteine and cystine. In the thiol headgroup adsorption on the sulfur-vacancy site, dissociative adsorption is found to be energetically favorable compared with molecular adsorption. In addition, the calculations indicate that, in the cystine adsorption on the defective surface under vacuum conditions, the formation of the S-Fe bond is energetically favorable compared with molecular adsorption. Raman spectroscopic measurements suggest the formation of cystine molecules through the S-S bond on the pyrite surface in aqueous solution. Our results might have implications for chemical evolution at mineral surfaces on the early Earth and the origin of iron-sulfur proteins, which are believed to be one of the most ancient families of proteins.

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

NASA Astrophysics Data System (ADS)

Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny

2018-02-01

Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

Viability of pyrite pulled metabolism in the ‘iron-sulfur world’ theory: Quantum chemical assessment

NASA Astrophysics Data System (ADS)

Michalkova, Andrea; Kholod, Yana; Kosenkov, Dmytro; Gorb, Leonid; Leszczynski, Jerzy

2011-04-01

The viability of pyrite-pulled metabolism in the 'iron-sulfur world' theory was assessed using a simple model of iron-nickel sulfide (Fe-Ni-S) surface and data obtained from quantum chemical calculations. We have investigated how the individual reactions in the carbon fixation cycle (carboxylic acids formation) on an Fe-Ni-S surface could have operated to produce carboxylic acids from carbon oxide and water. The proposed model cycle reveals how the individual reactions might have functioned and provides the thermodynamics of each step of the proposed pathway. The feasibility of individual reactions, as well the whole cycle was considered. The reaction of acetic acid production from CH 3SH and CO on an Fe-Ni sulfide surface was revealed to be endergonic with a few partial steps having positive Gibbs free energy. On the other hand, the pyrite formation was found to be slightly exergonic. The significance of the catalytic activity of transition metal sulfides in generation of acetic acid was shown. The Gibbs free energy values indicate that the acetic acid synthesis is unfavorable to proceed on the studied Fe-Ni-S model under simulated conditions. The importance of these results in terms of a primordial chemistry on iron-nickel sulfide surfaces is discussed.

Use of lectins to in situ visualize glycoconjugates of extracellular polymeric substances in acidophilic archaeal biofilms

PubMed Central

Zhang, R Y; Neu, T R; Bellenberg, S; Kuhlicke, U; Sand, W; Vera, M

2015-01-01

Biofilm formation and the production of extracellular polymeric substances (EPS) by meso- and thermoacidophilic metal-oxidizing archaea on relevant substrates have been studied to a limited extent. In order to investigate glycoconjugates, a major part of the EPS, during biofilm formation/bioleaching by archaea on pyrite, a screening with 75 commercially available lectins by fluorescence lectin-binding analysis (FLBA) has been performed. Three representative archaeal species, Ferroplasma acidiphilum DSM 28986, Sulfolobus metallicus DSM 6482T and a novel isolate Acidianus sp. DSM 29099 were used. In addition, Acidianus sp. DSM 29099 biofilms on elemental sulfur were studied. The results of FLBA indicate (i) 22 lectins bound to archaeal biofilms on pyrite and 21 lectins were binding to Acidianus sp. DSM 29099 biofilms on elemental sulfur; (ii) major binding patterns, e.g. tightly bound EPS and loosely bound EPS, were detected on both substrates; (iii) the three archaeal species produced various EPS glycoconjugates on pyrite surfaces. Additionally, the substratum induced different EPS glycoconjugates and biofilm structures of cells of Acidianus sp. DSM 29099. Our data provide new insights into interactions between acidophilic archaea on relevant surfaces and also indicate that FLBA is a valuable tool for in situ investigations on archaeal biofilms. PMID:25488256

Hydrogeochemical Processes Causing Persistent Low pH in Lakes within a Reclaimed Lignite Mine, East Texas

NASA Astrophysics Data System (ADS)

Paul, J. C.; Schwab, P.; Knappett, P.; Deng, Y.

2017-12-01

Surface water pH values ranging from 2.5 to 2.6 have been reported in three lakes at a reclaimed lignite mine located in the Wilcox Formation of East Texas (the site). Traditional neutralization processes using alkaline chemicals to neutralize the surface water were found to be temporary solutions at the site. Low pH conditions usually are caused by oxidation of pyritic materials in the original tailings, but that was not always apparent based on previous studies at this site. The objective of this study is to determine factors contributing to acid seepage to aid in developing pre- and post-mining strategies to mitigate persistent acidity in surface waters at this and other sites. Mineralogy, hydrogeology, and hydrogeochemical reactions were evaluated. A network of 30 wells was used to monitor the water table and chemistry of the shallow, unconfined aquifer surrounding the lakes. Pressure transducers were deployed in 18 of these wells and each of the lakes to measure high frequency water levels over approximately one year. These water levels were contoured to visualize changing hydraulic head over time and determine the correlation in time between ground water flow directions and local rainfall events. Boreholes at 15 of the monitoring wells were continuously cored, and samples were taken at selected depth intervals based on pH measurements. XRD, SEM, and TEM were used to determine the mineralogy of select soil samples. Ion chromatography was used to determine sulfate concentration, and ICP-MS was used to determine solute concentrations from water and digested soil samples. Framboidal and microcrystalline pyrite were identified in the vadose zone in silt and clay-sized fractions; these minerals have high surface area that is conducive to rapid oxidation and acidification as ground water permeates from the vadose into the saturated zone. Morphology in addition to quantity of weatherable pyrite plays a significant role in acidification. Computer models were used to evaluate the effect of dissolving and precipitating solid phases on water chemistry along identified subsurface flow pathways with a focus on metal sulfides and iron oxides as influential to acid mine seepage into the affected lakes.

Sulfur and iron cycling in deep-subsurface, coal bed-containing sediments off Shimokita (Japan)

NASA Astrophysics Data System (ADS)

Riedinger, N.; Smirnoff, M. N.; Gilhooly, W.; Phillips, S. C.; Lyons, T. W.; 337 Scientific Party, I.

2013-12-01

The main goal of IODP Expedition 337 was the identification and characterization of the deep coal bed biosphere and hydrocarbon system off the Shimokita Peninsula (Japan) in the northwestern Pacific using the D/V Chikyu. To accomplish this scientific objective, it was also necessary to investigate the inorganic biogeochemistry in order to identify possible electron acceptors and bio-essential nutrients. These biogeochemical parameters greatly influence both, the composition and abundance of microbial communities as well as the organic carbon cycle. In turn, the microbially mediated carbon cycle influences the diagenetic reactions in the subsurface, thus, altering geochemical and physical characteristics of the material. Here we present results from metal and sulfur geochemical analyses from the deep-subsurface sediments (about 1250 to 2466 mbsf) at Site C0020 off Shimokita. The measured concentrations of acid volatile sulfur (AVS) as well as chromium reducible sulfur (CRS) reflect the alteration of iron oxides to iron sulfides and indicate that the main sulfur-bearing phase in the investigated sediments is pyrite. Concentrations of intermediate sulfur species are minor and occur mainly in the coal-bearing interval. Our data show that the uppermost sediments contain higher amounts of pyrite (up to 1.2 wt.%) with an average of 0.5 wt.% compared to the deeper deposits (below about 1800 mbsf), which show an average of 0.16 wt.%. In contrast, iron oxide concentrations are highest in the deeper sediment sections (up to 0.4%), where pyrite concentrations are low. The alteration of iron oxides to sulfides in theses lower section was probably governed by the amount of available sulfide in the pore water. The occurrence of (bio-)reactive iron phases in these deeply buried sediments has implications for the deep biosphere as those minerals have the potential to serve as electron acceptors during burial, including reactions involving deep sourced electron donors, such as hydrogen and methane - related to the coal bed as the potential source. Thus, the deep subsurface coal beds off Shimokita provide an ideal environment to investigate microbial and metal interactions under extreme conditions.

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

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

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.

Textural and stable isotope studies of the Big Mike cupriferous volcanogenic massive sulfide deposit, Pershing County, Nevada.

USGS Publications Warehouse

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.

Radiometric reconnaissance in the Garfield and Taylor park quadrangles, Chaffee and Gunnison counties, Colorado

USGS Publications Warehouse

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.

Use of airborne hyperspectral data to estimate residual heavy metal contamination and acidification potential in the Guadiamar floodplain Andalusia, Spain after the Aznacollar mining accident

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.

Enabling Earth-Abundant Pyrite (FeS2) Semiconductor Nanostructures for High Performance Photovoltaic Devices

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

Experimental Oxidation of Iron Sulphides from Intertidal Surface Sediments: Stable Isotope Effects (S, O, C)

NASA Astrophysics Data System (ADS)

Ebersbach, F.; Böttcher, M. E.; Al-Raei, A. M.; Segl, M.

2009-04-01

Top intertidal sediments show a pronounced zone of activities of sulphate-reducing bacteria. Iron sulfides may be formed, but a substantial part is reoxidized to sulfate. Microbial or chemical reoxidation can be further enhanced by a resuspension of surface sediments by tidal currents or storms. The rates of the different processes depend on the site-secific sedimentological properties (e.g., grain size, iron and sulphur contents etc.). In the present study 3 different areas of the German Wadden Sea were studied: a mud flat in the Jade Bay, and sandy sediments in the intertidals of Spiekeroog and Sylt islands. The latter site is part of an in-situ lugworm-exclusion experiment. The goal was the experimental and field investigation of the fate of iron sulfides and the formation of sulphate upon resuspension of intertidal surface sediments in oxygenated seawater. All sites were geochemically analyzed for dissolved and solid phase iron, manganese, sulphur and carbon phases/species, and sulphate reduction rates were measured using radiotracers. Dissolved chloride and grain sizes analysis where additionally carried out. TOC, S and metal phase contents were higher in mud compared to sandy sediments. Field results demonstrate gross but only minor net sulphide production and a downcore increases in FeS contents, due to intense sulphide oxidation at the surface. Pyrite, on the other hand, was abundant through the sediments due to continuous sediment reworking. The fate of iron-sulphides and accumulation of sulphate as a function of time was followed in batch experiments using dark suspensions of surface sediments in site-bottom waters at room temperature. During the experiments, each sample was shaken continuously under exposition to oxygen, and sub-samples were taken at the beginning and after discrete time intervalls. A very fast oxidation rate of AVS led to a complete exhaustion within a day, whereas Cr(II)-reducible sulfur was inititially built up and then decreased. This observation can be explained by a formation of S° and FeOOH, followed by the oxidation of pyrite. The dissolved species (SO4/Cl ratios) reflected the continuous accumulation of sulphate as an oxidation product. Dissolved inorganic carbonate (DIC) concentrations decreased upon reaction progress, due to the liberation of protons upon iron sulphide oxidation and degassing of carbon dioxide. The 13C/12C ratio of the residual DIC increased due to the preferential desorption of 12CO2. 34S and 18O contents of dissolved sulphate further show process specific isotope discrimination. The experiments demonstrate the importance of oxidation on the fate of FeS , but less pyrite and the formation of sulphate from resuspended intertidal surface sediments. Acknowledgements: The authors gratefully acknowledge discussions and field advice by N. Volkenborn, and financial support from Deutsche Forschungsgemeinschaft during DFG-SPP ‚BioGeoChemistry of the Wadden Sea' (JO 307/4, BO 1584/4), Max Planck Society, and Leibniz-IO Warnemünde.

Improvement in grade of minerals using simultaneous Bio-oxidation of invisible gold concentrate and deep-sea manganese crust

NASA Astrophysics Data System (ADS)

Myung, EunJi; Cho, Kang Hee; Kim, Hyun Soo; Park, Cheon Young

2016-04-01

Many sulfides of metal such as galena, sphalerite, chalcopyrite, and pyrite, are semiconductors. When two kinds of such minerals contact each other in an electrolyte, a galvanic couple, where the mineral of lower rest potential as anode, and that of higher rest potential as cathode forms. Manganese dioxide is also a semiconductor with much higher rest potential than all sulfides mentioned above, so that a galvanic couple in which both the minerals would dissolve simultaneously can form, when it contacts with any of the sulfides. The aim of this study was to investigate the improvement in grade of minerals using the simultaneous bio-oxidation of deep-sea manganese crust and invisible gold concentrate. The samples(deep-sea manganese crust and invisible gold concentrate) were characterized by chemical and XRD analysis. The primary components of the invisible gold concentrate was pyrite and quartz and the deep-sea manganese crust was amorphous material, as detected using XRD. The result of chemical analysis showed that Au, Ag, Te contents in the invisible gold concentrate 130.2, 954.1 and 1,043.6 mg/kg, respectively. and that Mn, Ni, Co contents in the deep-sea manganese crust 19,501.5, 151.9, 400.4 mg/kg, respectively. In order to increase the bacteria's tolerance of heavy metals, the bacteria using bio-oxidation experiments were repeatedly subcultured in an Cu adaptation-medium containing of 382.98 mg/l for 20 periods of 21 days. The improvement in grade of samples of in present adapted bacteria condition was greater than another conditions(control and in present non-adapted bacteria). The Au-Ag-Te contents in the invisible gold concentrate was enhanced in the order of physical oxidation, simultaneous/non-adaptive bio-oxidation, adaptive/bio-oxidation, simultaneous/adaptive bio-oxidation. If the bacteria is adapted to heavy metal ions and an optimization of conditions is found in future bio-oxidation-leaching processes. Acknowledgment : "This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"

Río Tinto: A Geochemical and Mineralogical Terrestrial Analogue of Mars

NASA Astrophysics Data System (ADS)

Amils, Ricardo; Fernández-Remolar, David

2014-09-01

The geomicrobiological characterization of the water column and sediments of Río Tinto (Huelva, Southwestern Spain) have proven the importance of the iron and the sulfur cycles, not only in generating the extreme conditions of the habitat (low pH, high concentration of toxic heavy metals), but also in maintaining the high level of microbial diversity detected in the basin. It has been proven that the extreme acidic conditions of Río Tinto basin are not the product of 5000 years of mining activity in the area, but the consequence of an active underground bioreactor that obtains its energy from the massive sulfidic minerals existing in the Iberian Pyrite Belt. Two drilling projects, MARTE (Mars Astrobiology Research and Technology Experiment) (2003-2006) and IPBSL (Iberian Pyrite Belt Subsurface Life Detection) (2011-2015), were developed and carried out to provide evidence of subsurface microbial activity and the potential resources that support these activities. The reduced substrates and the oxidants that drive the system appear to come from the rock matrix. These resources need only groundwater to launch diverse microbial metabolisms. The similarities between the vast sulfate and iron oxide deposits on Mars and the main sulfide bioleaching products found in the Tinto basin have given Río Tinto the status of a geochemical and mineralogical Mars terrestrial analogue.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

Petrographic and geochemical contrasts and environmentally significant trace elements in marine-influenced coal seams, Yanzhou mining area, China

USGS Publications Warehouse

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.

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.

Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans

PubMed Central

Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu

2000-01-01

The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768

Bacterialike (filamentous) structures associated with pyritized burrow linings, Arnheim Formation (Upper Ordovician), southeastern Indiana

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.

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

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.

Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

USGS Publications Warehouse

Heard, I.; Senftle, F.E.

1984-01-01

Solutions of 30% H2O2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H2O2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions (pH < 1.5). After acid demineralization, samples of the same anthracite underwent a significant enhancement of oxidation in both acid and alkaline solutions (pH = 0.4-11.5). As all the iron had been removed from the surface and the reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H2O2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

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

PubMed

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.

Morphology, origin and infrared microthermometry of fluid inclusions in pyrite from the Radka epithermal copper deposit, Srednogorie zone, Bulgaria

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 connection between iron ore formations and "mud-shrimp" colonizations around sunken wood debris and hydrothermal sediments in a Lower Cretaceous continental rift basin, Mecsek Mts., Hungary

NASA Astrophysics Data System (ADS)

Jáger, Viktor; Molnár, Ferenc; Buchs, David; Koděra, Peter

2012-09-01

In the Early Cretaceous, the continental rift basin of the Mecsek Mts. (Hungary), was situated on the southern edge of the European plate. The opening of the North Atlantic Ocean created a dilatational regime that expanded to the southern edge of the European plate, where several extensional basins and submarine volcanoes were formed during the Early Cretaceous epoch. Permanent seaquake activity caused high swell events during which a large amount of terrestrial wood fragments entered into submarine canyons from rivers or suspended woods which had sunk into the deep seafloor. These fragments created extended wood-fall deposits which contributed large-scale flourishing of numerous burrowing thalassinid crustaceans. Twelve different thalassinid coprolite ichnospecies can be found in the Berriasian-Hauterivian volcano-sedimentary formations. According to the seladonitic crustacean burrows which associated with framboidal pyrite containing Zoophycos and Chondrites ichnofossils (i.e. a "fodinichnia" trace fossil association), the bottom water was aerobic and the pore water was anaerobic; in the latter sulfate reduction occurred. The preservation of wood fragments around thalassinid burrows can be explained by rapid sedimentation related to turbidity currents. Due to the low temperature hydrothermal circulations of seawater, large amounts of iron were released from intrusive, pillowed basaltic sills; these sills intruded into soft, water-saturated sediments containing large amounts of thalassinid excrement. In the coprolites can be found idiomorphic mineral particles originating from the basalts, and coprolites can often be found in peperitic interpillow sediments. This indicates that the life-activity of the decapoda crustaceans in many Lower Cretaceous occurrences initially preceded the first magmatic eruptions. The paroxysm of the rift volcanism took place during the Valanginian age, when some submarine volcanoes emerged above sea level, reaching a maximum height of 300 m (above sea level); from these volcanoes further terrestrial plant debris got into the basin. Hydrothermal vents, which periodically occurred around basaltic bodies until the Hauterivian, could have contributed to the creation of favourable temperature or nutritional conditions for some decapoda crustaceans - e.g the recently described new callianassid (Nihonotrypaea thermophila), which is known only from hydrothermally infuenced habitats. Around the intrusive pillow basalts, hydrothermal circulation of oxygenated seawater occured and thick seladonitic and goethitic fills formed along the cracks and cavities of pillowed basalts. When oxidized, sulfate-rich fluids passed into the crustacean coprolite-rich, reductive and anaerobic interpillow sediments, these fluids underwent an intensive sulfate reduction. This was primarily due to termophil sulfate reducers which as proved by the negative sulfur isotope values (- 35.9‰ and - 28.0‰ δ 34S) of sulfidic hydrothermal chimneys which contain framboidal pyrite and which were formed between the pillow basalts. The largest chimney structure reached a height of 1 m, with a mass of about 150 kg. The sulfide phase is characterized by Mo enrichments up to 511 ppm. The fluid inclusion measurements from the calcitic precipitations of the sulfide chimneys indicate low temperature (~ 129 °C) hydrothermal activity, and the salinity of the primary fluid inclusions proves the seawater origin of the hydrothermal fluids. In some thalassinid crustacean coprolite rich interpillow sediments and in the cracks of some hydrothermal calcite, there is the presence of black, lustrous bitumine (gilsonite) which is the distillation product of hydrothermal petroleum formed mainly by the coprolites. Hydrothermal circulations of oxygenated seawater caused subsequent oxidation of the sulfidic, interpillow sediments and chimneys; these were altered to form goethite. Due to the short-period of the hydrothermal activity among the intrusive pillowed basalts, sulfidized interpillow sediments could not be oxidized completely. The texture of the goethitic iron ore (as an interpillow sediment) is network-like and dentritic, which is very similar to the iron-oxidic and microbial textured sediments of the Juan de Fuca Ridge. The dendritic iron-oxide-hydroxide particles which were involved in this study are not hollow and exceed the size-domain characteristic for bacterial products. However, in some cases hollow- and tube-like particles having a diameter of 1.2-1.5 μm can refer to the activity of the Sphaerotilus-Leptothrix iron-oxidizer bacterial group.

Migration of trace elements from pyrite tailings in carbonate soils.

PubMed

Dorronsoro, C; Martin, F; Ortiz, I; García, I; Simón, M; Fernández, E; Aguilar, J; Fernández, J

2002-01-01

In the carbonate soils contaminated by a toxic spill from a pyrite mine (Aznalcóllar, southern Spain), a study was made of a thin layer (thickness = 4 mm) of polluted soil located between the pyrite tailings and the underlying soil. This layer, reddish-yellow in color due to a high Fe content, formed when sulfates (from the oxidation of sulfides) infiltrated the soil, causing acidification (to pH 5.6 as opposed to 8.0 of unaffected soil) and pollution (in Zn, Cu, As, Pb, Co, Cd, Sb, Bi, Tl, and In). The less mobile elements (As, Bi, In, Pb, Sb, and Tl) concentrated in the uppermost part of the reddish-yellow layer, with concentration decreasing downward. The more mobile elements (Co, Cd, Zn, and Cu) tended to precipitate where the pH was basic, toward the bottom of the layer or in the upper part of the underlying soil. The greatest accumulations occurred within the first 6 mm in overall soil depth, and were negligible below 15 mm. In addition, the acidity of the solution from the tailings degraded the minerals of the clay fraction of the soils, both the phyllosilicates as well as the carbonates. Also, within the reddish-yellow layer, gypsum formed autigenically, together with complex salts of sulfates of Fe, Al, Zn, Ca, and Mn, jarosite, and oxihydroxides of Fe.

Chemical investigations of aquifers affected by pyrite oxidation in the Bitterfeld lignite district.

PubMed

Grützmacher, G; Hindel, R; Kantor, W; Wimmer, R

2001-01-01

In a large area around the former open-pit lignite mines near Bitterfeld, Germany, groundwater taken from wells was analyzed for the major cations, anions, and trace elements. Quaternary and Tertiary sediments were collected from aquifers exposed on the sides of the pits and from boreholes outside the mines and analyzed for major and trace elements, as well as for carbonate, pyritic sulfur and total organic carbon. The pH and electrical conductivity of the sediments in suspension were measured. Significant differences were determined between the Tertiary sediments of the aquifers that were exposed to atmospheric oxygen during the lowering of the groundwater table and those outside the cone of depression. The greatest differences were found in the pyrite content, the pH values, and the electrical conductivity. In order to map the degree to which the mining of the lignite has affected the quality of the groundwater in the study area, the water samples were divided into six classes on the basis of their sulfate content. The neutralization potential was calculated to estimate the potential for acidification. Prediction of future groundwater quality is based on both (i) the present composition of the groundwater, surface water, and Quaternary and Tertiary aquifer sediments and (ii) the present and future groundwater flow directions. These studies have shown which parameters are important for future groundwater monitoring.

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

Microbial Diversity and Its Relationship to Physicochemical Characteristics of the Water in Two Extreme Acidic Pit Lakes from the Iberian Pyrite Belt (SW Spain)

PubMed Central

López-Pamo, Enrique; Gomariz, María; Amils, Ricardo; Aguilera, Ángeles

2013-01-01

The Iberian Pyrite Belt (IPB) hosts one of the world’s largest accumulations of acidic mine wastes and pit lakes. The mineralogical and textural characteristics of the IPB ores have favored the oxidation and dissolution of metallic sulfides, mainly pyrite, and the subsequent formation of acidic mining drainages. This work reports the physical properties, hydrogeochemical characteristics, and microbial diversity of two pit lakes located in the IPB. Both pit lakes are acidic and showed high concentrations of sulfate and dissolved metals. Concentrations of sulfate and heavy metals were higher in the Nuestra Señora del Carmen lake (NSC) by one order of magnitude than in the Concepción (CN) lake. The hydrochemical characteristics of NSC were typical of acid mine waters and can be compared with other acidic environments. When compared to other IPB acidic pit lakes, the superficial water of CN is more diluted than that of any of the others due, probably, to the strong influence of runoff water. Both pit lakes showed chemical and thermal stratification with well defined chemoclines. One particular characteristic of NSC is that it has developed a chemocline very close to the surface (2 m depth). Microbial community composition of the water column was analyzed by 16S and 18S rRNA gene cloning and sequencing. The microorganisms detected in NSC were characteristic of acid mine drainage (AMD), including iron oxidizing bacteria (Leptospirillum, Acidithiobacillus ferrooxidans) and facultative iron reducing bacteria and archaea (Acidithiobacillus ferrooxidans, Acidiphilium, Actinobacteria, Acidimicrobiales, Ferroplasma) detected in the bottom layer. Diversity in CN was higher than in NSC. Microorganisms known from AMD systems (Acidiphilium, Acidobacteria and Ferrovum) and microorganisms never reported from AMD systems were identified. Taking into consideration the hydrochemical characteristics of these pit lakes and the spatial distribution of the identified microorganisms, a model explaining their geomicrobiology is advanced. PMID:23840525

Trace Element Geochemistry of Magnetite and Accesory Phases from El Romeral Iron Oxide-Apatite Deposit, Northern Chile

NASA Astrophysics Data System (ADS)

Barra, F.; Rojas, P.; Reich, M.; Deditius, A.; Simon, A. C.

2017-12-01

Iron oxide-apatite (IOA) or "Kiruna-type" deposits are an important source of Fe, P, REE, among other essential elements for society. Three main hypotheses have been proposed to explain the genesis of these controversial deposits, which invoke liquid immiscibility, hydrothermal replacement or a magmatic-hydrothermal origin driven by flotation of magnetite-bubble pairs. Here we focus on the El Romeral, one of the largest IOA deposits located in the southernmost part of the Cretaceous Chilean Iron Belt. We combined SEM observations and EMPA analyses of magnetite, actinolite, pyrite, and apatite, with micro-Raman determinations of mineral inclusions within magnetite grains. Two textural types of magnetite were identified at El Romeral: (i) inclusion-rich magnetite (Mag I), and (ii) inclusion-poor magnetite (Mag II) that are commonly surrounding the inclusion-rich Mag I grains. Mag I is characterized by high V ( 2500-2800 ppm) and Ti (300-1000 ppm) contents with high-temperature mineral inclusions such as ilmenite, Ti-pargasite and clinochlore at depth, and quartz and phlogopite inclusions in shallower samples. These characteristics are consistent with a magmatic origin for Mag I. Inclusion-poor magnetite (Mag II) have high V (2400-2600 ppm) and lower Ti (70-200 ppm) contents than Mag I, which point to chemical changes of the mineralizing fluid(s). An increase in thermal gradient with depth is evidenced by the presence of high-temperature (low #Fe) actinolite, as well as F-rich apatite and pyrite with high Co:Ni (>1) in the deep zones. In contrast, lower Co:Ni ratios (<0.5) in pyrite and higher Cl contents in OH-rich apatite are detected in samples from shallower levels. This vertical chemical variation supports a magmatic-hydrothermal origin for the El Romeral deposit, and point to compositional changes driven by decompression of a magnetite-fluid suspension.

Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

USGS Publications Warehouse

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.

Simulation of pyrite oxidation in fresh mine tailings under near-neutral conditions.

PubMed

Alakangas, Lena; Lundberg, Angela; Nason, Peter

2012-08-01

Sulphidic residual products from ore processing may produce acid rock drainage, when exposed to oxygen and water. Predictions of the magnitude of ARD and sulphide oxidation rates are of great importance in mine planning because they can be used to minimize or eliminate ARD and the associated economic and environmental costs. To address the lack of field data of sulphide oxidation rate in fresh sulphide-rich tailings under near-neutral conditions, determination and simulation of the rate was performed in pilot-scale at Kristineberg, northern Sweden. The quality of the drainage water was monitored, along with oxygen and carbon dioxide concentrations. The chemical composition of the solid tailings was also determined. The field data were compared to predictions from simulations of pyrite oxidation using a 1-D numerical model. The simulations' estimates of the amount of Fe and S released over a seven year period (52 kg and 178 kg, respectively) were in reasonably good agreement with those obtained by analysing the tailings (34 kg and 155 kg, respectively). The discrepancy is probably due to the formation of secondary precipitates such as iron hydroxides and gypsum; which are not accounted for in the model. The observed mass transport of Fe and S (0.05 and 1.0 kg per year, respectively) was much lower than expected on the basis of the simulations and the core data. Neutralization reactions involving carbonates in the tailings result in a near-neutral pH at all depths except at the oxidation front (pH < 5), indicating that the dissolution of carbonates was too slow for the acid to be neutralized, which instead neutralized deeper down in the tailings. This was also indicated by the reduced abundance of solid Ca at greater depths and the high levels of carbon dioxide both of which are consistent with the dissolution of carbonates. It could be concluded that the near-neutral pH in the tailings has no decreasing effect on the rate of sulphide oxidation, but does reduce the concentrations of dissolved elements in the drainage water due to the formation of secondary minerals. This means that sulphide oxidation rates may be underestimated if determined from drainage alone.

Laboratory support for a methanogenesis driven

NASA Astrophysics Data System (ADS)

Navarro-Gonzalez, R.; Montoya, L.; Davis, W.; McKay, C.

Recent geological evidence strongly suggests that Europa may currently possess a global subsurface water ocean. Since liquid water is a fundamental requirement for life as we know it, there is great speculation on the possibility of life in Europa. For such organisms to survive, there must be an energy source available for metabolism, growth and reproduction. On Earth this energy is principally derived from sunlight through photosynthesis. Due to the expected large ice crust thickness (10 to 100 km) of the satellite, this energy source is unlikely to support a biosphere. Hydrothermal vents have been suggested as a potential environment for chemotrophs. However, for such organisms to obtain energy they depend on oxidants dissolved and transported from the oxygenic Earth's atmosphere to the deep ocean. Without a supply of oxidants from Europa's crust, methanogenesis associated to hydrothermal vents may potentially drive a biosphere in Europa's ocean. Here we explore this possibility experimentally by simulating a hydrothermal vent relevant to Europa and analyzing the resulting gas products by gas chromatography coupled to Fourier transform infrared and mass spectrometries. The chemical composition of the hydrothermal vent gases was derived from a thermochemical model assuming that Europa had a cometary (solar, less H) abundance at a high temperature characteristic of a vent. Specifically the following gas mixture was used: 45% CO2 , 45% CH4 and 10 % N2 . A 500 ml stainless steel reactor was filled with 200 ml triply distilled water and the gas mixture at 1 bar at 25 °C . In some experiments 3 g of pyrite were added into the reaction vessel. The system was heated for 24 hrs at 350 °C . At the completion of the experiment, the reaction was quenched to 25 °C and the gas mixture gas analyzed by GC-FTIR-MS techniques. In the absence of pyrite, methane is oxidized to carbon dioxide with the possible production of hydrogen. In contrast in the presence of pyrite, methane is converted into a suite of hydrocarbons from C2 to C7 containing all possible isomers. The production of these compounds was found at temperatures as low as 150 °C . In order to get a better understanding of the chemical mechanism involved in the synthesis of hydrocarbons and explore the effect on the initial oxidation state of the carbon used, we performed new experiments in which the oxidation state of carbon was varied from 100% methane to 100% carbon dioxide. In all cases, a suite of complex hydrocarbons were formed in the hydrothermal simulations. Therefore, our results strongly support two possible forms of methanogenesis in Europa driven by : 1) Reduction of CO2 to CH4 using H2 ; and 2) Cleavage of hydrocarbons back to CH 4 .

The Genesis of Precious and Base Metal Mineralization at the Miguel Auza Deposit, Zacatecas, Mexico

NASA Astrophysics Data System (ADS)

Findley, A. A.; Olivo, G. R.; Godin, L.

2009-05-01

The Miguel Auza mine located in Zacatecas State, Mexico, is a vein-type polymetallic epithermal deposit hosted in deformed argillite, siltstone and, greywacke of the Cretaceous Caracol Formation. Silver-rich base metal veins (0.2 m to >1.5 m wide) are spatially associated with the NE-striking, steeply SE- dipping (70-80°) Miguel Auza fault over a strike length of 1.6 km and a depth of 460 m. A 2 km2 monzonitic stock located in the proximity of the mineralized zones, has previously been interpreted as the source of the mineralizing fluids. Four distinct structural stages are correlated with hydrothermal mineral deposition: (I) The Pre-ore stage is characterized by normal faulting, fracturing of host rock, and rotation of bedding planes. This stage consists of quartz, illite, chlorite, +/- pyrite alteration of sedimentary wall rocks. (II) The Pyrite-vein stage is associated with reverse-sense reactivation of early normal faults, dilation of bedding planes/fractures, and deposition of generally barren calcite + pyrite veinlets. (III) The Main-ore stage is related to the development of reverse-fault- hosted massive sulphide veins. During this stage three phases of mineral deposition are recorded: early pyrite and arsenopyrite, intermediate chalcopyrite, pyrite, arsenopyrite, and base metals, and late base metals and Ag-bearing minerals. Associated gangue minerals during the main ore stage are quartz, muscovite, calcite and chlorite. (IV) The Post-ore stage involves late NW-SE striking block faulting, brecciation and calcite veining. Later supergene oxidation of veins led to deposition of Fe-oxides and hydroxides, commonly filling fractures or replacing early-formed sulphide assemblages. The various vein types display classic epithermal textures including open space filling, banding, comb quartz and brecciation. The Ag-bearing minerals comprise pyrargyrite [Ag3(Sb,As)S3], argentotennantite [(Cu,Ag)10(Zn,Fe)2(Sn,As)4S13], polybasite-pearceite [(Ag,Cu)16(Sb,As)2S11], and acanthite [AgS2]; associated sulphides include galena, sphalerite, chalcopyrite, arsenopyrite and pyrite. In the main ore zone, base metal sulphides are commonly intergrown with the Ag-bearing sulfosalts. Analyses of galena show no significant silver values indicating that silver grades are exclusively associated with the Ag-bearing sulfosalts and sulphides. The distribution of the Sb/(Sb + As) ratios in the silver sulfosalts indicate that the ore forming fluid(s) was consistently antimony-rich during the Ag-rich ore deposition with no significant variation laterally, vertically, or along strike of the vein systems. However, Ag/(Ag + Cu) values in argentotennantite decrease along-strike from NE to SW and with depth. Compositions of argentotennantite + pyrargyrite + sphalerite indicate a primary depositional temperature around 325-350° C for the late phase of the Main-ore stage. Compositions of sphalerite also show an increasing trend in FeS (mol %) along strike of the deposit from NE to SW. The geometric relationship between the various structures, vein types, and the regional Miguel Auza fault zone suggest episodic reverse-sense reactivation of normal faults. It is argued that the structural evolution of the area, and, in particular, the Main-ore stage, provided transport pathways for metal-rich fluids and controlled the orientations of ore-bearing veins. Variations in mineral chemistry suggest that the rocks in the NE sector interacted with hotter fluids than in the SW part of the deposit.

Adsorption and oxidation of SO₂in a fixed-bed reactor using activated carbon produced from oxytetracycline bacterial residue and impregnated with copper.

PubMed

Zhou, Baohua; Yu, Lei; Song, Hanning; Li, Yaqi; Zhang, Peng; Guo, Bin; Duan, Erhong

2015-02-01

The SO₂removal ability (including adsorption and oxidation ability) of activated carbon produced from oxytetracycline bacterial residue and impregnated with copper was investigated. The activated carbon produced from oxytetracycline bacterial residue and modified with copper was characterized by x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The effects of the catalysts, SO₂concentration, weight hourly space velocity, and temperature on the SO₂adsorption and oxidation activity were evaluated. Activated carbon produced from oxytetracycline bacterial residue and used as catalyst supports for copper oxide catalysts provided high catalytic activity for the adsorbing and oxidizing of SO₂from flue gases.

Treatment of Actual Chemical Wastewater by a Heterogeneous Fenton Process Using Natural Pyrite

PubMed Central

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

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

PubMed

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.

Multiple sulfur-isotopic evidence for a shallowly stratified ocean following the Triassic-Jurassic boundary mass extinction

NASA Astrophysics Data System (ADS)

Luo, Genming; Richoz, Sylvain; van de Schootbrugge, Bas; Algeo, Thomas J.; Xie, Shucheng; Ono, Shuhei; Summons, Roger E.

2018-06-01

The cause of the Triassic-Jurassic (Tr-J) boundary biotic crisis, one of the 'Big Five' mass extinctions of the Phanerozoic, remains controversial. In this study, we analyzed multiple sulfur-isotope compositions (δ33S, δ34S and δ36S) of pyrite and Spy/TOC ratios in two Tr-J successions (Mariental, Mingolsheim) from the European Epicontinental Seaway (EES) in order to better document ocean-redox variations during the Tr-J transition. Our results show that upper Rhaetian strata are characterized by 34S-enriched pyrite, low Spy/TOC ratios, and values of Δ33Spy (i.e., the deviation from the mass-dependent array) lower than that estimated for contemporaneous seawater sulfate, suggesting an oxic-suboxic depositional environment punctuated by brief anoxic events. The overlying Hettangian strata exhibit relatively 34S-depleted pyrite, high Δ33Spy, and Spy/TOC values, and the presence of green sulfur bacterial biomarkers indicate a shift toward to euxinic conditions. The local development of intense marine anoxia thus postdated the Tr-J mass extinction, which does not provide support for the hypothesis that euxinia was the main killing agent at the Tr-J transition. Sulfur and organic carbon isotopic records that reveal a water-depth gradient (i.e., more 34S-, 13C-depleted with depth) in combination with Spy/TOC data suggest that the earliest Jurassic EES was strongly stratified, with a chemocline located at shallow depths just below storm wave base. Shallow oceanic stratification may have been a factor for widespread deposition of black shales, a large positive shift in carbonate δ13C values, and a delay in the recovery of marine ecosystems following the Tr-J boundary crisis.

Origin of sulfide and phosphate deposits in Upper Proterozoic carbonate strata, Irece basin, Bahia, Brazil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyle, J.R.; Misi, A.

1991-03-01

Carbonate strata of the Una Group represent late Proterozoic platform sedimentation in the Irece basin of north-central Brazil. Stratabound sulfide- and phosphate-rich units occur within a 50-m thick tidal flat sequence of dolomitic limestone and cherty dolomite. Three types of primary phosphate concentrations are present: columnar stromatolitic, laminar stromatolitic, and intraclastic. Resedimented phosphate clasts and phosphatic units interbedded with non phosphatic dolomites suggest early diagenetic replacement of algal carbonate units. Local stratabound Zn-Pb-Ag sulfide concentrations at the Tres Irmas prospect occur within silty dolomite with shallow water sedimentary structures and local disturbed laminae, synsedimentary faults, and breccias. Sulfide minerals includemore » pyrite, sphalerite, galena, marcasite, jordanite, tetrahedrite, and covellite. Pyrite crystal aggregates commonly show bladed forms. Nodular aggregates of length-slow quartz are locally associated with sulfides. Sulfur isotope analyses indicate relatively uniform heavy {delta}{sup 34}S values. Barite shows a {delta}{sup 34}S range from +25.2 to +29.6{per thousand}, CDT. Pyrite and sphalerite representative of a variety of textural types have a {delta}{sup 34}S range of +20.2 to +22.6{per thousand}. Late Proterozoic evaporite sulfates show a wide range of {delta}{sup 34} S values from about +10 to +28{per thousand}. Thus, the {delta}{sup 34}S values for Irece barite could reflect original seawater sulfate values. However, the relatively heavy {delta}{sup 34}S values of the associated sulfides suggests that the original seawater sulfate was modified by bacterial sulfate reduction processes in shallow sea floor sediments. Textural and {delta}{sup 34}S evidence suggests that a later stage of metallic mineralization scavenged sulfur from preexisting sulfides or from direct reduction of evaporitic sulfate minerals.« less

Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis

USGS Publications Warehouse

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.

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

A contribution to improve the calculation of the acid generating potential of mining wastes.

PubMed

Chopard, Aurélie; Benzaazoua, Mostafa; Bouzahzah, Hassan; Plante, Benoît; Marion, Philippe

2017-05-01

Mine wastes from sulfide-bearing ore extraction and processing are often stored at the surface of mine sites and could generate mine drainage. Prediction tests are completed to predict the water quality associated with the deposition of mining wastes. Static tests can quickly assess the acid-generating potential (AP) and the neutralization potential (NP). Whereas some studies recommend to take into account a mineral reactivity factor for the NP determination, the reactivity rates of acidifying minerals are not considered in the AP calculation. The aim of this study is to bring contribution to the improvement of the static test determination by adding kinetic factors in the AP determination. Eight sulfides (pyrite, Ni-pyrite, pyrrhotite, Ni-pyrrhotite, chalcopyrite, galena, sphalerite, arsenopyrite) and a sulfosalt (gersdorffite) were separately submitted to kinetic tests in modified weathering cells. This test was selected for its rapidity of results and for the low amount of material used, as it is somewhat difficult to obtain pure minerals samples. Five synthetic tailings were composed by mixing pure sulfides in various proportions and submitted to the same kinetic tests. The oxidation rates of synthetic tailings were compared with the weighted combined oxidation rates of individual pure sulfides. The oxidation rates of the synthetic tailings calculated from those of pure sulfides are within the same order of magnitude than those obtained through the kinetic experiments. The AP of synthetic tailings were calculated according to standard equations of the literature and compared with the new method. Copyright © 2017 Elsevier Ltd. All rights reserved.

Arsenic control during aquifer storage recovery cycle tests in the Floridan Aquifer.

PubMed

Mirecki, June E; Bennett, Michael W; López-Baláez, Marie C

2013-01-01

Implementation of aquifer storage recovery (ASR) for water resource management in Florida is impeded by arsenic mobilization. Arsenic, released by pyrite oxidation during the recharge phase, sometimes results in groundwater concentrations that exceed the 10 µg/L criterion defined in the Safe Drinking Water Act. ASR was proposed as a major storage component for the Comprehensive Everglades Restoration Plan (CERP), in which excess surface water is stored during the wet season, and then distributed during the dry season for ecosystem restoration. To evaluate ASR system performance for CERP goals, three cycle tests were conducted, with extensive water-quality monitoring in the Upper Floridan Aquifer (UFA) at the Kissimmee River ASR (KRASR) pilot system. During each cycle test, redox evolution from sub-oxic to sulfate-reducing conditions occurs in the UFA storage zone, as indicated by decreasing Fe(2+) /H2 S mass ratios. Arsenic, released by pyrite oxidation during recharge, is sequestered during storage and recovery by co-precipitation with iron sulfide. Mineral saturation indices indicate that amorphous iron oxide (a sorption surface for arsenic) is stable only during oxic and sub-oxic conditions of the recharge phase, but iron sulfide (which co-precipitates arsenic) is stable during the sulfate-reducing conditions of the storage and recovery phases. Resultant arsenic concentrations in recovered water are below the 10 µg/L regulatory criterion during cycle tests 2 and 3. The arsenic sequestration process is appropriate for other ASR systems that recharge treated surface water into a sulfate-reducing aquifer. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.

Innovative Approach to Prevent Acid Drainage from Uranium Mill Tailings Based on the Application of Na-Ferrate (VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandes, H.M.; Reinhart, D.; Lettie, L.

2006-07-01

The operation of uranium mining and milling plants gives rise to huge amounts of wastes from both mining and milling operations. When pyrite is present in these materials, the generation of acid drainage can take place and result in the contamination of underground and surface waters through the leaching of heavy metals and radionuclides. To solve this problem, many studies have been conducted to find cost-effective solutions to manage acid mine drainage; however, no adequate strategy to deal with sulfide-ric h wastes is currently available. Ferrate (VI) is a powerful oxidizing agent in aqueous media. Under acidic conditions, the redoxmore » potential of the Ferrate (VI) ion is the highest of any other oxidant used in wastewater treatment processes. The standard half cell reduction potential of ferrate (VI) has been determined as +2.20 V to + 0.72 V in acidic and basic solutions, respectively. Ferrate (VI) exhibits a multitude of advantageous properties, including higher reactivity and selectivity than traditional oxidant alternatives, as well as disinfectant, flocculating, and coagulant properties. Despite numerous beneficial properties in environmental applications, ferrate (VI) has remained commercially unavailable. Starting in 1953, different methods for producing a high purity, powdered ferrate (VI) product were developed. However, producing this dry, stabilized ferrate (VI) product required numerous process steps which led to excessive synthesis costs (over $20/lb) thereby preventing bulk industrial use. Recently a novel synthesis method for the production of a liquid ferrate (VI) based on hypochlorite oxidation of ferric ion in strongly alkaline solutions has been discovered (USPTO 6,790,428; September 14, 2004). This on-site synthesis process dramatically reduces manufacturing cost for the production of ferrate (VI) by utilizing common commodity feedstocks. This breakthrough means that for the first time ferrate (VI) can be an economical alternative to treating acid mining drainage generating materials. The objective of the present study was to investigate a methodology of preventing the generation of acid drainage by applying ferrate (VI) to acid generating materials prior to the disposal in impoundments or piles. Oxidizing the pyritic material in mining waste could diminish the potential for acid generation and its related environmental risks and long-term costs at disposal sites. The effectiveness of toxic metals removal from acid mine drainage by applying ferrate (VI) is also examined. Preliminary results presented in this paper show that the oxidation of pyrite by ferrate is a first-order rate reaction in Fe(VI) with a half-life of about six hours. The stability of Fe(VI) in water solutions will not influence the reaction rate in a significant manner. New low-cost production methods for making liquid ferrate on-site makes this technology a very attractive option to mitigate one of the most pressing environmental problems in the mining industry. (authors)« less

Selective flotation of inorganic sulfides from coal

DOEpatents

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.

Study on the surface sulfidization behavior of smithsonite at high temperature

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Mössbauer study of Fe mineralogy with respect to rank, type and Colombian carboniferous zone

NASA Astrophysics Data System (ADS)

Caballero, F. Reyes; Martínez Ovalle, S. A.; Díaz Lagos, M.; Gómez, O. P.; Blandón, A.

2017-11-01

The transmission mode of Fe-57 Mössbauer spectroscopy was used to identify iron bearing minerals and establish relationships between and among these minerals and the ranks and types of various carboniferous zones in Colombia. Maceral and mineral compositions vary significantly among Colombian carboniferous zones. These variations determine some of the final characteristics and potential uses of coal, and therefore significantly contribute to defining coal quality. A comparison of spectroscopy results shows that the thermal maturity of the Colombian coals ranges from lignite to semianthracite. Similarities and differences exist with respect to conventional parameters. The coals of Córdoba and Cauca have higher sulfur contents > 2 % ash contents. Iron bearing minerals identified included pyrite, which was, found everywhere, and illite, ankerite, siderite, iron sulfates were found in particular areas. Coals from Valle del Cauca, Córdoba, Caldas and Santander are characterized by oxidation of pyrite and its transformation into ferrous or ferric sulfate.

Origin of oxygen in sulfate during pyrite oxidation with water and dissolved oxygen: an in situ horizontal attenuated total reflectance infrared spectroscopy isotope study.

PubMed

Usher, Courtney R; Cleveland, Curtis A; Strongin, Daniel R; Schoonen, Martin A

2004-11-01

FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.

Fe-FeS2 adsorbent prepared with iron powder and pyrite by facile ball milling and its application for arsenic removal.

PubMed

Min, Xiaobo; Li, Yangwenjun; Ke, Yong; Shi, Meiqing; Chai, Liyuan; Xue, Ke

2017-07-01

Arsenic is one of the major pollutants and a worldwide concern because of its toxicity and chronic effects on human health. An adsorbent of Fe-FeS 2 mixture for effective arsenic removal was successfully prepared by mechanical ball milling. The products before and after arsenic adsorption were characterized with scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent shows high arsenic removal efficiency when molar ratio of iron to pyrite is 5:5. The experimental data of As(III) adsorption are fitted well with the Langmuir isotherm model with a maximal adsorption capacity of 101.123 mg/g. And As(V) data were described perfectly by the Freundlich model with a maximal adsorption capacity of 58.341 L/mg. As(III) is partial oxidized to As(V) during the adsorption process. High arsenic uptake capability and cost-effectiveness of waste make it potentially attractive for arsenic removal.

Global transcriptional responses of Acidithiobacillus ferrooxidans Wenelen under different sulfide minerals.

PubMed

Latorre, Mauricio; Ehrenfeld, Nicole; Cortés, María Paz; Travisany, Dante; Budinich, Marko; Aravena, Andrés; González, Mauricio; Bobadilla-Fazzini, Roberto A; Parada, Pilar; Maass, Alejandro

2016-01-01

In order to provide new information about the adaptation of Acidithiobacillus ferrooxidans during the bioleaching process, the current analysis presents the first report of the global transcriptional response of the native copper mine strain Wenelen (DSM 16786) oxidized under different sulfide minerals. Microarrays were used to measure the response of At. ferrooxidans Wenelen to shifts from iron supplemented liquid cultures (reference state) to the addition of solid substrates enriched in pyrite or chalcopyrite. Genes encoding for energy metabolism showed a similar transcriptional profile for the two sulfide minerals. Interestingly, four operons related to sulfur metabolism were over-expressed during growth on a reduced sulfur source. Genes associated with metal tolerance (RND and ATPases type P) were up-regulated in the presence of pyrite or chalcopyrite. These results suggest that At. ferrooxidans Wenelen presents an efficient transcriptional system developed to respond to environmental conditions, namely the ability to withstand high copper concentrations. Copyright © 2015 Elsevier Ltd. All rights reserved.

An evaluation of problems arising from acid mine drainage in the vicinity of Shasta Lake, Shasta County, California

USGS Publications Warehouse

Fuller, Richard H.; Shay, J.M.; Ferreira, R.F.; Hoffman, R.J.

1978-01-01

Streams draining the mined areas of massive sulfide ore deposits in the Shasta Mining Districts of northern California are generally acidic and contain large concentrations of dissolved metals, including iron, copper, and zinc. The streams, including Flat, Little Backbone, Spring, West Squaw, Horse, and Zinc Creeks, discharge into Shasta Reservoir and the Sacramento River and have caused numerous fish kills. The sources of pollution are discharge from underground mines, streams that flow into open pits, and streams that flow through pyritic mine dumps where the oxidation of pyrite and other sulfide minerals results in the production of acid and the mobilization of metals. Suggested methods of treatment include the use of air and hydraulic seals in the mines, lime neutralization of mine effluent, channeling of runoff and mine effluent away from mine and tailing areas, and the grading and sealing of mine dumps. A comprehensive preabatement and postabatement program is recommended to evaluate the effects of any treatment method used. (Woodard-USGS)

Insights into Paleogene biogeochemistry from coupled carbon and sulfur isotopes in foraminiferal calcite.

NASA Astrophysics Data System (ADS)

Rennie, V.; Paris, G.; Abramovitch, S.; Sessions, A. L.; Adkins, J. F.; Turchyn, A. V.

2014-12-01

The Paleogene witnessed large-scale environmental changes, including the beginning of long-term Cenozoic cooling. The carbon isotope composition of foraminiferal calcite suggests a major reorganization of the carbon cycle over the Paleogene, with enhanced organic carbon burial in the Paleocene, and subsequent oxidation of this organic carbon or increased volcanism throughout the Eocene. The sulfur cycle is linked to the carbon cycle via the breakdown of organic carbon during bacterial sulfate reduction. Over geological time, carbon and sulfur isotopic shifts are often coupled due to enhanced pyrite burial being coupled to enhanced organic carbon burial, and enhanced pyrite weathering being coupled to enhanced organic carbon weathering. However, over the Paleogene, carbon and sulfur isotopes are fully decoupled, with the sulfur isotope record showing only one major shift in the early Eocene, after most of the carbon isotope variability is complete. One complication of interpreting the evolution of the sulfur cycle over the Cenozoic, is the fact that the mineral proxies used (typically barite) may not be temporally coincident with those used to reconstruct the carbon cycle (typically carbonate). Furthermore, these minerals are preserved in different locations, and therefore often must be extracted from different sediment cores in different ocean basins, leading to age-model uncertainty when the records are merged. To properly ascertain the phasing between early Cenozoic changes in the carbon cycle and the sulfur cycle, we would ideally measure all isotope records on the same mineral. A new sulfur isotope analytical technique [1] has been optimised for foraminiferal calcite as a proxy for seawater δ34SSO4. The δ34SSO4 in foraminiferal calcite can then be tied to records of carbon isotopes from stratigraphically identical samples, resolving previous age model uncertainties. We present coupled carbon and sulfur isotope records from the same core over the early-to-mid Eocene, to better resolve the relative timing of changes in the carbon and sulfur cycles. We use a numerical model to explore the environmental changes necessary for the observed evolution in both the carbon and sulfur cycles. [1] Paris et al, 2013 Chemical Geology, 345, 50-61

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

USGS Publications Warehouse

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.

Mechanistic study on antibacterial action of zinc oxide nanoparticles synthesized using green route.

PubMed

Happy Agarwal; Soumya Menon; Venkat Kumar, S; Rajeshkumar, S

2018-04-25

A large array of diseases caused by bacterial pathogens and origination of multidrug resistance in their gene provokes the need of developing new vectors or novel drug molecules for effective drug delivery and thus, better treatment of disease. The nanoparticle has emerged as a novel drug molecule in last decade and has been used in various industrial fields like cosmetics, healthcare, agricultural, pharmaceuticals due to their high optical, electronic, medicinal properties. Use of nanoparticles as an antibacterial agent remain in current studies with metal nanoparticles like silver, gold, copper, iron and metal oxide nanoparticles like zinc oxide, copper oxide, titanium oxide and iron oxide nanoparticles. The high anti-bacterial activity of nanoparticles is due to their large surface area to volume ratio which allows binding of a large number of ligands on nanoparticle surface and hence, its complexation with receptors present on the bacterial surface. Green synthesis of Zinc Oxide Nanoparticle (ZnO NP) and its anti-bacterial application has been particularly discussed in the review literature. The present study highlights differential nanoparticle attachment to gram + and gram - bacterial surface and different mechanism adopted by nanoparticle for bacterial control. Pharmacokinetics and applications of ZnO NP are also discussed briefly. Copyright © 2018 Elsevier B.V. All rights reserved.

Acid Saline Weathering of A Massive Sulfide and Gossan Formation: Implications for Development and Preservation of Biosignatures on Mars

NASA Astrophysics Data System (ADS)

Williams, A. J.; Sumner, D. Y.; Zierenberg, R. A.

2010-12-01

The surface of modern Mars is rich in S and Fe minerals. Variations in water activity and the weathering reactions of these minerals have been integral to developing Martian surface conditions during the last 2 Ga. Terrestrial gossans, especially those formed from acid-saline solutions at low water-rock ratio, provide an important analog for understanding how S and Fe minerals may have weathered on Mars. Acidophiles and chemolithotrophs have been identified in these environments on Earth, so they also comprise a model system for putative biosignature formation and preservation that is relevant to conditions on early Mars. The Iron Mountain massive sulfide deposit is capped by a gossan, parts of which were exposed at the surface prior to mining, and parts of which have been exposed for several decades. The deposit is located in seasonally dry northern CA with high late spring to early fall evaporation rates. Samples of pyrite, iron-oxide-rich, and sulfate-rich gossan were collected during the dry season in late spring 2010. Mineral species identified with SEM-EDS, XRD, and optical microscopy include: pyrite, goethite, lepitocrocite, hematite, schwartmanite, gypsum, quartz, and acanthite. As yet unidentified soluble sulfate minerals formed by evaporative concentration are also present. Distilled water added to a pyrite-sulfate sample yielded a pH of ~2.5 once the evaporites dissolved. The spatial variability of minerals and the extent of alteration provide the opportunity to study weathering gradients and solution/reprecipitation in this system. Putative microbial communities containing filaments have been observed in small patches on sample surfaces and in fractures with FEG-SEM and optical microscopy. Although present, textural features interpreted to have formed microbially are sparse. The relative paucity of microbial morphologies in this analog acid-saline system combined with their heterogeneous spatial distribution presents a challenge for remote detection by a rover. In addition, long-term preservation of organics in the oxidizing environments indicated by the presence of iron oxides is difficult. Thus, poor preservation of organic biomarkers might be expected even if microbial colonization of the Fe-rich substrate was present on Mars. However, if microbial activity influences local mineralogy or mineral morphology, this may provide evidence for microbial activity even in the absence of chemical biosignatures.

Selective flotation of inorganic sulfides from coal

DOEpatents

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.

Adhesion of Ferroplasma acidiphilum onto pyrite calculated from the extended DLVO theory using the van Oss-Good-Chaudhury approach.

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Río Tinto: A Geochemical and Mineralogical Terrestrial Analogue of Mars

PubMed Central

Amils, Ricardo; Fernández-Remolar, David

2014-01-01

The geomicrobiological characterization of the water column and sediments of Río Tinto (Huelva, Southwestern Spain) have proven the importance of the iron and the sulfur cycles, not only in generating the extreme conditions of the habitat (low pH, high concentration of toxic heavy metals), but also in maintaining the high level of microbial diversity detected in the basin. It has been proven that the extreme acidic conditions of Río Tinto basin are not the product of 5000 years of mining activity in the area, but the consequence of an active underground bioreactor that obtains its energy from the massive sulfidic minerals existing in the Iberian Pyrite Belt. Two drilling projects, MARTE (Mars Astrobiology Research and Technology Experiment) (2003–2006) and IPBSL (Iberian Pyrite Belt Subsurface Life Detection) (2011–2015), were developed and carried out to provide evidence of subsurface microbial activity and the potential resources that support these activities. The reduced substrates and the oxidants that drive the system appear to come from the rock matrix. These resources need only groundwater to launch diverse microbial metabolisms. The similarities between the vast sulfate and iron oxide deposits on Mars and the main sulfide bioleaching products found in the Tinto basin have given Río Tinto the status of a geochemical and mineralogical Mars terrestrial analogue. PMID:25370383

Formative Processes of a Sliding Zone in Pelitic Schist - Implications of Microscopic Analyses on High-quality Drilled Cores

NASA Astrophysics Data System (ADS)

Yamasaki, S.; Chigira, M.

2009-04-01

Pelitic schist has been known to be easily deformed by gravitational force to form characteristic topographic and geologic features, but little is known about how they develop. This is mainly due to the fact that deformed politic schist is so fragile that it could not be obtained from subsurface without disturbance. We analyzed high-quality undisturbed cores obtained by using a sophisticated drilling technique from two typical pelitic schist landslide sites in Japan. We made analyses on physical, chemical, mineralogical properties and observations from mesoscopic to microscopic rock textures of these cores and found that a special layering of rock-forming minerals determines the locations of shearing by gravity and that there is specific water-rock interaction processes in pelitic schist. Pelitic schist consists of thinly alternating beds of black layers and quartz-rich layers, and a black layer has numerous microscopic layers containing abundant pyrite and graphite grains (pyrite-graphite layers). Many of the black layers were observed to have microfractures connected to open cracks, suggesting that relatively thick, continuous black layers are easily sheared to form an incipient sliding layer. Thus unevenly distributed pyrite-graphite layers likely to determine the potential location of microscopic slip in a rock mass. Shear displacement along black layers occurs unevenly, depending upon the microscopic heterogeneity in mineral composition as well as undulating shape of the layers. Open micro-cracks nearly perpendicular to the schistosity were commonly observed in quartz-rich layers in contact with black layers, suggesting that the shearing occurred with heterogeneous displacements along the black layer and that it occurred under the low confining pressure. This is in the incipient stage of a fracture zone. When shearing occurs along two thick neighboring black layers, the rock in between would be fractured, rotated and pulverized. In some cases, quartz-rich layers were fractured in a brittle manner and their fragments were rearranged to form micro-folds. Rocks are thus pulverized with multiple shear surfaces. Incipient fracture zones and their surroundings have many voids because they are made under low confining pressures near the ground surface, so oxidizing surface water easily percolates through them. Oxidizing water reacts with pyrite which is contained in pelitic schist, producing sulfuric acid through. The rocks therefore become deteriorated by the water-rock interaction and would be easily deformed. Such a combination of the physical processes of deformation and fracturing and the chemical process of weathering develop a sliding zone.

Acid rock drainage in Nevado Pastoruri glacier area (Huascarán National Park, Perú): hydrochemical and mineralogical characterization and associated environmental implications.

PubMed

Santofimia, Esther; López-Pamo, Enrique; Palomino, Edwin Julio; González-Toril, Elena; Aguilera, Ángeles

2017-11-01

The generation of acid rock drainage (ARD) was observed in an area of Nevado Pastoruri as a result of the oxidative dissolution of pyrite-rich lutites and sandstones. These ARDs are generated as abundant pyrite becomes exposed to atmospheric conditions as a result of glacier retreat. The proglacial zone contains lagoons, springs, streams and wetlands, scant vegetation, and intense fluvioglacial erosion. This work reports a comprehensive identification and the results of sampling of the lagoons and springs belonging to the microbasin, which is the headwaters of the Pachacoto River, as well as mapping results based on the hydrochemical data obtained in our study. The physical properties and water chemistry of 12 springs and 22 lagoons from the proglacial zone are also presented. Water springs are far from being chemically uniform, with pH and EC values ranging between 2.55-6.42 and 23-1110 μS/cm respectively, which suggests a strong geologic control on water chemistry. Fe-SO 4 -2 concentrations confirm the intense process of pyrite oxidative dissolution. Many of the lagoons are affected by ARD, with low pH (~ 3), and high EC (256-1092 μS/cm) values when compared with unaffected lagoons (EC between 7 and 59 μS/cm), indicating a high degree of mineralization. The affected lagoons show higher concentrations of SO 4 2- and SiO 2 , and elements as Fe, Al, Mg, Mn, Zn, Co, and Ni, which are related to the alteration of pyrite and the dissolution of aluminosilicate minerals. Schwertmannite-goethite appears to be the most important mineral phases controlling the Fe solubility at a pH of 2-3.5. Moreover, they act as a sorbent of trace elements (As, Sb, V, Pb, Zn, Cr), which is an efficient mechanism of natural attenuation. Despite of this, the water flowing out from the basin is acid (pH 3.1) and contains significant concentrations of Fe (0.98 mg/L) and Al (3.76 mg/L) that confer mineral acidity to water. The Pachacoto River located 5.5 km downstream from this point showed a strong natural attenuation, with a pH of 6.9 and low concentration of metals. This mitigating process is possible due to (i) the formation of precipitates that retain toxic elements and (ii) the mixing with natural waters that promote dilution, which favor the increase of pH until circumneutral conditions.

Evolution of biogeochemical cycling of phosphorus during 45~50 Ma revealed by sequential extraction analysis of IODP Expedition 302 cores from the Arctic Ocean

NASA Astrophysics Data System (ADS)

Hashimoto, S.; Yamaguchi, K. E.; Takahashi, K.

2012-12-01

The modern Arctic Ocean plays crucial roles in controlling global climate system with the driving force of global thermohaline circulation through the formation of dense deep water and high albedo due to the presence of perennial sea-ice. However, the Arctic sea-ice has not always existed in the past. Integrated Ocean Drilling Program (IODP) Expedition 302 Arctic Coring Expedition (ACEX) has clarified that global warming (water temperature: ca. 14~16○C) during 48~49 Ma Azolla Event induced the loss of sea-ice and desalination of surface ocean, and that sea-ice formed again some million years later (45 Ma). In the Arctic Ocean, warming and cooling events repeated over and over (e.g., Brinkhuis et al., 2006; Moran et al., 2006; März et al., 2010). Large variations in the extent of thermohaline circulation through time often caused stagnation of seawater and appearance of anaerobic environment where hydrogen sulfide was produced by bacterial sulfate reduction. Ogawa et al. (2009) confirmed occurrence of framboidal pyrite in the ACEX sediments, and suggested that the Arctic Ocean at the time was anoxic, analogous to the modern Black Sea, mainly based on sulfur isotope analysis. To further clarify the variations in the nutrient status of the Arctic Ocean, we focus on the geochemical cycle of phosphorus. We performed sequential extraction analysis of sedimentary phosphorus in the ACEX sediments, using the method that we improvped based on the original SEDEX method by Ruttenberg (1992) and Schenau et al. (2000). In our method, phosphorus fractions are divided into five forms; (1) absorbed P, (2) Feoxide-P, (4) carbonate fluorapatite (CFAP) + CaCO3-P + hydroxylapatite (HAP), (4) detrital P, and (5) organic P. Schenau et al. (2000) divided the (3) fraction into non-biological CFAP and biological HAP and CaCO3-P. When the Arctic Ocean was closed and in its warming period, the water mass was most likely stratified and an anaerobic condition would have prevailed where bacterial sulfate reduction was active. In this case, most of the phosphorus in sediment was stored as organic P, which was originally derived as sinking particles of detrital plankton from the surface ocean. Increased rainfalls during such a warming period would have enhanced continental weathering and delivery of phosphorus to the surface ocean, and biological activity using increased amounts of phosphorus supply would also have increased. Feoxide-P is considered to be less important as a sink for phosphorus because of the likely formation of pyrite through the reductive dissolution of Fe oxide. CFAP could be a sink for phosphorus, because the formation of CFAP tends to increase with increasing age and depth.

Greigite as a marker of paleo sulphate methane transition zone (SMTZ) in cold seep environment of Krishna-Godavari (KG) Basin, Bay of Bengal, India.

NASA Astrophysics Data System (ADS)

B, F. K.; Dewangan, P.; Usapkar, A.; Mazumdar, A.; Kocherla, M.; Tammisetti, R.; Khalap, S. T.; Satelkar, N. P.; Mehrtens, T.; Rosenauer, A.

2014-12-01

Rockmagnetic results and electron microscopic observations on a sediment core retrieved from a proven cold seep environment of Krishna-Godavari (KG) Basin revealed an anomalously magnetically enhanced zone (17 - 23 mbsf) below the present-day SMTZ in the KG offshore basin. This zone is characterized by higher SIRM / k, kARM / SIRM and kfd % values indicating the presence of fine grained superparamagnetic (SP) sized ferrimagnetic iron sulphides minerals such as greigite formed due to anaerobic oxidation of methane (AOM). Identification of such mineral phases and understanding the mechanism of their formation and preservation is of vital importance which could provide better understanding of the geochemical processes on the paleo - SMTZ. Magnetic concentrates extracted from this zone were characterised by transmission electron microscopy and energy dispersive X- ray spectrometry. We observed two possible occurrences of magnetic phases within this sediment depths 17 - 23 mbsf. (a) authigenically formed SP sized ferrimagnetic inclusions of magnetite, pyrite and greigite within matrix of host siliceous grain, (b) poorly crystallized fine-grained magnetite with ill defined grain boundary possibily formed extracellulary by magnetotactic bacterias through biologically-induced mineralization. High methane fluxes as observed in this basin provides suitable environment for the formation of greigite in the vicinity of SMTZ. We hypothesize that due to availability of residual iron and low supply of hydrogen sulphide caused by downwards diffusion lead to preservation of greigite. The occurence of greigite as inclusion within the host silicate matrix might explain its preservation in this zone in spite of intense pyritization. The greigite would otherwise be converted to stable-form pyrite. It is challenging to explain the origin of biologically produced magnetite within 17 - 23 mbsf as it is expected to dissolve in this zone due to intense pyritization.

Identifying sources and processes controlling the sulphur cycle in the Canyon Creek watershed, Alberta, Canada.

PubMed

Nightingale, Michael; Mayer, Bernhard

2012-01-01

Sources and processes affecting the sulphur cycle in the Canyon Creek watershed in Alberta (Canada) were investigated. The catchment is important for water supply and recreational activities and is also a source of oil and natural gas. Water was collected from 10 locations along an 8 km stretch of Canyon Creek including three so-called sulphur pools, followed by the chemical and isotopic analyses on water and its major dissolved species. The δ(2)H and δ(18)O values of the water plotted near the regional meteoric water line, indicating a meteoric origin of the water and no contribution from deeper formation waters. Calcium, magnesium and bicarbonate were the dominant ions in the upstream portion of the watershed, whereas sulphate was the dominant anion in the water from the three sulphur pools. The isotopic composition of sulphate (δ(34)S and δ(18)O) revealed three major sulphate sources with distinct isotopic compositions throughout the catchment: (1) a combination of sulphate from soils and sulphide oxidation in the bedrock in the upper reaches of Canyon Creek; (2) sulphide oxidation in pyrite-rich shales in the lower reaches of Canyon Creek and (3) dissolution of Devonian anhydrite constituting the major sulphate source for the three sulphur pools in the central portion of the watershed. The presence of H(2)S in the sulphur pools with δ(34)S values ∼30 ‰ lower than those of sulphate further indicated the occurrence of bacterial (dissimilatory) sulphate reduction. This case study reveals that δ(34)S values of surface water systems can vary by more than 20 ‰ over short geographic distances and that isotope analyses are an effective tool to identify sources and processes that govern the sulphur cycle in watersheds.

Habitability: where lo look for life? Halophilic habitats: earth analogs to study Mars and Europá s habitability

NASA Astrophysics Data System (ADS)

Gómez, F.; Gómez-Elvira, J.; Rodríguez, N.; Caballero Castrejón, J. F.; Amils, R.; Rodríguez-Manfredi, J. A.

2009-04-01

Current Mars exploration is producing a considerable amount of information which requires comparison with terrestrial analogs in order to interpret and evaluate compatibility with possible extinct and/or extant life on the planet. The first astrobiological mission specially designed to detect life on Mars, the Viking missions, thought life unlikely, considering the amount of UV radiation bathing the surface of the planet, the resulting oxidative conditions, and the lack of adequate atmospheric protection. The necessity of the Europa surface exploration comes from the idea of a water ocean existence in its interior. Europa surface presents evidence of an active geology showing many tectonic features that seems to be connected with some liquid interior reservoir. Life needs several requirements for its establishment but, the only sine qua nom elements is the water, taking into account our experience on Earth extreme ecosystems The discovery of extremophiles on Earth widened the window of possibilities for life to develop in the universe, and as a consequence on Mars. The compilation of data produced by the ongoing missions (Mars Global Surveyor, Mars Odyssey, Mars Express and Mars Exploration Rover Opportunity) offers a completely different view: signs of an early wet Mars and rather recent volcanic activity. The discovery of important accumulations of sulfates, and the existence of iron minerals like jarosite, goethite and hematite in rocks of sedimentary origin has allowed specific terrestrial models related with this type of mineralogy to come into focus. Río Tinto (Southwestern Spain, Iberian Pyritic Belt) is an extreme acidic environment, product of the chemolithotrophic activity of microorganisms that thrive in the massive pyrite-rich deposits of the Iberian Pyritic Belt. The high concentrations of ferric iron and sulfates, products of the metabolism of pyrite, generate a collection of minerals, mainly gypsum, jarosite, goethite and hematites, all of which have been detected in different regions of Mars (Fernández-Remolar et al., 2004). But, where to look for life in other planetary bodies? Planet's or Icy Moon`s surface are adverse for life. Harsh conditions for life to wheal with. Similar harsh conditions as the primordial Earth ones during the time when origin of life occurred. In the last case, life was originated under high irradiation conditions, meteorite bombardment and high temperature. Some particular protective environments or elements should house the organic molecules and the first bacterial life forms (Gómez F. et al., 2007). Terrestrial analogues work could help us to afford its comprehension. We are reporting here some preliminary studies about endolithic niches inside salt deposits used by phototrophs for taking advantage of sheltering particular light wavelengths. These acidic salts deposits located in Río Tinto shelter life forms which are difficult to localize by eye. Molecular ecology techniques are needed for its localization and study. Bibliography Fernández-Remolar, D., Gómez-Elvira, J., Gómez, F., Sebastián, E., Martín, J., Manfredi, J.A., Torres, J., González Kesler, C. and Amils, R. Planetary and Space Science 52 (2004) 239 - 248 Gómez, F., Aguilera, A. and Amils, R. Icarus 191 (2007) 352-359. Acknowledgments This study was funded by the project ESP2006-06640 from Spanish Ministry of Education and Science and FEDER funds from European Community.

Nitrate, nitrite and nitric oxide reductases: from the last universal common ancestor to modern bacterial pathogens

PubMed Central

Vázquez-Torres, Andrés; Bäumler, Andreas

2016-01-01

The electrochemical gradient that ensues from the enzymatic activity of cytochromes such as nitrate reductase, nitric oxide reductase, and quinol oxidase contributes to the bioenergetics of the bacterial cell. Reduction of nitrogen oxides by bacterial pathogens can, however, be uncoupled from proton translocation and biosynthesis of ATP or NH4+, but still linked to quinol and NADH oxidation. Ancestral nitric oxide reductases, as well as cytochrome coxidases and quinol bo oxidases evolved from the former, are capable of binding and detoxifying nitric oxide to nitrous oxide. The NO-metabolizing activity associated with these cytochromes can be a sizable source of antinitrosative defense in bacteria during their associations with host cells. Nitrosylation of terminal cytochromes arrests respiration, reprograms bacterial metabolism, stimulates antioxidant defenses and alters antibiotic cytotoxicity. Collectively, the bioenergetics and regulation of redox homeostasis that accompanies the utilization of nitrogen oxides and detoxification of nitric oxide by cytochromes of the electron transport chain increases fitness of many Gram-positive and –negative pathogens during their associations with invertebrate and vertebrate hosts. PMID:26426528

Hydrogeochemistry of prairie pothole region wetlands: Role of long-term critical zone processes

USGS Publications Warehouse

Goldhaber, Martin B.; Mills, Christopher T.; Morrison, Jean M.; Stricker, Craig A.; Mushet, David M.; LaBaugh, James W.

2014-01-01

Results from the CWLSA were scaled up to a 9700 km2 area surrounding CWLSA using ~ 1800 drill logs and literature data on wetland water chemistry for 178 wetlands within this larger area. The oxidized brown zone depth and wetland water compositional trends are very similar to the CWLSA. Additionally, surface water data from 176 southern Canadian pothole wetlands that conform to the same wetland water geochemical trends as those recorded in the CWLSA further corroborate that SO42 − accumulation driven by pyrite oxidation is a nearly ubiquitous process in the prairie pothole region and distinguishes PPR wetlands from other wetlands worldwide that have a similar overall hydrology.

Mapping and prediction of Coal Workers' Pneumoconiosis with bioavailable iron content in the bituminous coals

USGS Publications Warehouse

Huang, X.; Li, W.; Attfield, M.D.; Nadas, A.; Frenkel, K.; Finkelman, R.B.

2005-01-01

Based on the first National Study of Coal Workers' Pneumoconiosis (CWP) and the U.S. Geological Survey database of coal quality, we show that the prevalence of CWP in seven coal mine regions correlates with levels of bioavailable iron (BAI) in the coals from that particular region (correlation coefficient r = 0.94, p < 0.0015). CWP prevalence is also correlated with contents of pyritic sulfur (r = 0.91, p < 0.0048) or total iron (r = 0.85, p < 0.016) but not with coal rank (r = 0.59, p < 0.16) or silica (r = 0.28, p < 0.54). BAI was calculated using our model, taking into account chemical interactions of pyrite, sulfuric acid, calcite, and total iron. That is, iron present in coals can become bioavailable by pyrite oxidation, which produces ferrous sulfate and sulfuric acid. Calcite is the major component in coals that neutralizes the available acid and inhibits iron's bioavailabiity. Therefore, levels of BAI in the coals are determined by the available amounts of acid after neutralization of calcite and the amount of total iron in the coals. Using the linear fit of CWP prevalence and the calculated BAI in the seven coal mine regions, we have derived and mapped the pneumoconiotic potencies of 7,000 coal samples. Our studies indicate that levels of BAI in the coals may be used to predict coal's toxicity, even before large-scalen mining.

Mapping and Prediction of Coal Workers’ Pneumoconiosis with Bioavailable Iron Content in the Bituminous Coals

PubMed Central

Huang, Xi; Li, Weihong; Attfield, Michael D.; Nádas, Arthur; Frenkel, Krystyna; Finkelman, Robert B.

2005-01-01

Based on the first National Study of Coal Workers’ Pneumoconiosis (CWP) and the U.S. Geological Survey database of coal quality, we show that the prevalence of CWP in seven coal mine regions correlates with levels of bioavailable iron (BAI) in the coals from that particular region (correlation coefficient r = 0.94, p < 0.0015). CWP prevalence is also correlated with contents of pyritic sulfur (r = 0.91, p < 0.0048) or total iron (r = 0.85, p < 0.016) but not with coal rank (r = 0.59, p < 0.16) or silica (r = 0.28, p < 0.54). BAI was calculated using our model, taking into account chemical interactions of pyrite, sulfuric acid, calcite, and total iron. That is, iron present in coals can become bioavailable by pyrite oxidation, which produces ferrous sulfate and sulfuric acid. Calcite is the major component in coals that neutralizes the available acid and inhibits iron’s bioavailability. Therefore, levels of BAI in the coals are determined by the available amounts of acid after neutralization of calcite and the amount of total iron in the coals. Using the linear fit of CWP prevalence and the calculated BAI in the seven coal mine regions, we have derived and mapped the pneumoconiotic potencies of 7,000 coal samples. Our studies indicate that levels of BAI in the coals may be used to predict coal’s toxicity, even before large-scale mining. PMID:16079064

The rate of chemical weathering of pyrite on the surface of Venus

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lodders, K.

1993-01-01

This abstract reports results of an experimental study of the chemical weathering of pyrite (FeS2) under Venus-like conditions. This work, which extends the earlier study by Fegley and Treiman, is part of a long range research program to experimentally measure the rates of thermochemical gas-solid reactions important in the atmospheric-lithospheric sulfur cycle on Venus. The objectives of this research are (1) to measure the kinetics of thermochemical gas-solid reactions responsible for both the production (e.g., anhydrite formation) and destruction (e.g., pyrrhotite oxidation) of sulfur-bearing minerals on the surface of Venus and (2) to incorporate these and other constraints into holistic models of the chemical interactions between the atmosphere and surface of Venus. Experiments were done with single crystal cubes of natural pyrite (Navajun, Logrono, Spain) that were cut and polished into slices of known weight and surface area. The slices were isothermally heated at atmospheric pressure in 99.99 percent CO2 (Coleman Instrument Grade) at either 412 C (685 K) or 465 C (738 K) for time periods up to 10 days. These two isotherms correspond to temperatures at about 6 km and 0 km altitude, respectively, on Venus. The reaction rate was determined by measuring the weight loss of the reacted slices after removal from the furnace. The reaction products were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy on the SEM.

A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

2017-03-01

The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

Evidence of ancient microbial activity on Mars

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 a relatively rare secondary iron arsenate-sulphate mineral named bukovskýite - Fe3+ 2(As5+O4)(S6+O4)(OH)•7(H2O) - found in a shock melt vein of the Tissint Martian meteorite. It is hypothesised that the mineral formed when high concentrations of aqueous H+, Fe(III), SO4 and AsO4 were maintained for long periods of time in microenvironments created within wet subsurface Martian clays. The aqueous H+, Fe(III), SO4 and AsO4 species arose from the microbial oxidation of FeS2 with concurrent release of sequestrated As. The availability of aqueous AsO4 would also be complemented by dissolution by-products of the microbial reduction of Feoxides influenced by dissolved organic matter that alters the redox state and the complexation of As, thus shifting As partitioning in favour of the solute phase. This hypothesis is substantially supported by SEM analysis of a 15μm spherical structure comprising of a carbonaceous outer coating with a inner core of FeS2 (pyrite) that showed the pyrite surface with spherical pits, and chains of pits, with morphologies distinct from abiotic alteration features. The pits and channels have a clustered, geometric distribution, typical of microbial activity, and are closely comparable to biologically mediated microstructures created by Fe- and S-oxidising microbes in the laboratory. These microstructures are interpreted as trace fossils resulting from the attachment of bacteria to the pyrite surfaces.

Importance of Extracellular Polymeric Substances from Thiobacillus ferrooxidans for Bioleaching

PubMed Central

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

Porosity evolution during weathering of Marcellus shale

NASA Astrophysics Data System (ADS)

Gu, X.; Brantley, S.

2017-12-01

Weathering is an important process that continuously converts rock to regolith. Shale weathering is of particular interest because 1) shale covers about 25% of continental land mass; 2) recent development of unconventional shale gas generates large volumes of rock cuttings. When cuttings are exposed at earth's surface, they can release toxic trace elements during weathering. In this study, we investigated the evolution of pore structures and mineral transformation in an outcrop of Marcellus shale - one of the biggest gas shale play in North America - at Frankstown, Pennsylvania. A combination of neutron scattering and imaging was used to characterize the pore structures from nm to mm. The weathering profile of Marcellus shale was also compared to the well-studied Rose Hill shale from the Susquehanna Shale Hills critical zone observatory nearby. This latter shale has a similar mineral composition as Marcellus shale but much lower concentrations of pyrite and OC. The Marcellus shale formation in outcrop overlies a layer of carbonate at 10 m below land surface with low porosity (<3%). All the shale samples above the carbonate layer are almost completely depleted in carbonate, plagioclase, chlorite and pyrite. The porosities in the weathered Marcellus shale are twice as high as in protolith. The pore size distribution exhibits a broad peak for pores of size in the range of 10s of microns, likely due to the loss of OC and/or dissolution of carbonate during weathering. In the nearby Rose Hill shale, the pyrite and carbonate are sharply depleted close to the water table ( 15-20 m at ridgetop); while chlorite and plagioclase are gradually depleted toward the land surface. The greater weathering extent of silicates in the Marcellus shale despite the similarity in climate and erosion rate in these two neighboring locations is attributed to 1) the formation of micron-size pores increases the infiltration rate into weathered Marcellus shale and therefore promotes mineral weathering; 2) the pyrite/carbonate ratio is higher in the Marcellus shale than in Rose Hill shale, and thus excess acidity generated through pyrite oxidation enhances the dissolution of silicates. We seek to use these and other observations to develop a global model for shale weathering that incorporates both mineral composition and porosity change.

Sulfur amino acids and alanine on pyrite (100) by X-ray photoemission spectroscopy: Surface or molecular role?

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.

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

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.

Sulfur Geochemistry of a Lacustrine Record from Taiwan Reveals Enhanced Marine Aerosol Input during the Early Holocene

PubMed Central

Ding, Xiaodong; Li, Dawei; Zheng, Liwei; Bao, Hongyan; Chen, Huei-Fen; Kao, Shuh-Ji

2016-01-01

Lacustrine record of marine aerosol input has rarely been documented. Here, we present the sulfur geochemistry during the last deglaciation and early Holocene of a sediment core retrieved from the Dongyuan Lake in southern Taiwan. An unusually high sulfur peak accompanying pyrite presence is observed at 10.5 ka BP. Such high sulfur content in lacustrine record is unusual. The δ34S of sulfur varied from +9.5 to + 17.1‰ with two significant positive shifts at 10.5 and 9.4 ka BP. The sources of sulfur and potential processes involving the sulfur isotope variation including bacterial sulfate reduction, volcanic emissions, in-catchment sulfide oxidation and marine aerosol input are discussed. Enhanced marine aerosol input is the most likely explanation for such sulfur peaks and δ34S shifts. The positive δ34S shifts appeared concurrently with the maximum landslide events over Taiwan resulted from enhanced typhoon activities. The synchronicity among records suggests that increased typhoon activities promoted sea spray, and consequently enhanced the marine aerosol input with 34S-enriched sulfate. Our sulfur geochemistry data revealed sea spray history and marine influence onto terrestrial environment at coastal regions. Wider coverage of spatial-temporal lacustrine sulfur geochemistry record is needed to validate the applicability of sulfur proxy in paleoenvironmental research. PMID:27941864

Seasonal cycling of sulfur and iron in porewaters of a Delaware salt marsh

NASA Technical Reports Server (NTRS)

Luther, George W., III; Church, Thomas M.

1987-01-01

An extensive pore water data set has been gathered in the Great Marsh, Delaware over various seasons, salinities, and tides. The data all point to a complimentary redox cycle for sulfur and iron which operates seasonally and tidally. Surface oxidizing conditions prevail in summer, with more reducing conditions at depth during the winter. During the spring tides which flood the marsh, pyrite oxidation occurs releasing excess dissolved iron (II) and sulfate to the porewaters, and precipitating authigenic solid iron phases. The redox conditions in the porewaters of the upper zone during the summer is poised between mildly oxidizing and mildly reducing conditions as shown by pE calculations. This redox environment and intermediate iron-sulfur redox species may be important for the stimulation of plant growth (photosynthesis) and sustenance of a viable microbial community (heterotrophy and chemoautropy).

Multiple sulfur isotope characteristics of 3.46-2.7 Ga sedimentary rocks from drill cores of the Archean Biosphere Drilling Project (Invited)

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.

The La Unión Au ± Cu prospect, Camagüey District, Cuba: fluid inclusion and stable isotope evidence for ore-forming processes

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.

Anthropogenic organic matter in the Great Marsh of the Indiana Dunes National Lakeshore and its implications

USGS Publications Warehouse

Mastalerz, Maria; Souch, C.; Filippelli, G.M.; Dollar, N.L.; Perkins, S.M.

2001-01-01

Cores from the Great Marsh area of the Indiana Dunes National Lakeshore were examined in order to document variations in concentration, type and size of anthropogenic organic matter (AnOM-coal, coke, etc.) and discuss their relationship to the concentration of such trace elements as Pb, Zn, and Mn in the near-surface sediment section. The results indicate that the first appearance of AnOM corresponds to the onset of industrialization in the area. There is also a general relationship between the occurrence of AnOM and Zn, Pb, and Mn. Trace metals were likely transported from the industrial sites to the area of their deposition as sulfur-bearing coatings on small anthropogenic particles. After deposition, these sulfur-bearing compounds reacted with organic matter within the marsh. As a result of bacterial reduction, the pyrite was produced, as suggested by a close relationship between the pyrite and AnOM. Distance from the industrial complex upwind as well as local hydrologic conditions are among the major factors controlling distribution of AnOM and trace elements. At the same distance from the source, types and sizes of AnOM are influenced by the duration and frequency of flooding. ?? 2001 Elsevier Science B.V. All rights reserved.

Increased electrical output when a bacterial ABTS oxidizer is used in a microbial fuel cell

USDA-ARS?s Scientific Manuscript database

Microbial fuel cells (MFCs) are a technology that provides electrical energy from the microbial oxidation of organic compounds. Most MFCs use oxygen as the oxidant in the cathode chamber. The present study examined the formation in culture of an unidentified bacterial oxidant and investigated the ...

Some Ecological Mechanisms to Generate Habitability in Planetary Subsurface Areas by Chemolithotrophic Communities: The Ro Tinto Subsurface Ecosystem as a Model System

NASA Astrophysics Data System (ADS)

Fernández-Remolar, David C.; Gómez, Felipe; Prieto-Ballesteros, Olga; Schelble, Rachel T.; Rodríguez, Nuria; Amiols, Ricardo

2008-02-01

Chemolithotrophic communities that colonize subsurface habitats have great relevance for the astrobiological exploration of our Solar System. We hypothesize that the chemical and thermal stabilization of an environment through microbial activity could make a given planetary region habitable. The MARTE project ground-truth drilling campaigns that sampled cryptic subsurface microbial communities in the basement of the Ro Tinto headwaters have shown that acidic surficial habitats are the result of the microbial oxidation of pyritic ores. The oxidation process is exothermic and releases heat under both aerobic and anaerobic conditions. These microbial communities can maintain the subsurface habitat temperature through storage heat if the subsurface temperature does not exceed their maximum growth temperature. In the acidic solutions of the Ro Tinto, ferric iron acts as an effective buffer for controlling water pH. Under anaerobic conditions, ferric iron is the oxidant used by microbes to decompose pyrite through the production of sulfate, ferrous iron, and protons. The integration between the physical and chemical processes mediated by microorganisms with those driven by the local geology and hydrology have led us to hypothesize that thermal and chemical regulation mechanisms exist in this environment and that these homeostatic mechanisms could play an essential role in creating habitable areas for other types of microorganisms. Therefore, searching for the physicochemical expression of extinct and extant homeostatic mechanisms through physical and chemical anomalies in the Mars crust (i.e., local thermal gradient or high concentration of unusual products such as ferric sulfates precipitated out from acidic solutions produced by hypothetical microbial communities) could be a first step in the search for biological traces of a putative extant or extinct Mars biosphere.

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

NASA Astrophysics Data System (ADS)

Censi, P.; Raso, M.; Yechieli, Y.; Ginat, H.; Saiano, F.; Zuddas, P.; Brusca, L.; D'Alessandro, W.; Inguaggiato, C.

2017-03-01

Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

Ground-water quality and geochemistry of aquifers associated with coal in the Allegheny and Monongahela formations, southeastern Ohio

USGS Publications Warehouse

Razem, A.C.; Sedam, A.C.

1985-01-01

Ground water from aquifers associated with coal beds in the Allegheny and Monongahela Formations in southeastern Ohio is predominantly a calcium magnesium bicarbonate type. Sodium bicarbonate type water is less common. Isolated areas of sodium chloride and calcium sulfate types also are present. The water is predominantly very hard, and has a median hardness concentration of 258 milligrams per liter as calcium carbonate and a median dissolved-solids concentration of 436 milligrams per liter. Few wells contain water with dissolved-solids concentrations in excess of 1,000 milligrams per liter. Bicarbonate concentration in ground water was found to be significantly different among coals, whereas concentrations of bicarbonate, hardness, calcium, magnesium, sodium, iron, manganese, and strontium were significantly different between ground water in the Allegheny and Monongahela Formations. Many constituents are significantly correlated, but few correlation coefficients are high. The presence of sulfate or iron is attributed to the kinetic mechanism operating during the oxidation of pyrite. The position along the sulfide or ferrous-iron oxidation pathways controls the reaction products of pyrite found in solution, and the formation of either the sulfate of iron constituents. The availability and rate of diffusion of oxygen in the formations exerts control on the water quality. Discriminant-function analysis correctly classifies 89 percent of the observations into the Allegheny or Monongahela Formations. As a verifications, 39 of 41 observations from another study were correctly classified by formation. The differences in water chemistry between the Allegheny and the Monongahela Formations are gradational and are attributed the oxidation of iron sulfide. The diffusion and availability of oxygen, which controls the chemical reaction, is regulated by the porosity and permeability of the rock with respect to oxygen and the presence or absence of carbonates, which controls the pH.

Some ecological mechanisms to generate habitability in planetary subsurface areas by chemolithotrophic communities: the Río Tinto subsurface ecosystem as a model system.

PubMed

Fernández-Remolar, David C; Gómez, Felipe; Prieto-Ballesteros, Olga; Schelble, Rachel T; Rodríguez, Nuria; Amils, Ricardo

2008-02-01

Chemolithotrophic communities that colonize subsurface habitats have great relevance for the astrobiological exploration of our Solar System. We hypothesize that the chemical and thermal stabilization of an environment through microbial activity could make a given planetary region habitable. The MARTE project ground-truth drilling campaigns that sampled cryptic subsurface microbial communities in the basement of the Río Tinto headwaters have shown that acidic surficial habitats are the result of the microbial oxidation of pyritic ores. The oxidation process is exothermic and releases heat under both aerobic and anaerobic conditions. These microbial communities can maintain the subsurface habitat temperature through storage heat if the subsurface temperature does not exceed their maximum growth temperature. In the acidic solutions of the Río Tinto, ferric iron acts as an effective buffer for controlling water pH. Under anaerobic conditions, ferric iron is the oxidant used by microbes to decompose pyrite through the production of sulfate, ferrous iron, and protons. The integration between the physical and chemical processes mediated by microorganisms with those driven by the local geology and hydrology have led us to hypothesize that thermal and chemical regulation mechanisms exist in this environment and that these homeostatic mechanisms could play an essential role in creating habitable areas for other types of microorganisms. Therefore, searching for the physicochemical expression of extinct and extant homeostatic mechanisms through physical and chemical anomalies in the Mars crust (i.e., local thermal gradient or high concentration of unusual products such as ferric sulfates precipitated out from acidic solutions produced by hypothetical microbial communities) could be a first step in the search for biological traces of a putative extant or extinct Mars biosphere.

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

PubMed

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.

Formation of Neogenic Ores on the Dump-Heaps of Old Uranium Mines and on the Mine-Head of Mines under Exploitation; FORMATION DE MINERAUX NEOGENES SUR LES HALDES D'ANCIENNES MINES D'URANIUM ET SUR LE CARREAU DES MINES EN EXPLOITATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chervet, J.

1960-01-01

The major degradations suffered by primary and secondary uranium ores under the weathering action of air and water are assessed. Pyritic ores were found to be the most vunerable. The interactions between pynite oxidation products and urantferous compounds often lead to the formation of neogentc ores. (C.J.G.)

Trace element abundances in major minerals of Late Permian coals from southwestern Guizhou province, China

USGS Publications Warehouse

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.

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.

HVOF Thermal Spray TiC/TiB 2 Coatings for AUSC Boiler/Turbine Components for Enhanced Corrosion Protection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mondal, Kanchan; Koc, Rasit; Fan, Chinbay

The high temperatures of operations still pose significant risk of degradation and fatigue from oxidizing, corroding and eroding environment. In addition to unused O 2, water from combustion and SO x from the coal sulfur oxidation that result in highly corrosive environment, acid gases such as HCl and other sulfur compounds may also be present. These adverse effects are further accelerated due to the elevated temperatures. In addition, ash particulates and unburnt carbon and pyritic sulfur can cause erosion of the surface and thus loss of material. Unburnt carbon and pyritic sulfur may also cause localized reduction sites. Thus, firesidemore » corrosion protection and steam oxidation protection alternatives to currently used Ni-Cr overlays need to be identified and evaluated. Titanium carbide (TiC) is a suitable alternative on account of the material features such as the high hardness, the high melting point, the high strength and the low density for the substitution or to be used in conjunction with NiCr for enhancing the fireside corrosion and erosion of the materials. Another alternative is the use of titanium boride as a coating for chemical stability required for long-term service and high erosion resistance over the state-of-the-art, high fracture toughness (K 1C ~12 MPam 1/2) and excellent corrosion resistance (kp~1.9X10 -11 g 2/cm 4/s at 800°C in air). The overarching aim of the research endeavor was to synthesize oxidation, corrosion and wear resistant TiC and TiB 2 coating powders, apply thermal spray coating on existing boiler materials and characterize the coated substrates for corrosion resistance for applications at high temperatures (500 -750 °C) and high pressures (~350 bars) using the HVOF process and to demonstrate the feasibility of these coating to be used in AUSC boilers and turbines.« less

Enhancement of gold recovery using bioleaching from gold concentrate

NASA Astrophysics Data System (ADS)

Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

2012-04-01

The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

Method of synthesizing pyrite nanocrystals

DOEpatents

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.

Enabling iron pyrite (FeS2) and related ternary pyrite compounds for high-performance solar energy applications

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.

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. [Fourth quarterly techical progress report, September 1990--November 1990

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

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

Origin of the Mariano Lake uranium deposit, McKinley County, New Mexico

USGS Publications Warehouse

Fishman, Neil S.; Reynolds, Richard L.

1982-01-01

The Mariano Lake uranium deposit, hosted by the Brushy Basin Member of the Jurassic Morrison Formation, occurs in the trough of an east-west trending syncline at the western end of the Smith Lake-Mariano Lake group of uranium deposits near Crownpoint, New Mexico. The orebody, which contains abundant amorphous organic material, is situated on the reduced side of a regional reduction-oxidation (redox) interface. The presence of amorphous organic material suggests the orebody may represent a tabular (primary) deposit, whereas the close proximity of the orebody to the redox interface is suggestive that uranium was secondarily redistributed by oxidative processes from pre-existing tabular orebodies. Uranium contents correlate positively with both organic carbon and vanadium contents. Petrographic evidence and scanning electron microscope-energy dispersive analyses point to uranium residence in the epigentically introduced amorphous organic material, which coats detrital grains and fills voids. Uranium mineralization was preceded by the following diagenetic alterations: precipitation of pyrite (d34S values ranging from-11.0 to-38.2 per mil); precipitation of mixed-layer smectite-illite clays; partial dissolution of some of the detrital feldspar population; and precipitation of quartz and adularia overgrowths. Alterations associated with uranium mineralization include emplacement of amorphous organic material (possibly uranium bearing); destruction of detrital iron-titanium oxide grains; coprecipitation of chlorite and microcrystalline quartz, and precipitation of pyrite and marcasite (d34S values for these sulfides ranging from -29.4 to -41.6 per mil). After mineralization, calcite, dolomite, barite, and kaolinite precipitated, and authigenic iron disulfides were replaced by ferric oxides and hydroxides. Geochemical data (primarily the positive correlation of uranium content to both organic carbon and vanadium contents) and petrographic observations (epigentically introduced amorphous organic matter and uranium residence in this organic matter) indicate that the Mariano Lake orebody is a tabular-type uranium deposit. Oxidative processes have not noticeably redistributed and reconcentrated primary uranium in the immediate vicinity of the deposit nor have they greatly modified geochemical characteristics in the ore. Preservation of the Mariano Lake deposit may not only be related to its position along the synclinal trough, where oxidative destruction of the orebody has been inhibited by stagnation of oxidizing ground waters by the structure, but also due to the deflection of ground waters (resulting from low orebody porosity) around the orebody.

Pyrite-uranium polycrystal

USGS Publications Warehouse

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.

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.

Carbon monoxide detection of chemisorbed oxygen in coal and other carbonaceous materials

USGS Publications Warehouse

Hinckley, C.C.; Wiltowski, T.; Wiltowska, T.; Ellison, D.W.; Shiley, R.H.; Wu, L.

1990-01-01

The oxidation of carbon monoxide by mildly oxidized and devolatilized coal samples was studied thermogravimetrically. The oxidation was attributed to oxygen chemisorbed on inorganic components of the coals. The reaction of CO with pyrite producing carbonyl sulphide, OCS, accompanied the oxidation. A mechanism for CO oxidation is proposed in which active oxygen chemisorbed on the inorganic components of the coal directly oxidized CO to CO2, and facilitates the chemisorption of CO on the coal as carbonate. A factor, ?? = ( 11 14) [1 - ( Wn Wc)], was derived where Wn is the sample weight loss not attributed to OCS formation, and Wc is the estimated weight of evolved CO2. This quantity is proportional to the fraction of CO2 produced by the direct oxidation of CO, and was used to compare the coal samples studied. Samples of an Illinois No. 5 coal yielded average ?? values of 0.7 and those of an Illinois No. 6 coal yielded values of 0.6, indicating that in these cases, the majority of CO2 produced came from the direct oxidation of CO. The results obtained for the coal samples are compared with a selection of carbonaceous samples for which the proposed mechanism does not apply. ?? 1990.

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

PubMed

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

USGS Publications Warehouse

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.

Inhibition of bacterial and leukocyte adhesion under shear stress conditions by material surface chemistry.

PubMed

Patel, Jasmine D; Ebert, Michael; Stokes, Ken; Ward, Robert; Anderson, James M

2003-01-01

Biomaterial-centered infections, initiated by bacterial adhesion, persist due to a compromised host immune response. Altering implant materials with surface modifying endgroups (SMEs) may enhance their biocompatibility by reducing bacterial and inflammatory cell adhesion. A rotating disc model, which generates shear stress within physiological ranges, was used to characterize adhesion of leukocytes and Staphylococcus epidermidis on polycarbonate-urethanes and polyetherurethanes modified with SMEs (polyethylene oxide, fluorocarbon and dimethylsiloxane) under dynamic flow conditions. Bacterial adhesion in the absence of serum was found to be mediated by shear stress and surface chemistry, with reduced adhesion exhibited on materials modified with polydimethylsiloxane and polyethylene oxide SMEs. In contrast, bacterial adhesion was enhanced on materials modified with fluorocarbon SMEs. In the presence of serum, bacterial adhesion was primarily neither material nor shear dependent. However, bacterial adhesion in serum was significantly reduced to < or = 10% compared to adhesion in serum-free media. Leukocyte adhesion in serum exhibited a shear dependency with increased adhesion occurring in regions exposed to lower shear-stress levels of < or = 7 dyne/cm2. Additionally, polydimethylsiloxane and polyethylene oxide SMEs reduced leukocyte adhesion on polyether-urethanes. In conclusion, these results suggest that surface chemistry and shear stress can mediate bacterial and cellular adhesion. Furthermore, materials modified with polyethylene oxide SMEs are capable of inhibiting bacterial adhesion, consequently minimizing the probability of biomaterial-centered infections.

Natural inorganic nanoparticles--formation, fate, and toxicity in the environment.

PubMed

Sharma, Virender K; Filip, Jan; Zboril, Radek; Varma, Rajender S

2015-12-07

The synthesis, stability, and toxicity of engineered metal nanoparticles (ENPs) have been extensively studied during the past two decades. In contrast, research on the formation, fate, and ecological effects of naturally-occurring nanoparticles (NNPs) has become a focus of attention only recently. The natural existence of metal nanoparticles and their oxides/sulfides in waters, wastewaters, ore deposits, mining regions, and hydrothermal vents, as exemplified by the formation of nanoparticles containing silver and gold (AgNPs and AuNPs), Fe, Mn, pyrite (FeS2), Ag2S, CuS, CdS, and ZnS, is dictated largely by environmental conditions (temperature, pH, oxic/anoxic, light, and concentration and characteristics of natural organic matter (NOM)). Examples include the formation of nanoparticles containing pyrite, Cu and Zn-containing pyrite, and iron in hydrothermal vent black smoker emissions. Metal sulfide nanoparticles can be formed directly from their precursor ions or indirectly by sulfide ion-assisted transformation of the corresponding metal oxides under anaerobic conditions. This tutorial focuses on the formation mechanisms, fate, and toxicity of natural metal nanoparticles. Natural waters containing Ag(I) and Au(III) ions in the presence of NOM generate AgNPs and AuNPs under thermal, non-thermal, and photochemical conditions. These processes are significantly accelerated by existing redox species of iron (Fe(II)/Fe(III)). NOM, metal-NOM complexes, and reactive oxygen species (ROS) such as O2˙(-), ˙OH, and H2O2 are largely responsible for the natural occurrence of nanoparticles. AgNPs and AuNPs emanating from Ag(I)/Au(III)-NOM reactions are stable for several months, thus indicating their potential to be transported over long distances from their point of origin. However, endogenous cations present in natural waters can destabilize the nanoparticles, with divalent cations (e.g., Ca(2+), Mg(2+)) being more influential than their monovalent equivalents (e.g., Na(+), K(+)). The toxicity of NNPs may differ from that of ENPs because of differences in the coatings on the nanoparticle surfaces. An example of this phenomenon is presented and is briefly discussed.

Geochemical element mobility during the hydrothermal alteration in the Tepeoba porphyry Cu-Mo-Au deposits at Balikesir, NW Turkey

NASA Astrophysics Data System (ADS)

Abdelnasser, Amr; Kiran Yildirim, Demet; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Tepeoba porphyry Cu-Mo-Au deposit represents one of the important copper source and mineral deposits in the Anatolian tectonic belt at Balikesir province, NW Turkey. It considered as a vein-type deposit locally associated with intense hydrothermal alteration within the brecciation, quartz stockwork veining, and brittle fracture zones in the main host rock that represented by hornfels, as well as generally related to the shallow intermediate to silicic intrusive Eybek pluton. Based on the field and geologic relationships and types of ore mineral assemblages and the accompanied alteration types, there are two mineralization zones; hypogene (primary) and oxidation/supergene zones are observed associated with three alteration zones; potassic, phyllic, and propylitic zones related to this porphyry deposit. The phyllic and propylitic alterations locally surrounded the potassic alteration. The ore minerals related to the hypogene zone represented by mostly chalcopyrite, Molybdenite, and pyrite with subordinate amount of marcasite, enargite, and gold. On the other hand they include mainly cuprite with chalcopyrite, pyrite and gold as well as hematite and goethite at the oxidation/supergene zone. This study deals with the quantitative calculations of the mass/volume changes (gains and losses) of the major and trace elements during the different episodes of alteration in this porphyry deposit. These mass balance data reveal that the potassic alteration zone that the main Cu- and Mo-enriched zone, has enrichment of K, Si, Fe, and Mg, and depletion of Na referring to replacement of plagioclase and amphibole by K-feldspar, sericite and biotite. While the propylitic alteration that is the main Mo- and Au-enriched zone is accompanied with K and Na depletion with enrichment of Si, Fe, Mg, and Ca forming chlorite, epidote, carbonate and pyrite. On the other hand the phyllic alteration that occurred in the outer part around the potassic alteration, characterized by less amount of Cu and Mo mineralization having addition of Si and K with removal of Fe, Mg, Ca, and Na. Keywords: Mass balance calculation; Tepeoba porphyry Cu-Mo-Au deposits; Balikesir; Turkey

High spatial resolution U-Pb geochronology and Pb isotope geochemistry of magnetite-apatite ore from the Pea Ridge iron oxide-apatite deposit, St. Francois Mountains, southeast Missouri, USA

USGS Publications Warehouse

Neymark, Leonid; Holm-Denoma, Christopher S.; Pietruszka, Aaron; Aleinikoff, John N.; Fanning, C. Mark; Pillers, Renee M.; Moscati, Richard J.

2016-01-01

The Pea Ridge iron oxide-apatite (IOA) deposit is one of the major rhyolite-hosted magnetite deposits of the St. Francois Mountains terrane, which is located within the Mesoproterozoic (1.5–1.3 Ga) Granite-Rhyolite province in the U.S. Midcontinent. Precise and accurate determination of the timing and duration of oreforming processes in this deposit is crucial for understanding its origin and placing it within a deposit-scale and regional geologic context. Apatite and monazite, well-established U-Pb mineral geochronometers, are abundant in the Pea Ridge orebody. However, the potential presence of multiple generations of dateable minerals, processes of dissolution-reprecipitation, and occurrence of micrometer-sized intergrowths and inclusions complicate measurements and interpretations of the geochronological results. Here, we employ a combination of several techniques, including ID-TIMS and high spatial resolution geochronology of apatite and monazite using LA-SC-ICPMS and SHRIMP, and Pb isotope geochemistry of pyrite and magnetite to obtain the first direct age constraints on the formation and alteration history of the Pea Ridge IOA deposit. The oldest apatite TIMS 207Pb*/206Pb* dates are 1471 ± 1 and 1468 ± 1 Ma, slightly younger than (but within error of) the ~1474 to ~1473 Ma U-Pb zircon ages of the host rhyolites. Dating of apatite and monazite inclusions within apatite provides evidence for at least one younger metasomatic event at ~1.44 Ga, and possibly multiple superimposed metasomatic events between 1.47 and 1.44 Ga. Lead isotop analyses of pyrite show extremely radiogenic 206Pb/204Pb ratios up to ~80 unsupported by in situ U decay. This excess radiogenic Pb in pyrite may have been derived from the spatially associated apatite as apatite recrystallized several tens of million years after its formation. The low initial 206Pb/204Pb ratio of ~16.5 and 207Pb/204Pb ratio of ~15.4 for individual magnetite grains indicate closed U-Pb system behavior in this mineral and are consistent with derivation of the Pb from a mantle-like source.

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

PubMed Central

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

USGS Publications Warehouse

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.

PubMed

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

USGS Publications Warehouse

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

USGS Publications Warehouse

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 stable isotope geochemistry of acid sulfate alteration

USGS Publications Warehouse

Rye, R.O.; Bethke, P.M.; Wasserman, M.D.

1992-01-01

Acid sulfate wall-rock alteration, characterized by the assemblage alunite + kaolinite + quartz ?? pyrite, results from base leaching by fluids concentrated in H2SO4. Requisite amounts of H2SO4 can be generated by different mechanisms in three principal geologic environments: 1) by atmospheric oxidation of sulfides in the supergene environment, 2) by atmospheric oxidation at the water table in the steam-heated environment of H2S released by deeper, boiling fluids, and 3) by the disproportionation of magmatic SO2 to H2S and H2SO4 during condensation of a magmatic vapor plume at intermediate depths in magmatic hydrothermal environments in silicic and andesitic volcanic terranes. In addition, coarse vein alunite may form in a magmatic steam environment. -from Authors

The Historical Use Of Mine-Drainage And Pyrite-Oxidation Waters In Central And Eastern England, United Kingdom

NASA Astrophysics Data System (ADS)

Banks, David; Younger, Paul L.; Dumpleton, Steve

1996-04-01

Waters draining from abandoned coal or metals mines are often regarded as an environmental threat. Historical examples from the lead and coal mining industries of central and northeastern England illustrate that mine waters can also be regarded as an important resource in terms of 1) baseflow for effluent dilution; 2) drinking or industrial waters; 3) flocculating agents for sewage or water treatment; 4) spa waters; 5) sources of industrial minerals, including alkali metals and barium; and 6) a source of iron oxides or sulphates for tanning or pigmentation purposes. An appreciation of the potential economic value of mine waters and their contents is essential for the design of cost-effective treatment options.

Argillization by descending acid at Steamboat Springs, Nevada

USGS Publications Warehouse

Schoen, Robert; White, Donald E.; Hemley, J.J.

1974-01-01

Steamboat Springs, Nevada, an area of present-day hot springs, clearly illustrates the genetic dependence of some kaolin deposits on hot-spring activity. Andesite, granodiorite and arkosic sediments are locally altered at the land surface to siliceous residues consisting of primary quartz and anatase, plus opal from primary silicates. These siliceous residues commonly exhibit the textural and structural features of their unaltered equivalents. Beneath the siliceous residues, kaolin and alunite replace primary silicates and fill open spaces, forming a blanketlike deposit. Beneath the kaolin-alunite zone, montmorillonite, commonly accompanied by pyrite, replaces the primary silicates. On the ground surface, the same alteration mineral zones can be traced outward from the siliceous residue; however, hematite rather than pyrite accompanies montmorillonite.Chemical analysis indicates that sulfuric acid is the active altering agent. The acid forms from hydrogen sulfide that exsolves from deep thermal water, rises above the water table and is oxidized by sulfur-oxidizing bacteria living near the ground surface. This acid dissolves in precipitation or condensed water vapor and percolates downward destroying most of the primary minerals producing a siliceous residue. Coincidence of the water table with the downward transition from siliceous residue to kaolin-alunite signifies decreasing hydrogen metasomatism because of dilution of descending acid by ground water.In hot-spring areas, beds of siliceous sinter deposited at the surface by hypogene thermal water look, superficially, like areas of surficial acid alteration. Features diagnostic of a surficial alteration are the relict rock structures of a siliceous residue and a kaolin-alunite zone immediately beneath.

Multiscale Characterization and Quantification of Arsenic Mobilization and Attenuation During Injection of Treated Coal Seam Gas Coproduced Water into Deep Aquifers

NASA Astrophysics Data System (ADS)

Rathi, Bhasker; Siade, Adam J.; Donn, Michael J.; Helm, Lauren; Morris, Ryan; Davis, James A.; Berg, Michael; Prommer, Henning

2017-12-01

Coal seam gas production involves generation and management of large amounts of co-produced water. One of the most suitable methods of management is injection into deep aquifers. Field injection trials may be used to support the predictions of anticipated hydrological and geochemical impacts of injection. The present work employs reactive transport modeling (RTM) for a comprehensive analysis of data collected from a trial where arsenic mobilization was observed. Arsenic sorption behavior was studied through laboratory experiments, accompanied by the development of a surface complexation model (SCM). A field-scale RTM that incorporated the laboratory-derived SCM was used to simulate the data collected during the field injection trial and then to predict the long-term fate of arsenic. We propose a new practical procedure which integrates laboratory and field-scale models using a Monte Carlo type uncertainty analysis and alleviates a significant proportion of the computational effort required for predictive uncertainty quantification. The results illustrate that both arsenic desorption under alkaline conditions and pyrite oxidation have likely contributed to the arsenic mobilization that was observed during the field trial. The predictive simulations show that arsenic concentrations would likely remain very low if the potential for pyrite oxidation is minimized through complete deoxygenation of the injectant. The proposed modeling and predictive uncertainty quantification method can be implemented for a wide range of groundwater studies that investigate the risks of metal(loid) or radionuclide contamination.

Fe-rich carbonate chimney in Okinawa Trough Implication for Fe-driven Microbial Anaerobic Oxidation of Methane (AMO)

NASA Astrophysics Data System (ADS)

Peng, X.; Guo, Z.

2016-12-01

Marine sediments associated with cold seeps at continental margins discharge substantial amounts of methane. Microbial anaerobic oxidation of methane (AMO) is a key biogeochemical process in these environments, which can trigger the formation of carbonate chimneys within sediments. The exact biogeochemical mechanism of how AMO control the formation of carbonate chimneys and influence their mineralogy and chemistry remains poorly constrained. Here, we use nano-scale secondary ion mass spectrometry to characterize the petrology and geochemistry of methane-derived Fe-rich carbonate chimneys formed between 5-7 Ma in the Northern Okinawa Trough. We find abundant framboid pyrites formed in the authigenic carbonates in the chimneys, indicating a non-Fe limitation sedimentary system. The δ13C values of carbonate (-18.9‰ to -45.9‰, PDB) show their probable origin from a mixing source of biogenic and thermogenic methane. The δ34S values range from -3.9 ± 0.5‰ to 23.2 ± 0.5‰ (VCDT), indicative of a strong exhaustion of sulfates in a local sulfate pool. We proposed that Fe-rich carbonate chimneys formed at the bottom of the sulfate-methane transition zone, beneath which Fe-driven AOM may happen and provide available ferrous for the extensive precipitation of pyrite in carbonate chimneys. The accumulation of reductive Fe in sediments via this process may widely occur in other analogous settings, with important application for Fe and S biogeochemical cycling within deep sediments at continental margins.

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

PubMed

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

2017-03-06

Oxidation of pyrite (FeS 2 ) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O 2 and H 2 O, releasing sulfoxy species (e.g., S 2 O 3 2- , SO 4 2- ) and ferrous iron (Fe 2+ ) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H 2 O 2 ) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H 2 O 2 formation in aqueous suspensions of FeS 2 microparticles by monitoring, in real time, the H 2 O 2 and dissolved O 2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS 2 dissolution and the degradation of H 2 O 2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H 2 O 2 , showing that FeS 2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

Geothermal Potential of Adak Island, Alaska

DTIC Science & Technology

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

Whole rock and discrete pyrite geochemistry as complementary tracers of ancient ocean chemistry: An example from the Neoproterozoic Doushantuo Formation, China

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.

Derivation of S and Pb in phanerozoic intrusion-related metal deposits from neoproterozoic sedimentary pyrite, Great Basin, United States

USGS Publications Warehouse

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.

Isotope Biogeochemistry of Sulfur in a Cold-Water Carbonate Mound (IODP Site 1317)

NASA Astrophysics Data System (ADS)

Ferdelman, T. G.; Boettcher, M. E.

2007-12-01

To establish a depositional model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled during IODP Expedition 307 in May 2005. Although a role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession, interstitial water profiles of sulfate, alkalinity, Mg, and Sr indicated a tight coupling between carbonate diagenesis and mircrobial sulfate reduction. The reaction of sulfide with siliciclastic iron-bearing minerals to form pyrite was proposed to account for enhanced diagenetic carbonate precipitation (Ferdelman et al., 2006; Proc. IODP, vol. 307; doi:10.2204/iodp.proc.307.2006). To characterize these geomicrobial sulfur transformations in the carbonate mound sediments, the inorganic and stable isotope geochemical compositions of pore water sulfate and solid phase reduced sulfur compounds were performed. Acid-volatile sulfur (AVS) and pyrite del 34S compositions were usually similar and exhibited an increasing trend of from -40 per mil near surface to -20 per mil at the mound base at 132 mbsf. However, several excursions to more 34S sulfur enriched pyrite to values >0 per mil were observed in the deeper sections of the mound sequence. These excursions may be linked transitory changes in the depth of the methane-sulfate transition zone during mound build-up. The oxygen isotopic composition of residual dissolved sulfate indicates intracellular isotope exchange processes within the cells of SRBs, leading to increasing equilibration between extracellular pore water and sulfate.

Environmental controls on sulfur isotopic composition of sulfide minerals in seep carbonates from the South China Sea

NASA Astrophysics Data System (ADS)

Gong, S.; Li, N.; Liang, Q.; Chen, D.; Feng, D.

2017-12-01

Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34Spy value of authigenic sulfide has been used to trace the AOM-related processes. However, the detail mechanism for this is unknown. We proposed the δ34Spy characteristics result from high sulfate reduction rate and its competition with sulfate supply rate. To test this hypothesis, we investigated Mo content, Sr/Ca and Mg/Ca ratios, pyrite content, and its sulfur isotopic compositions in methane-derived carbonates from Site F and Haima in northern South China Sea. Calcite and aragonite were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo content and pyrite have good linear correlations in both aragonites and calcites, and aragonites have more positive slope than calcites. This indicates that there is more Mo available from seawater during the aragonite precipitation. The data suggest that the low δ34Spy values are formed at higher supply rate of sulfate under relatively open system, and high δ34Spy values result from a deep sulfate methane transition zone where dissolve sulfate near to complete exhausted via AOM. The combination of a detailed elemental study of authigenic carbonate with sulfur isotopes of sulfide minerals in carbonates are promising tools for reconstructing the dynamics of seep intensities in modern and, potentially, geological record.

Hydrogeochemie von Eisenausfällungen an Grundwasseraustritten der Abraumkippe Berrenrath (Rheinisches Braunkohlenrevier)

NASA Astrophysics Data System (ADS)

Lenk, Stephan; Wisotzky, Frank; Cremer, Nils

2013-03-01

Groundwater at the abandoned lignite mine in Berrenrath (Germany) is acidic and highly mineralised. Average iron concentrations of 588 mg/l indicate a high potential for acidification. Furthermore, investigations revealed a complete depletion of the carbonate buffer capacity (CaCO3 and HCO3-) during chemical groundwater evolution. Over the next few decades, no decrease of dissolved pyrite oxidation products is expected. On the contrary, within the drainage ditches at the edges of the dump, an intense precipitation of iron oxides is occurring. However, despite oxygen saturation, precipitation of iron oxides is incomplete due to strong acidification of the surface water (pH<3.0). The main contamination of the iron sludge is caused by high nickel concentrations. This element is only loosely bound to the iron oxides and is easily mobilised. Because of high nickel- and sulphate-concentrations, the excavated material has to be deposited in a controlled landfill (German dump category of 2 to 3).

[Investigation of stages of chemical leaching and biooxidation during the extraction of gold from sulfide concentrates].

PubMed

Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T V

2015-01-01

We examined the chemical leaching and biooxidation stages in a two-stage biooxidation process of an auriferous sulfide concentrate containing pyrrhotite, arsenopyrite and pyrite. Chemical leaching of the concentrate (slurry density at 200 g/L) by ferric sulfate biosolvent (initial concentration at 35.6 g/L), which was obtained by microbial oxidation of ferrous sulfate for 2 hours at 70°C at pH 1.4, was allowed to oxidize 20.4% ofarsenopyrite and 52.1% of sulfur. The most effective biooxidation of chemically leached concentrate was observed at 45°C in the presence of yeast extract. Oxidation of the sulfide concentrate in a two-step process proceeded more efficiently than in one-step. In a two-step mode, gold extraction from the precipitate was 10% higher and the content of elemental sulfur was two times lower than in a one-step process.

Growth of ammonia-oxidizing archaea in soil microcosms is inhibited by acetylene.

PubMed

Offre, Pierre; Prosser, James I; Nicol, Graeme W

2009-10-01

Autotrophic ammonia-oxidizing bacteria were considered to be responsible for the majority of ammonia oxidation in soil until the recent discovery of the autotrophic ammonia-oxidizing archaea. To assess the relative contributions of bacterial and archaeal ammonia oxidizers to soil ammonia oxidation, their growth was analysed during active nitrification in soil microcosms incubated for 30 days at 30 degrees C, and the effect of an inhibitor of ammonia oxidation (acetylene) on their growth and soil nitrification kinetics was determined. Denaturing gradient gel electrophoresis (DGGE) analysis of bacterial ammonia oxidizer 16S rRNA genes did not detect any change in their community composition during incubation, and quantitative PCR (qPCR) analysis of bacterial amoA genes indicated a small decrease in abundance in control and acetylene-containing microcosms. DGGE fingerprints of archaeal amoA and 16S rRNA genes demonstrated changes in the relative abundance of specific crenarchaeal phylotypes during active nitrification. Growth was also indicated by increases in crenarchaeal amoA gene copy number, determined by qPCR. In microcosms containing acetylene, nitrification and growth of the crenarchaeal phylotypes were suppressed, suggesting that these crenarchaea are ammonia oxidizers. Growth of only archaeal but not bacterial ammonia oxidizers occurred in microcosms with active nitrification, indicating that ammonia oxidation was mostly due to archaea in the conditions of the present study.

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

Subsurface geomicrobiology in a Mars terrestrial analogue, Río Tinto (SW, Spain)

NASA Astrophysics Data System (ADS)

Amils, R.; Fernández-Remolar, D.; Gómez, F.; González-Toril, E.; Rodríguez, N.; Prieto-Ballesteros, O.; Sanz, J. L.; Díaz, E.; Stoker, C.

2008-09-01

Since its discovery, only few years ago, subsurface geomicrobiology is a matter of growing interest [1]. From a fundamental point of view, it seeks to determine whether life can be sustained in the absence of radiation. From an astrobiological point of view, it is an interesting model for life in other planetary bodies, e.g., Mars, as well as early life on Earth. Río Tinto is an unusual extreme acidic environment due to its size (around 100 km), constant acidic pH (mean pH 2.3), high concentrations of heavy metals and high level of microbial diversity [2]. Río Tinto rises in the core of the Iberian Pyritic Belt, one of the biggest sulfidic ore deposits in the world [3]. Today it is well stablished that the extreme characteristics of Río Tinto are not due to acid mine drainage from mining activity, as has been suggested in the past. To explore the hypothesis that a continuous underground reactor of chemolithotrophic microorganisms thriving in the rich sulfidic minerals of the Iberian Pyritic Belt is responsible for the extreme conditions found in the system, a drilling project has been developed to detect evidence of subsurface microbial activity and potential resources to support these microbial communities in situ (MARTE project) [4]. Here we report a search for subsurface life in volcanically hosted massive sulfidic deposits from the Iberian Pyritic Belt. Aseptic core samples were obtained within and down-gradient from the massive sulfide deposits and formation water was sampled within the resulting bore holes. Microbial activity was detected in un-contaminated samples by culture-dependent and culture-independent methods. Aerobic iron- and sulfide- oxidizing bacteria, and anaerobic denitrifying thiosulfate-oxidizing bacteria, sulfate reducing bacteria and methanogenic archaea have been identified. Potential energy fluxes detected in the system include oxidation of reduced iron and sulfur, or hydrogen gas coupled to nitrite, sulfate, ferric iron, inorganic carbon or transient oxygen. These results suggest that multiple energy sources are available from sulfide-mineral weathering to support microbial metabolism, even in the absence of atmospheric oxygen. [1] Stevens, T.O and McKinley, J.P. (1995) Scienc,, 270, 450-454. [2] Amis, R. et al. (2007) Planet Space Sci, 55, 370- 381. [3] Fernández-Remolar, D. et al. (2005) Earth Planet Sci Lett, 240, 149-167. [4] Amils, R. et al. (2008) Microbiology of Extreme Soils, 205-223.

Hydrothermal synthesis of hydrocarbons at low temperature. Implications for sustaining a biosphere in Europa

NASA Astrophysics Data System (ADS)

Navarro-Gonzalez, Rafael; Montoya, Lilia; Davis, Wanda; McKay, Chris

Observational evidence from Earth-borne systems and space missions as well as theoretical arguments suggest that Jupiter's satellite Europa could be geologically active today and may possess an ocean of liquid water of about 100 km deep underneath the icy surface about 10 km thickness. The existence of an aqueous ocean is an important requirement for life, as we know it. However, a biosphere also depends of an adequate energy source to drive the most fundamental biological processes such as metabolism, growth, reproduction, etc. Methanogenesis associated with hydrothermal vents may potentially drive a biosphere in an European ocean. We report here on the production of a large variety of hydrocarbons in hydrothermal systems at low temperatures (150° C). The chemical composition of the hydrothermal vent gases was derived from a thermochemical model that assumes that Europa had a cometary (solar, less H) abundance at high temperatures characteristic of a vent. Specifically the following gas mixture was used: 45% CO2 , 45% CH4, and 10 % N2 . A 500 ml stainless steel reactor was filled with 200 ml triply distilled water and the gas mixture at 1 bar at 25° C. In some experiments 3 g of pyrite were added into the reaction vessel. The system was heated for 24 hrs in the temperature range from 100 to 375° C. At the completion of the experiment, the reaction was quenched to 25° C and the gas mixture was analyzed by GC-FTIR-MS techniques. In the absence of pyrite, methane is oxidized to carbon dioxide with the possible production of hydrogen. In contrast in the presence of pyrite, methane is converted into a suite of hydrocarbons from C2 to C7 containing all possible isomers. The production of these compounds was found at temperatures as low as 150° C. In order to get a better understanding of the chemical mechanism involved in the synthesis of hydrocarbons and explore the effect on the initial oxidation state of the carbon used, we performed additional experiments in which the oxidation state of carbon varied from 100% methane to 100% carbon dioxide. In all cases, a suite of complex hydrocarbons were formed in the hydrothermal simulations. Therefore, our results strongly support two possible forms of methanogenesis in Europa driven by: 1. Reduction of CO2 to CH4 using H2 ; and 2) Cleavage of hydrocarbons back to CH4 .

Isotopic Evidence for Microbial Activity in Crystalline Bedrock Fractures - a Case Study from Olkiluoto, SW Finland

NASA Astrophysics Data System (ADS)

Sahlstedt, E. K.; Karhu, J.; Pitkänen, P.

2015-12-01

Changes in the geochemical environment in crystalline bedrock fractures were investigated using the stable isotopes of C, O and S in fracture filling minerals as tracers. Of special interest were the possible changes which may occur in the subsurface at low temperatures. Especially, the influence of microbial activity was recognized as a catalyst for inducing changes in the geochemical environment. The study site is the Olkiluoto island located on the western coast of Finland, planned to host a geological repository for nuclear waste. Fracture surfaces were investigated to recognize the latest mineralizations at the site. These fillings were comprised of thin plates or small euhedral crystals of calcite and pyrite. The carbon and sulfur isotope compositions of calcite and pyrite were measured from bulk material by conventional IRMS, and in situ by secondary ion mass spectrometry. A notable feature of the late-stage fillings was high variabilities in the δ13C values of calcite and the δ34S values of pyrite, which ranged from -53.8 ‰ to +31.6 ‰ and from -50.4 ‰ to +77.7 ‰, respectively. Based on the isotopic compositions of the fillings, several features in the past hydrogeochemical environment could be recognized. The isotopic composition of the fracture fillings indicate an environment which was stratified with respect to depth. Characteristic features include bacterial sulfate reduction (BSR) occurring at depths <111 m (bsl), and a methanogenetic environment at depths >50 m. It appears that methanic conditions were replaced by sulfate reduction at depths >50 m likely due to infiltration of SO42--rich brackish waters. Sulfate reducing bacteria used mainly surface derived organic carbon as electron donors. Some indication of minor methanotrophic activity was recognized in anomalously low δ13C values of calcite, down to -53.8 ‰, at the depth range of 34-54 m. This methanotrophic activity may have been related to bacteria using CH4 as an electron donor in BSR.

A Multi-proxy Approach to Understanding the Diagenesis of Carbonates in Pennsylvanian Mudrocks in the Midland Basin

NASA Astrophysics Data System (ADS)

Reis, A.; McGlue, M. M.; Waite, L.; Erhardt, A. M.

2017-12-01

Diagenetic processes influenced by changing climate, eustatic fluctuations, and porewater evolution led to the formation and alteration of carbonate layers in the Pennsylvanian Wolfcamp D Formation of the Midland Basin. Preliminary evidence from bulk geochemistry, oxygen and carbon stable isotopes, and petrographic analysis of the carbonates recovered from two drill cores indicate multiple generations of diagenesis. High Mg calcite and dolomite layers predominantly occur in the fine grained intervals of both cores. Whereas there are less carbonate layers in the central basin core, more of the layers underwent diagenesis compared to the carbonates in the southern core. δ13CPDB values ranging from -6‰ to -4‰ and the presence of framboidal pyrite indicate initial dolomite precipitation occurring in the zone of bacterial sulfate reduction. Later stages alteration occurred following the burial diagenesis of clay, releasing Mg2+ and Fe2+ into the pore waters allowing ferroan dolomite rims to precipitate on the precursor iron-poor dolomite rhombs. δ13CPDB and δ18OPDBvalues from altered beds in the southern core show a positive 4-6‰ offset from the central basin beds. Petrographic analysis of the carbonate intervals shows a larger allochem size, and lower pyrite abundance in the southern core. These differences can be associated with a shorter source-to-sink distance and less frequent bottom water anoxia, leading to reduced rates of sulfate reduction. One possibility we will explore is if increased circulation due to the proximity of the southern core to the Sheffield Channel could stabilize the bottom water conditions in this region of the basin. In addition to dolomite precipitation and replacement, scanning electron microscopy reveals the replacement of silica cements by calcite, suggesting an increase in porewater pH during or following sulfate reduction coinciding with pyrite formation. Changing bottom water chemistry tied to fluctuations in sea-level through time led to porewater conditions favorable to several generations of post-depositional diagenesis.

SEM-EDX and isotope characterization of the organic sulfur in macerals and chars in Illinois Basin coals

USGS Publications Warehouse

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.

Population Structure of Manganese-Oxidizing Bacteria in Stratified Soils and Properties of Manganese Oxide Aggregates under Manganese–Complex Medium Enrichment

PubMed Central

Zhang, Zhongming; Chen, Hong; Liu, Jin; Ali, Muhammad; Liu, Fan; Li, Lin

2013-01-01

Manganese-oxidizing bacteria in the aquatic environment have been comprehensively investigated. However, little information is available about the distribution and biogeochemical significance of these bacteria in terrestrial soil environments. In this study, stratified soils were initially examined to investigate the community structure and diversity of manganese-oxidizing bacteria. Total 344 culturable bacterial isolates from all substrata exhibited Mn(II)-oxidizing activities at the range of 1 µM to 240 µM of the equivalent MnO2. The high Mn(II)-oxidizing isolates (>50 mM MnO2) were identified as the species of phyla Actinobacteria, Firmicutes and Proteobacteria. Seven novel Mn(II)-oxidizing bacterial genera (species), namely, Escherichia, Agromyces, Cellulomonas, Cupriavidus, Microbacterium, Ralstonia, and Variovorax, were revealed via comparative phylogenetic analysis. Moreover, an increase in the diversity of soil bacterial community was observed after the combined enrichment of Mn(II) and carbon-rich complex. The phylogenetic classification of the enriched bacteria represented by predominant denaturing gradient gel electrophoresis bands, was apparently similar to culturable Mn(II)-oxidizing bacteria. The experiments were further undertaken to investigate the properties of the Mn oxide aggregates formed by the bacterial isolates with high Mn(II)-oxidizing activity. Results showed that these bacteria were closely encrusted with their Mn oxides and formed regular microspherical aggregates under prolonged Mn(II) and carbon-rich medium enrichment for three weeks. The biotic oxidation of Mn(II) to Mn(III/IV) by these isolates was confirmed by kinetic examinations. X-ray diffraction assays showed the characteristic peaks of several Mn oxides and rhodochrosite from these aggregates. Leucoberbelin blue tests also verified the Mn(II)-oxidizing activity of these aggregates. These results demonstrated that Mn oxides were formed at certain amounts under the enrichment conditions, along with the formation of rhodochrosite in such aggregates. Therefore, this study provides insights into the structure and diversity of soil-borne bacterial communities in Mn(II)-oxidizing habitats and supports the contribution of soil-borne Mn(II)-oxidizing bacteria to Mn oxide mineralization in soils. PMID:24069232

A Mutator Phenotype Promoting the Emergence of Spontaneous Oxidative Stress-Resistant Mutants in Campylobacter jejuni.

PubMed

Dai, Lei; Sahin, Orhan; Tang, Yizhi; Zhang, Qijing

2017-12-15

Campylobacter jejuni is a leading cause of foodborne illnesses worldwide. As a microaerophilic organism, C. jejuni must be able to defend against oxidative stress encountered both in the host and in the environment. How Campylobacter utilizes a mutation-based mechanism for adaptation to oxidative stress is still unknown. Here we present a previously undescribed phenotypic and genetic mechanism that promotes the emergence of oxidative stress-resistant mutants. Specifically, we showed that a naturally occurring mutator phenotype, resulting from a loss of function mutation in the DNA repair enzyme MutY, increased oxidative stress resistance (OX R ) in C. jejuni We further demonstrated that MutY malfunction did not directly contribute to the OX R phenotype but increased the spontaneous mutation rate in the peroxide regulator gene perR , which functions as a repressor for multiple genes involved in oxidative stress resistance. Mutations in PerR resulted in loss of its DNA binding function and derepression of PerR-controlled oxidative stress defense genes, thereby conferring an OX R phenotype and facilitating Campylobacter survival under oxidative stress. These findings reveal a new mechanism that promotes the emergence of spontaneous OX R mutants in bacterial organisms. IMPORTANCE Although a mutator phenotype has been shown to promote antibiotic resistance in many bacterial species, little is known about its contribution to the emergence of OX R mutants. This work describes the link between a mutator phenotype and the enhanced emergence of OX R mutants as well as its underlying mechanism involving DNA repair and mutations in PerR. Since DNA repair systems and PerR are well conserved in many bacterial species, especially in Gram positives, the same mechanism may operate in multiple bacterial species. Additionally, we developed a novel method that allows for rapid quantification of spontaneous OX R mutants in a bacterial population. This method represents a technical innovation and may also be applied to other bacterial species. These findings significantly advance our understanding of bacterial mechanisms for survival under oxidative stress. Copyright © 2017 American Society for Microbiology.

Communities of ammonia-oxidizing bacteria in activated sludge of various sewage treatment plants in Tokyo.

PubMed

Limpiyakorn, Tawan; Shinohara, Yuko; Kurisu, Futoshi; Yagi, Osami

2005-10-01

We investigated ammonia-oxidizing bacteria in activated sludge collected from 12 sewage treatment systems, whose ammonia removal and treatment processes differed, during three different seasons. We used real-time PCR quantification to reveal total bacterial numbers and total ammonia oxidizer numbers, and used specific PCR followed by denaturing gel gradient electrophoresis, cloning, and sequencing of 16S rRNA genes to analyze ammonia-oxidizing bacterial communities. Total bacterial numbers and total ammonia oxidizer numbers were in the range of 1.6 x 10(12) - 2.4 x 10(13) and 1.0 x 10(9) - 9.2 x 10(10)cellsl(-1), respectively. Seasonal variation was observed in the total ammonia oxidizer numbers, but not in the ammonia-oxidizing bacterial communities. Members of the Nitrosomonas oligotropha cluster were found in all samples, and most sequences within this cluster grouped within two of the four sequence types identified. Members of the clusters of Nitrosomonas europaea-Nitrosococcus mobilis, Nitrosomonas cryotolerans, and unknown Nitrosomonas, occurred solely in one anaerobic/anoxic/aerobic (A2O) system. Members of the Nitrosomonas communis cluster occurred almost exclusively in association with A2O and anaerobic/aerobic systems. Solid residence time mainly influenced the total numbers of ammonia-oxidizing bacteria, whereas dissolved oxygen concentration primarily affected the ammonia-oxidizing activity per ammonia oxidizer cell.

Structurally bound sulfide and sulfate in apatite from the Philips Mine iron oxide - apatite deposit, New York, USA: A tracer of redox changes

NASA Astrophysics Data System (ADS)

Sadove, G.; Konecke, B.; Fiege, A.; Simon, A. C.

2017-12-01

Multiple competing hypotheses attempt to explain the genesis of iron oxide-apatite (IOA) ore deposits. Many studies have investigated the chemistry of apatite because the abundances of F and Cl can distinguish magmatic vs. hydrothermal processes. Recent experiments demonstrate that apatite incorporates S6+, S4+, and S2-, and that total sulfur (∑S) as well as the S6+/∑S ratio in apatite vary systematically as a function of oxygen fugacity [1], providing information about sulfur budget and redox. Here, we present results from X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, electron microprobe analyses, cathodoluminescence (CL) imaging, and element mapping of apatite from the Philip's Mine IOA deposit, southern Adirondack Mountains, USA. The Philip's Mine apatite contains inclusions of pyrite and pyrrhotite, where the latter includes iron oxide and Ni-rich domains. The apatite also contains inclusions of monazite, and exhibits complex CL zonation coincident with variations in the abundances of REE and S. The presence of monazite fingerprints fluid-mediated dissolution-reprecipitation of originally REE-enriched apatite [2]. The S XANES spectra reveal varying proportions of structurally bound S6+ and S2-, as the S6+/∑S ratio ranges from sulfide-only to sulfate-only. Notably, sulfide-dominated domains contain higher S contents than sulfate-dominated regions. These observations are consistent with co-crystallization of apatite and monosulfide solid solution (MSS) at reducing conditions, followed by decomposition of MSS to pyrrhotite, pyrite and intermediate solid solution (ISS, which is not preserved; [3]). Metasomatism of that assemblage by an oxidized fluid resulted in formation of monazite in apatite and iron oxide domains in pyrrhotite. We conclude that the deposit formed by a H2S-Fe-rich volatile phase, possibly evolved from a rather primitive magmatic source, which is consistent with the low Ti content of magnetite. The deposit was subsequently altered by a rather oxidized SO2-poor volatile phase more typical of evolved felsic source regions. [1] Konecke et al. (2017) American Mineralogist 102-3, 548-557; [2] Harlov (2015) Elements 11-3, 171-176; [3] Edmonds & Mather (2017) Elements 13-2, 105-110.

In situ trace metal analysis of Neoarchaean--Ordovician shallow-marine microbial-carbonate-hosted pyrites.

PubMed

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.

World Hydrogen Energy Conference, 5th, Toronto, Canada, July 15-19, 1984, Proceedings

NASA Astrophysics Data System (ADS)

Veziroglu, T. N.; Taylor, J. B.

Among the topics discussed are thermochemical and hybrid processes for hydrogen production, pyrite-assisted water electrolysis, a hydrogen distribution network for industrial use in Western Europe, the combustion of alternative fuels in spark-ignition engines, the use of fuel cells in locomotive propulsion, hydrogen storage by glass microencapsulation, and FeTi compounds' hydriding. Also covered are plasmachemical methods of energy carrier production, synthetic fuels' production in small scale plants, products found in the anodic oxidation of coal, hydrogen embrittlement, and the regulating step in LaNi5 hydride formation.

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

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.

Chemical and physical characteristics of coal and carbonaceous shale samples from the Salt Range coal field, Punjab Province, Pakistan

USGS Publications Warehouse

Warwick, Peter D.; Shakoor, T.; Javed, Shahid; Mashhadi, S.T.A.; Hussain, H.; Anwar, M.; Ghaznavi, M.I.

1990-01-01

Sixty coal and carbonaceous shale samples collected from the Paleocene Patala Formation in the Salt Range coal field, Punjab Province, Pakistan, were analyzed to examine the relationships between coal bed chemical and physical characteristics and depositional environments. Results of proximate and ultimate analyses, reported on an as received basis, indicate that coal beds have an average ash yield of 24.23 percent, average sulfur content of 5.32 percent, average pyritic sulfur content of 4.07 percent, and average calorific value of 8943 Btu (4972 kcal/kg). Thirty five coal samples, analyzed on a whole coal, dry basis for selected trace elements and oxides, have anomalously high average concentrations of Ti, at O.3& percent; Zr, at 382 ppm; and Se, at 11.4 ppm, compared to world wide averages for these elements in coal.Some positive correlation coefficients, significant at a 0.01 level, are those between total sulfur and As, pyritic sulfur and As, total sulfur and sample location, organic sulfur and Se, calorific value (Btu) and sample location, and coal bed thickness and Se. Calorific values -for the samples, calculated on a moist, mineral matter free basis, indicate that the apparent rank of the coal is high volatile C bituminous.Variations observed in the chemical and physical characteristics of the coal beds may be related to depositional environments. Total ash yields and concentrations of Se and organic sulfur increase toward more landward depositional environments and may be related to an increase of fluvial influence on peat deposition. Variations in pyritic sulfur concentrations may be related to post-peat pyrite filled burrows commonly observed in the upper part of the coal bed. The thickest coal beds that have the lowest ash content, and highest calorific values, formed from peats deposited in back barrier, tidal flat environments of the central and western parts of the coal field. The reasons for correlations between Se and coal bed thickness and Se and ash content are not clear and may be a product of averaging.

Sulfur isotope change across the Early Mississippian K-O (Kinderhookian-Osagean) δ13C excursion

NASA Astrophysics Data System (ADS)

Maharjan, Dev; Jiang, Ganqing; Peng, Yongbo; Nicholl, Michael J.

2018-07-01

Paired carbonate associate sulfate (CAS) sulfur isotopes (δ34SCAS), pyrite sulfur isotopes (δ34SPY) and CAS oxygen isotopes (δ18OCAS) across the Early Mississippian K-O δ13C excursion are documented from two sections of a west-dipping carbonate ramp in the southern Great Basin, western U.S.A. A 4-6‰ positive δ34SCAS anomaly, accompanied by negative shifts in δ34SPY and δ18OCAS, is found within the K-O δ13C excursion. In the section with a broader δ13C excursion, Δ34S (Δ34 S =δ34SCAS-δ34SPY) increases from 15‰ to 45‰ and δ13Ccarb drops from 7‰ to 4‰ at the same stratigraphic interval. If this δ34SCAS anomaly represents a global phenomenon, the large magnitude (4-6‰) and short duration (shorter than that of δ13C) suggest an unusual pyrite burial event that expanded from sediments to the ocean water column. In this scenario, the areal and volumetric expansion of sulfate reduction and pyrite burial was likely triggered by abundantly available organic matter near the peak of the K-O δ13C excursion, during which organic carbon production and burial may have reached a maximum, thus substantially expanding the oxygen minimum zone (OMZ). Numerical simulations suggest that pyrite burial rates 2.5-5 times higher than that of the modern ocean followed by sulfide oxidation are required to produce the observed δ34SCAS anomaly in a sulfate-rich ([SO4] ≥28 mM) Early Mississippian ocean. Alternatively, the sulfur and CAS oxygen isotope anomalies may record local sulfur cycling in a foreland basin where changes in weathering input and bottom-water redox conditions in response to sea-level fall and cooling resulted in isotope changes. In both scenarios (either local or global), the integrated carbon, sulfur, and CAS-oxygen isotope data suggest a much more dynamic sulfur cycle across the K-O δ13C excursion than has been previously suggested.

Peralkaline- and calc-alkaline-hosted volcanogenic massive sulfide deposits of the Bonnifield District, East-Central Alaska

USGS Publications Warehouse

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.

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

Sulfur Isotope Analysis of Minerals and Fluids in a Natural CO2 Reservoir, Green River, Utah

NASA Astrophysics Data System (ADS)

Chen, F.; Kampman, N.; Bickle, M. J.; Busch, A.; Turchyn, A. V.

2013-12-01

Predicting the security of geological CO2 storage sites requires an understanding of the geochemical behavior of the stored CO2, especially of fluid-rock reactions in reservoirs, caprocks and fault zones. Factors that may influence geochemical behavior include co-injection of sulfur gases along with the CO2, either in acid-gas disposal or as contaminants in CO2 storage sites, and microbial activity, such as bacterial sulfate reduction. The latter may play an important role in buffering the redox chemistry of subsurface fluids, which could affect toxic trace metal mobilization and transport in acidic CO2-rich fluids. These processes involving sulfur are poorly understood. Natural CO2-reservoirs provide natural laboratories, where the flow and reactions of the CO2-charged fluids and the activity of microbial communities are integrated over sufficient time-scales to aid prediction of long-term CO2 storage. This study reports on sulfur isotope analyses of sulfate and sulfide minerals in rock core and in CO2-charged fluids collected from a stacked sequence of natural CO2 reservoirs at Green River, Utah. Scientific drilling adjacent to a CO2-degassing normal fault to a depth of 325m retrieved core and fluid samples from two CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were collected from CO2-charged springs that discharge through the faults. Sulfur exists as sulfate in the fluids, as sedimentary gypsum beds in the Carmel Formation, as remobilized gypsum veins within a fault damage zone in the Carmel Fm. and in the Entrada Sandstone, and as disseminated pyrite and pyrite-mineralized open fractures throughout the cored interval. We use the stable sulfur (δ34S) and oxygen (δ18OSO4) isotopes of the sulfate, gypsum, and pyrite to understand the source of sulfur in the reservoir as well as the timing of gypsum vein and pyrite formation. The hydration water of the gypsum is also reported to explore the different timing of gypsum vein formation. Macroscopic and microscopic gradients in the sulfur isotope composition of pyrite throughout the core and at discernible redox-reaction fronts were examined in detail to assess the role of bacteria in mediating sulfate reduction, sulfide mineralization and buffering of groundwater redox chemistry. The CO2 charged fluids and gypsum veins within the Entrada Sandstone have a narrow and very similar range in both δ34SSO4 and δ18OSO4, suggesting that the fluids (9.1-10.7‰) are the most likely source of the sulfate in the veins (11.4-12.8‰) and that the veins formed during recent fluid flow through the Entrada, with sulfate coming from remobilized gypsum beds in the Carmel. The Carmel also contains two isotopically distinct types of gypsum veins: one with δ34SSO4 values similar to the Entrada veins and one with much higher δ34SSO4 values (15.1-16.1‰). The latter are likely primary gypsum, while the former are likely secondary gypsum. Sulfur isotope fractionation between pyrite (-16.5‰ to -35.7‰) at the Carmel-Navajo interface and reservoir fluids (9.1-10.7‰) suggest that sulfur reducing bacteria play a role in producing the deposited sulfide. This data demonstrates active sulfur cycling in CO2 reservoirs with many different sulfur species cycled among various pools creating the wide isotope dispersion we observe.

Sulfur speciation and isotope analysis of the 2.7 Ga shallow- and deep-facies black shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Minami, H.; Yamaguchi, K. E.; Naraoka, H.

2014-12-01

It has been widely believed that Great Oxidation Event (GOE: Holland, 1994) occurred at ~2.4-2.2 Ga ago. However, some previous studies have found evidence for oxic ocean and atmosphere from earlier rock records (e.g., Hoashi et al., 2009). In order to explore if such oxic environment was local or global and if there was redox heterogeneity in a sedimentary basin before the inferred GOE, using the 2.7 Ga pyrite-bearing drillcore black shales (deep-facies WRL1 and shallow-facies RHDH2A drillcores) from Pilbara, Western Australia, we separately quantified abundance of S-bearing species (SAVS (acid-volatile sulfide), Spy (pyrite), SSO4 (sulfate), Sorg (organic-S), and S0 (elemental S) and Fe-bearing species (Fecarb, Feox, and Femag) by using sequential extraction methods. These samples were previously used by Brocks et al. (1999), Yamaguchi (2002), Yamaguchi et al. (2005), and Eigenbrode and Freeman (2006). The shallow samples have high S contents and are interpreted to have deposited in relatively anoxic environment, but most of deep samples with elevated Fe contents deposited in relatively oxic environment. The DOP values and δ34Spy values are relatively higher in shallow samples, suggesting active bacterial sulfate reduction in reducing environment created due to near-complete consumption of dissolved O2by decomposition of organic matter produced by photosynthesizers living in the surface ocean. All of these observations consistently suggest that the shallower part was anoxic and deeper part was oxic in the 2.7 Ga ocean. The surface ocean would have been oxygenated due to activity of oxygenic photosynthesis. Such redox stratification of the ocean, i.e., development of mid-depth (shallow) OMZ in an essentially oxic ocean, is typically seen in highly productive regions in the modern ocean. Modern-style oceanic redox structure could have existed as far back as 2.7 Ga ago, much earlier than the inferred GOE at ~2.4-2.2 Ga. Brocks et al. (1999) Science 285, 1033-1036; Eigenbrode & Freeman (2006) PNAS 103, 15759-15764; Hoashi et al. (2009) Nature Geosc. 2, 301-306; Holland (1994) Early Life on Earth, Columbia Univ. Press; Yamaguchi (2002) Ph.D. dissertation, Penn State Univ.; Yamaguchi et al. (2005) Chem. Geol. 218, 135- 169.

Sulfur variability and petrology of the Lower Block Coal Member (Pennsylvanian) in Southwest Indiana

USGS Publications Warehouse

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.

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

PubMed

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.

Tracking selenium behaviour in chalk aquifer (northern France): Sr and 34S-sulphates isotopes constraints.

NASA Astrophysics Data System (ADS)

Cary, Lise; Benabderraziq, Hind; Elkhattabi, Jamal; Parmentier, Marc; Gourcy, Laurence; Négrel, Philippe

2014-05-01

Groundwaters in parts of the Paris Basin (France) are facing increasing selenium (Se) contents that can exceed the drinking water limit of 10 μg/L according to the European Framework Directive in the field of water policy (2000/60/EC). To better understand the groundwater origins and the selenium dynamics, the water chemistry of the Chalk aquifer supplying drinkable water to Lille city was studied. This area is submitted to quantitative and qualitative pressure from industrial, urban and agriculture origins. An integrated study was settled to determine the water sources and dynamics of elements, with a focus on Se. After a large chemical characterisation of the groundwater chemistry in the four field wells, a monthly monitoring was held in four wells and in the Deûle channel. Chemical analysis of major and trace elements, stable isotopes (δ18O, δ2H), strontium isotopes, and δ34S and δ18O of sulphates were realised. The chemical composition of solids sampled at various depths at vicinity of the four wells was also analysed. The specific geochemical signature of groundwater as revealed by Sr isotopes, in addition to element concentrations ratios like Mg/Sr and Se/Sr, highlighted mixture of three main groundwaters bodies: (1) the upstream groundwaters in the recharge area with the most radiogenic 87Sr/86Sr isotopic signature; (2) the confined groundwaters with high Sr concentrations due to water-rock interactions and the lowest 87Sr/86Sr isotopic signature close to the one of the chalk in Paris and London basins; (3) the Se-rich formations of Tertiary and Quaternary. The contents of Se, mainly present as SeV I (and locally as SeIV ), displayed spatial and temporal disparities that can be explained by geological and hydrogeological conditions. Se-rich clayed sediments originating from the dismantling of Se-rich tertiary formations (i.e. Ypresian) overlay the chalk formation and can be found in saturated conditions depending of the water table level. Oxidation of Se0, Se-pyrite and Se linked to organic matters happens according to two pathways. The first one is oxidation of Se species present in the reductive clayed sediments by oxidizing groundwaters during periods of high piezometric levels. The decrease of the piezometric level induces a decrease of the Se contents in groundwaters. Negative δ34S (0 to -28 ) coherent with pyrite oxidation are observed in groundwater. The second one is linked to the infiltration of nitrate-rich recharge waters through quaternary loess which also contain Se. In this case, δ34S of groundwaters are slightly positive and close to the signature of fertilizers. Denitrification by pyrite or Se0 oxidation plays a great role in enhancing Se mobility in a very reactive system. To limit the Se content in groundwaters, a precise water management is needed, e.g. mainly maintaining low piezometric levels in the chalk aquifer or avoiding mixings between contaminated wells, together with a precise knowledge of the geology of the quaternary clayed sediments.

Triple oxygen isotope data characterize oxidation processes that produce sulfate on Earth (and Mars?)

NASA Astrophysics Data System (ADS)

Christensen, J.; Kohl, I.; Coleman, M. L.

2011-12-01

The Rio Tinto, a river in southwest Spain, has a long history of acid, iron and sulfate rich water resulting primarily from the oxidation of pyrite (ferrous iron sulfide). Its geochemistry and extremophile microbiology make it an exciting and ideal mars-analogue research site, as relatively recent discoveries have shown Mars to be rich in sulfates believed to have formed in an acidic environment. Current models for the oxidation pathways of pyrite sulfur to sulfate, and the microbial influences on those pathways are incomplete. Traditionally, studies have only focused on d18O as a tracer for the oxygen sources in sulfate and determination of the oxidation pathways. The d18O method has always been fraught with uncertainty due to isotope fractionation during oxygen incorporation from the two dominant sources, atmospheric oxygen and water. A relatively new method utilizing 17O measures the relationship between d17O/d18O. The average relationship has been defined as the Terrestrial Fractionation Line, with a slope of 0.52. Deviations from this relationship are represented as Cap delta 17O, the difference of delta 17O from the expected value. Cap17O values are useful because they depend only on the relationship between d17O/d18O, which remains constant during mass dependent fractionation. During O2 generation from solid BaSO4, some fractionation can occur due to incomplete oxygen yield. This can produce uncertainties in d17O and d18O, but Cap17O is dependent only on the d17O/d18O ratio and is therefore not affected. The relationship mentioned above between d17O/d18O (slope=0.52) is an average for terrestrial materials and it is becoming increasingly clear that process specific slopes can be defined. This offers an exciting opportunity to characterize potential biomarkers on Mars. If a biologically specific slope could be determined, then its signature will be preserved through subsequent mass dependent fractionation processes. Our approach is to use Río Tinto field and laboratory data to define a process specific slope for natural sulfate, produced via oxidation of pyrite. This study presents field data collected in May of 2011 from various inputs on the Rio Tinto system. The pH range was 0.91-3.18, Eh ranged from 556-831mV. Iron and sulfate were the major ionic species and range from 0.105-587mM and 9.6-989mM, respectively. Initial d18O values are between (-1.5 to +6.0) and are reproducible to (0.8). Cap17O values (calculated with a slope=0.528) range between (0.07-0.192) and are reproducible to (0.007). There is a strong linear relationship between d17O and d18O, which defines a slope or maybe process specific slope of 0.5184, with an R squared value of 0.9995. We will present our update on this ongoing work and our conclusion on whether we have developed a new signature of either or both inorganic and biological oxidation to characterize terrestrial and martian sulfates.

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

NASA Astrophysics Data System (ADS)

Roden, Eric E.

2004-08-01

Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.

In Situ Hydrocarbon Degradation by Indigenous Nearshore Bacterial Populations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherrier, J.

Potential episodic hydrocarbon inputs associated with oil mining and transportation together with chronic introduction of hydrocarbons via urban runoff into the relatively pristine coastal Florida waters poses a significant threat to Florida's fragile marine environment. It is therefore important to understand the extent to which indigenous bacterial populations are able to degrade hydrocarbon compounds and also determine factors that could potentially control and promote the rate at which these compounds are broken down in situ. Previous controlled laboratory experiments carried out by our research group demonstrated that separately both photo-oxidation and cometabolism stimulate bacterial hydrocarbon degradation by natural bacterial assemblagesmore » collected from a chronically petroleum contaminated site in Bayboro Bay, Florida. Additionally, we also demonstrated that stable carbon and radiocarbon abundances of respired CO{sub 2} could be used to trace in situ hydrocarbon degradation by indigenous bacterial populations at this same site. This current proposal had two main objectives: (a) to evaluate the cumulative impact of cometabolism and photo-oxidation on hydrocarbon degradation by natural bacterial assemblages collected the same site in Bayboro Bay, Florida and (b) to determine if in situ hydrocarbon degradation by indigenous bacterial populations this site could be traced using natural radiocarbon and stable carbon abundances of assimilated bacterial carbon. Funds were used for 2 years of full support for one ESI Ph.D. student, April Croxton. To address our first objective a series of closed system bacterial incubations were carried out using photo-oxidized petroleum and pinfish (i.e. cometabolite). Bacterial production of CO{sub 2} was used as the indicator of hydrocarbon degradation and {delta}{sup 13}C analysis of the resultant CO{sub 2} was used to evaluate the source of the respired CO{sub 2} (i.e. petroleum hydrocarbons or the pinfish cometabolite). Results from these time series experiments demonstrated that short-term exposure of petroleum to UV light enhanced hydrocarbon degradation by 48% over that observed for non-photo-oxidized petroleum. Despite the greater bio-availability of the photo-oxidized over the non-photo-oxidized petroleum, an initial lag in CO{sub 2} production was observed indicating potential phototoxicity of the photo- by-products. {delta}{sup 13}C analysis and mass balance calculations reveal that co-metabolism with pinfish resulted in increased hydrocarbon degradation for both photo-oxidized and non-photo-oxidized petroleum each by over 100%. These results demonstrate the cumulative effect of photo-oxidation and co-metabolism on petroleum hydrocarbon degradation by natural bacterial populations indigenous to systems chronically impacted by hydrocarbon input. To address the second objective of this proposal bacterial concentrates were collected from Bayboro Harbor in April 2001 for nucleic acid extraction and subsequent natural radiocarbon abundance analyses. Unfortunately, however, all of these samples were lost due to a faulty compressor in our -70 freezer. The freezer was subsequently repaired and samples were again collected from Bayboro Harbor in June 2002 and again December 2002. Several attempts were made to extract the nucleic acid samples--however, the student was not able to successfully extract and an adequate amount of uncontaminated nucleic acid samples for subsequent natural radiocarbon abundance measurements of the bacterial carbon by accelerator mass spectrometry (i.e. require at least 50 {micro}g carbon for AMS measurement). Consequently, we were not able to address the second objective of this proposed work.« less

Ecogeochemistry of the subsurface food web at pH 0-2.5 in Iron Mountain, California, U.S.A.

USGS Publications Warehouse

Robbins, E.I.; Rodgers, T.M.; Alpers, Charles N.; Nordstrom, D. Kirk

2000-01-01

Pyrite oxidation in the underground mining environment of Iron Mountain, California, has created the most acidic pH values ever reported in aquatic systems. Sulfate values as high as 120 000 mg l-1 and iron as high as 27 600 mg l-1 have been measured in the mine water, which also carries abundant other dissolved metals including Al, Zn, Cu, Cd, Mn, Sb and Pb. Extreme acidity and high metal concentrations apparently do not preclude the presence of an underground acidophilic food web, which has developed with bacterial biomass at the base and heliozoans as top predators. Slimes, oil-like films, flexible and inflexible stalactites, sediments, water and precipitates were found to have distinctive communities. A variety of filamentous and non-filamentous bacteria grew in slimes in water having pH values < 1.0. Fungal hyphae colonize stalactites dripping pH 1.0 water; they may help to form these drip structures. Motile hypotrichous ciliates and bdelloid rotifers are particularly abundant in slimes having a pH of 1.5. Holdfasts of the iron bacterium Leptothrix discophora attach to biofilms covering pools of standing water having a pH of 2.5 in the mine. The mine is not a closed environment - people, forced air flow and massive flushing during high intensity rainfall provide intermittent contact between the surface and underground habitats, so the mine ecosystem probably is not a restricted one.

Ecogeochemistry of the subsurface food web at pH 0–2.5 in Iron Mountain, California, U.S.A.

USGS Publications Warehouse

Robbins, Eleanora I.; Rodgers , Teresa M.; Alpers, Charles N.; Nordstrom, D. Kirk

2000-01-01

Pyrite oxidation in the underground mining environment of Iron Mountain, California, has created the most acidic pH values ever reported in aquatic systems. Sulfate values as high as 120 000 mg l−1 and iron as high as 27 600 mg l−1 have been measured in the mine water, which also carries abundant other dissolved metals including Al, Zn, Cu, Cd, Mn, Sb and Pb. Extreme acidity and high metal concentrations apparently do not preclude the presence of an underground acidophilic food web, which has developed with bacterial biomass at the base and heliozoans as top predators. Slimes, oil-like films, flexible and inflexible stalactites, sediments, water and precipitates were found to have distinctive communities. A variety of filamentous and non-filamentous bacteria grew in slimes in water having pH values <1.0. Fungal hyphae colonize stalactites dripping pH 1.0 water; they may help to form these drip structures. Motile hypotrichous ciliates and bdelloid rotifers are particularly abundant in slimes having a pH of 1.5. Holdfasts of the iron bacterium Leptothrix discophora attach to biofilms covering pools of standing water having a pH of 2.5 in the mine. The mine is not a closed environment – people, forced air flow and massive flushing during high intensity rainfall provide intermittent contact between the surface and underground habitats, so the mine ecosystem probably is not a restricted one.

Process for removing pyritic sulfur from bituminous coals

DOEpatents

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.

Pyrite-Induced Hydrogen Peroxide Formation as a Driving Force in the Evolution of Photosynthetic Organisms on an Early Earth

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.

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

PubMed

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

Age and paragenesis of mineralisation at Coronation Hill uranium deposit, Northern Territory, Australia

NASA Astrophysics Data System (ADS)

Orth, Karin; Meffre, Sebastien; Davidson, Garry

2014-06-01

Coronation Hill is a U + Au + platinum group elements deposit in the South Alligator Valley (SAV) field in northern Australia, south of the better known unconformity-style U East Alligator Rivers (EAR) field. The SAV field differs from the EAR by having a more complex basin-basement architecture. A volcanically active fault trough (Jawoyn Sub-basin) developed on older basement and then was disrupted by renewed faulting, before being buried beneath regional McArthur Basin sandstones that are also the main hanging wall to the EAR deposits. Primary mineralisation at Coronation Hill formed at 1607 ± 26 Ma (rather than 600-900 Ma as previously thought), and so it is likely that the SAV was part of a single west McArthur Basin dilational event. Most ore is hosted in sub-vertical faults and breccias in the competent volcanic cover sequence. This favoured fluid mixing, acid buffering (forming illite) and oxidation of Fe2+ and reduced C-rich assemblages as important uranium depositional mechanisms. However, reduction of U in fractured older pyrite (Pb model age of 1833 ± 67 Ma) is an important trap in diorite. Some primary ore was remobilised at 675 ± 21 Ma to form coarse uraninite + Ni-Co pyrite networks containing radiogenic Pb. Coronation Hill is polymetallic, and in this respect resembles the `egress'-style U deposits in the Athabascan Basin (Canada). However, these are all cover-hosted. A hypothesis for further testing is that Coronation Hill is also egress-style, with ores formed by fluids rising through basement-hosted fault networks (U reduction by diorite pyrite and carbonaceous shale), and into veins and breccias in the overlying Jawoyn Sub-basin volcano-sedimentary succession.

Arsenic-bearing pyrite and marcasite in the Fire Clay coal bed, Middle Pennsylvanian Breathitt Formation, eastern Kentucky

USGS Publications Warehouse

Ruppert, L.F.; Hower, J.C.; Eble, C.F.

2005-01-01

Arsenic concentrations determined on 11 lithotype samples from the Middle Pennsylvanian Breathitt Group Fire Clay coal bed, Leslie County, KY, range from 1 to 418 ppm (whole coal basis). The 11 lithotype samples, which vary in thickness from 4 to 18 cm, were sampled from a continuous 1.38 m channel sample, and were selected based on megascopic appearance (vitrain-rich versus attrital-rich). A lithotype that contains 418 ppm As is located near the top of the coal bed and is composed of 10.5 cm of bright clarain bands containing fusain that, within short distances, grade laterally into Fe sulfide bands. To determine the mode of occurrence of As in this lithotype, the coal was examined with scanning electron microscopy and analyzed by energy dispersive X-ray fluorescence. Massive, framboidal, cell filling, cell-wall replacement, and radiating forms of Fe sulfide were observed in the high As lithotype; many of the radiating Fe sulfide forms, and one of the cell-wall replacements contained As. Examination of the grains with optical light microscopy shows that the majority of radiating morphologies are pyrite, the remainder are marcasite. Selected Fe sulfide grains were also analyzed by electron microprobe microscopy. Arsenic concentrations within individual grains range from 0.0 wt.% to approximately 3.5 wt.%. On the basis of morphology, these Fe sulfides are presumed to be of syngenetic origin and would probably be removed from the coal during physical coal cleaning, thus eliminating a potential source of As from the coal combustion process. However, because the grains are radiating and have high surface area, dissolution and release of As could occur if the pyrite is oxidized in refuse ponds.

Research on genesis of pyrite near the Permian-Triassic boundary in meishan, Zhejiang, China

USGS Publications Warehouse

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.

Ammonium supply rate influences archaeal and bacterial ammonia oxidizers in a wetland soil vertical profile.

PubMed

Höfferle, Špela; Nicol, Graeme W; Pal, Levin; Hacin, Janez; Prosser, James I; Mandić-Mulec, Ines

2010-11-01

Oxidation of ammonia, the first step in nitrification, is carried out in soil by bacterial and archaeal ammonia oxidizers and recent studies suggest possible selection for the latter in low-ammonium environments. In this study, we investigated the selection of ammonia-oxidizing archaea and bacteria in wetland soil vertical profiles at two sites differing in terms of the ammonium supply rate, but not significantly in terms of the groundwater level. One site received ammonium through decomposition of organic matter, while the second, polluted site received a greater supply, through constant leakage of an underground septic tank. Soil nitrification potential was significantly greater at the polluted site. Quantification of amoA genes demonstrated greater abundance of bacterial than archaeal amoA genes throughout the soil profile at the polluted site, whereas bacterial amoA genes at the unpolluted site were below the detection limit. At both sites, archaeal, but not the bacterial community structure was clearly stratified with depth, with regard to the soil redox potential imposed by groundwater level. However, depth-related changes in the archaeal community structure may also be associated with physiological functions other than ammonia oxidation. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Investigation of mineral transformations and ash deposition during staged combustion. Quarterly technical progress report, April 1, 1997--June 30, 1997

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

New insight into the mechanism of peroxymonosulfate activation by sulfur-containing minerals: Role of sulfur conversion in sulfate radical generation.

PubMed

Zhou, Yang; Wang, Xiaolei; Zhu, Changyin; Dionysiou, Dionysios D; Zhao, Guangchao; Fang, Guodong; Zhou, Dongmei

2018-06-04

Peroxymonosulfate (PMS) or persulfate activation by sulfur-containing minerals has been applied extensively for the degradation of contaminants; however, the role of sulfur conversion in this process has not been fully explored. In this study, pyrite (FeS 2 )-based PMS activation process was developed for diethyl phthalate (DEP) degradation, and its underlying mechanisms were elucidated. PMS was found to be efficiently activated by FeS 2 for DEP degradation and mineralization, achieving 58.9% total organic carbon removal using 0.5 g/L FeS 2 and 2.0 mM PMS. Sulfides were the dominant electron donor for PMS activation, and mediated Fe(II) regeneration to activate PMS on the surface of FeS 2 particles. Meanwhile, different sulfur conversion intermediates, such as S 5 2- , S 8 0 , S 2 O 3 2- , and SO 3 2- , were formed from the oxidation of sulfides by Fe(III) and PMS, and determined by X-ray photoelectron spectroscopy and in-situ attenuated total reflectance Fourier transform infrared spectroscopy analysis. SO 3 2- was the dominant sulfur species responsible for sulfate radicals (SO 4 - ) generation by activating PMS directly or activating Fe(III) to initiate a radical chain reaction, which was supported by the electron paramagnetic resonance results. This study highlights the important role of sulfur conversion in PMS activation by pyrite and provides new insights into the mechanism of oxidant activation by sulfur-containing minerals. Copyright © 2018. Published by Elsevier Ltd.

Geochemical and mineralogical studies of a South Texas roll-front uranium deposit

USGS Publications Warehouse

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.

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

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.

Iron sulfide deposits at Wadi Wassat, Kingdom of Saudi Arabia

USGS Publications Warehouse

Roberts, R.J.; Rossman, D.L.; Bagdady, A.Y.; Conway, C.M.; Helaby, A.M.

1981-01-01

Massive and disseminated iron sulfide deposits in Wadi Wassat form lenticular, stratabound deposits in cherty Precambrian sedimentary rocks interlayered with Precambrian calcareous sedimentary rocks, pyroclastic rocks, and andesitic flow rocks. These rocks have been cut by a wide variety of plutonic and dike rocks including gabbro, diorite, granodiorite, diabase, rhyolite, and granite. The zone containing the sulfide lenses is nearly 16 km long and is cut off by granitic rocks at both the northern and southern ends. The lenses are as much as 200 m thick; one can be traced along strike for more than 4 km. The lenses consist mostly of iron sulfides. Pyrite is the principal sulfide mineral; near intrusive bodies the pyrite has been partially converted to pyrrhotite and locally mobilized into fractures. The sulfides have been oxidized to a depth of about 25 m. Preliminary calculations indicate that about 107,500,000 tons of sulfides, averaging 40 percent iron and 35 percent sulfur, are available to a depth of i00 m. Small amounts of nickel, cobalt, zinc, and copper are also present, but at metal prices prevailing in early 1981, these do not constitute significant resources.

Acid-rock drainage at Skytop, Centre County, Pennsylvania, 2004

USGS Publications Warehouse

Hammarstrom, Jane M.; Brady, Keith; Cravotta, Charles A.

2005-01-01

Recent construction for Interstate Highway 99 (I?99) exposed pyrite and associated Zn-Pb sulfide minerals beneath a >10-m thick gossan to oxidative weathering along a 40-60-m deep roadcut through a 270-m long section of the Ordovician Bald Eagle Formation at Skytop, near State College, Centre County, Pennsylvania. Nearby Zn-Pb deposits hosted in associated sandstone and limestone in Blair and Centre Counties were prospected in the past; however, these deposits generally were not viable as commercial mines. The pyritic sandstone from the roadcut was crushed and used locally as road base and fill for adjoining segments of I?99. Within months, acidic (pH1,000 mg/L), seep waters at the base of the cut contain >100 mg/L dissolved Zn and >1 mg/L As, Co, Cu, and Ni. Lead is relatively immobile (<10 ?g/L in seep waters). The salts sequester metals and acidity between rainfall events. Episodic salt dissolution then contributes pulses of contamination including acid to surface runoff and ground water. The Skytop experience highlights the need to understand dynamic interactions of mineralogy and hydrology in order to avoid potentially negative environmental impacts associated with excavation in sulfidic rocks.

A novel bioreactor system for simultaneous mutli-metal leaching from industrial pyrite ash: Effect of agitation and sulphur dosage.

PubMed

Panda, Sandeep; Akcil, Ata; Mishra, Srabani; Erust, Ceren

2018-01-15

Simultaneous multi-metal leaching from industrial pyrite ash is reported for the first time using a novel bioreactor system that allows natural diffusion of atmospheric O 2 and CO 2 along with the required temperature maintenance. The waste containing economically important metals (Cu, Co, Zn & As) was leached using an adapted consortium of meso-acidophilic Fe 2+ and S oxidising bacteria. The unique property of the sample supported adequate growth and activity of the acidophiles, thereby, driving the (bio) chemical reactions. Oxido-reductive potentials were seen to improve with time and the system's pH lowered as a result of active S oxidation. Increase in sulphur dosage (>1g/L) and agitation speed (>150rpm) did not bear any significant effect on metal dissolution. The consortium was able to leach 94.01% Cu (11.75% dissolution/d), 98.54% Co (12.3% dissolution/d), 75.95% Zn (9.49% dissolution/d) and 60.80% As (7.6% dissolution/d) at 150rpm, 1g/L sulphur, 30°C in 8days. Copyright © 2017 Elsevier B.V. All rights reserved.

Geochemical Study on an Abandoned Copper Smelting Plant Using Rare Earth Elements

NASA Astrophysics Data System (ADS)

Sun, S. H.

2017-12-01

The Shuei Nan Dong Copper Smelting Plant smelting is located on the northern coast of New Taipei City, Taiwan. The plant built in 1906 for but has been shut down since 1987. However, the watershed is continuing to discharge acid mine water into the sea; and, the acid mine drainage releases high amounts of sulfate, heavy metals without any treatment. In this study, the water samples were sequentially collected along the main channel and its tributaries in the watershed. The results of hydrochemical analysis show that the untreated inflow water can be characterized with low pH value of <3 and enriched sulfate, copper and arsenic. However, the water is much less contaminated in the upstream area until a major tributary converge. The results of principal component analysis (PCA) demonstrate that the first principal component (PC) can explain >80% of the total variance and almost all chemical components have high loadings in the PC. Therefore, the hydrochemical properties in the watershed are mainly dominated by the mixing process between main channel and the major tributary but the geochemical reactions during flow down the channel is insignificant. Rare earth elements (REE) are an excellent tracer, which can indicate sources of chemical components and geochemical reactions in water. The analysis results demonstrate two distinct REE patterns. The water with low REE can be characterized by prominent Eu positive anomaly and Ce negative anomaly, which may result from the alteration of Na-plagioclase in sandstone and oxidation reaction when contact with air, respectively. On the contrary, the water with high REE shows only minor Ce negative anomaly and insignificant Eu positive anomaly. In addition, there is an enrichment of middle REE in high-REE water, which is quite different with the REE pattern of pyrite. According to the Grawunder's study (2014), it corresponds to the complexation to sulphite during pyrite oxidation. It is worth noting that REE show no considerable fractionation along the channel and confirms the results from PCA. It can be derived that the water may not reached equilibrium condition. A simple aerated retention pool could dramatically reduce the pollutants due to coprecipitation of iron oxide and aluminum oxide.

Re-Os systematics and age of pyrite associated with stratiform Zn-Pb mineralization in the Howards Pass district, Yukon and Northwest Territories, Canada

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.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-03-01

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.

Sediment Sulfur Isotopes Reflect Seawater Oxygen Rise in Neoarchean

NASA Astrophysics Data System (ADS)

Fakhraee, M.; Crowe, S.; Katsev, S.

2017-12-01

The oxygenation of the ocean-atmosphere system is recorded in S isotopes preserved in sedimentary pyrites. Disappearance of mass independent fractionation of S (S-MIF) around 2.45 Ga signals the first large-scale oxygenation of the atmosphere (the GOE), while a narrow range of pyritic δ34S during the Archean eon suggests limited oxidative cycling of S. Both δ34S and S-MIF ranges, however, undergo a clear and unexplained expansion in the Neoarchean between 2.7 and 2.45 Ga, indicating a change in global S-cycling. By analyzing the preservation patterns of isotopic signals with a 1D reaction-transport model, we show that the rock record points to the rise of oxygen in shallow marine environments around 2.7 billion years ago. The model tracks d34S and Δ33S isotopic transformations during early diagenesis in a reaction-transport framework. The results indicate that δ34S and MIF signatures in >2.7Ga sulfides require deposition from anoxic or minimally oxygenated seawater, whereas the 2.7-2.4 Ga expansion in both δ34S and D33S ranges points to at least localized accumulation oxygen to low μM levels, accompanied by a moderate rise in sulfate from low μM concentrations to up to 200 μM. In contrast to the role of oxygen in the atmosphere where it suppresses the production of MIF, oxygen in seawater at levels below 25 μM does not necessarily suppress the MIF preservation, which instead depends on the availability of reactive organic matter, sulfate, and electron acceptors for sulfide re-oxidation. The S-isotopes in Neoarchean sulfides thus paint a picture of gradual oxygenation of shallow marine environments under a nearly anoxic atmosphere where the atmospherically produced S isotopic signals are overprinted by increasingly oxidative diagenesis, rising sulfate levels, and increasing organic sedimentation.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers (1): New insights from short-term batch experiments.

PubMed

Aquilina, Luc; Roques, Clément; Boisson, Alexandre; Vergnaud-Ayraud, Virginie; Labasque, Thierry; Pauwels, Hélène; Pételet-Giraud, Emmanuelle; Pettenati, Marie; Dufresne, Alexis; Bethencourt, Lorine; Bour, Olivier

2018-04-01

We investigate denitrification mechanisms through batch experiments using crushed rock and groundwater from a granitic aquifer subject to long term pumping (Ploemeur, France). Except for sterilized experiments, extensive denitrification reaction induces NO 3 decreases ranging from 0.3 to 0.6mmol/L. Carbon concentrations, either organic or inorganic, remain relatively stable and do not document potential heterotrophic denitrification. Batch experiments show a clear effect of mineral dissolution which is documented through cation (K, Na, Ca) and Fluoride production. These productions are tightly related to denitrification progress during the experiment. Conversely, limited amounts of SO 4 , systematically lower than autotrophic denitrification coupled to sulfur oxidation stoichiometry, are produced during the experiments which indicates that sulfur oxidation is not likely even when pyrite is added to the experiments. Analysis of cation ratios, both in isolated minerals of the granite and within water of the batch, allow the mineral dissolution during the experiments to be quantified. Using cation ratios, we show that batch experiments are characterized mainly by biotite dissolution. As biotite contains 21 to 30% of Fe and 0.3 to 1.7% of F, it constitutes a potential source for these two elements. Denitrification could be attributed to the oxidation of Fe(II) contained in biotite. We computed the amount of K and F produced through biotite dissolution when entirely attributing denitrification to biotite dissolution. Computed amounts show that this process may account for the observed K and F produced. We interpret these results as the development of microbial activity which induces mineral dissolution in order to uptake Fe(II) which is used for denitrification. Although pyrite is probably available, SO 4 and cation measurements favor a large biotite dissolution reaction which could account for all the observed Fe production. Chemical composition of groundwater produced from the Ploemeur site indicates similar denitrification processes although original composition shows mainly plagioclase dissolution. Copyright © 2017 Elsevier B.V. All rights reserved.