Potential Aquifer Vulnerability in Regions Down-Gradient from ...

EPA Pesticide Factsheets

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

Synchrotron X-ray characterization of mackinawite and uraninite relevant to bio-remediation of groundwater contaminated with uranium

NASA Astrophysics Data System (ADS)

Carpenter, J.; Hyun, S.; Hayes, K. F.

2010-12-01

Uranium (U) originating from mining operations for weapon manufacturing and nuclear energy production is a significant radionuclide contaminant in groundwater local to uranium mining, uranium milling, and uranium mill tailing (UMT) storage sites. In the USA, the Department of Energy (DOE) is currently overseeing approximately 24 Uranium Mill Tailing Remediation Action (UMTRA) sites which have collectively processed over 27 million tons of uranium ore1,2. In-Situ microbial bio-reduction of the highly mobile U6+ ion into the dramatically less mobile U4+ ion has been demonstrated as an effective remedial process to inhibit uranium migration in the aqueous phase3. The resistance of this process to oxidization and possible remobilization of U when bioremediation stops (and oxidants such as oxygen from the air or nitrate in water diffuse into the formation) in the long term is not known. UMTRA site studies3 have shown that iron sulfide solids are produced by sulfate reducing bacteria (SRB) during U bioremediation, and some forms of these iron sulfide solids are known to be effective oxidant scavengers, potentially protecting against re-oxidation and thus remobilization of U. This work is investigating the role of iron sulfide solids in the long-term immobilization of reduced U compounds after bioremediation is completed in groundwater local to UMTRA sites. Re-oxidation tests are being performed in packed media columns loaded with both FeS and U solids. High quality mackinawite (FeS), and uraninite (UO2) have been synthesized in our laboratory via a wet chemistry approach. These synthetic materials are expected to mimic the naturally occurring and biogenic materials present in biologically stimulated UMTRA sites. In order to establish the initial conditions of the prepared experimental columns and to compare synthetic and biogenic FeS and UO2, these synthesized materials have been characterized with synchrotron radiation at the Stanford Synchrotron Radiation Lightsource using synchrotron x-ray powder diffraction (SXRD) and extended x-ray absorption fine structure (EXAFS). SXRD data were collected and analyzed with profile fitting to determine lattice parameters and crystallite size for comparison with published values for both biogenic and synthetic materials. This is particularly of interest for UO2, as there is very little information on particle size and lattice parameters for synthetic UO2 in the literature. Profile fitting of the SXRD data for FeS gives lattice parameters of a = b = 3.668 and a mean crystallite size of 5 to 8 nm. Both of these values are in good agreement with published values. For fresh UO2, lattice parameters were determined as a = b = c = 5.4 nm for both freshly synthesized and aged (3 months) UO2 and particle size was determined to be 3.5 nm for fresh UO2 and 5.83 nm for aged UO2. This suggests a growth mechanism for crystallites over time, and an inferred decrease in reactivity.

LEACHING OF URANIUM ORES USING ALKALINE CARBONATES AND BICARBONATES AT ATMOSPHERIC PRESSURE

DOEpatents

Thunaes, A.; Brown, E.A.; Rabbits, A.T.; Simard, R.; Herbst, H.J.

1961-07-18

A method of leaching uranium ores containing sulfides is described. The method consists of adding a leach solution containing alkaline carbonate and alkaline bicarbonate to the ore to form a slurry, passing the slurry through a series of agitators, passing an oxygen containing gas through the slurry in the last agitator in the series, passing the same gas enriched with carbon dioxide formed by the decomposition of bicarbonates in the slurry through the penultimate agitator and in the same manner passing the same gas increasingly enriched with carbon dioxide through the other agitators in the series. The conditions of agitation is such that the extraction of the uranium content will be substantially complete before the slurry reaches the last agitator.

U-Pb dating of uranium deposits in collapse breccia pipes of the Grand Canyon region

USGS Publications Warehouse

Ludwig, K. R.; Simmons, K.R.

1992-01-01

Two major periods of uranium mineralization are indicated by U-Pb isotope dating of uranium ores from collapse breccia pipes in the Grand Canyon region, northern Arizona. The Hack 2 and 3, Kanab North, and EZ 1 and 2 orebodies apparently formed in the interval of 200 ?? 20 Ma, similar to ages inferred for strata-bound, Late Triassic-hosted uranium deposits in southern Utah and northern Arizona. Samples from the Grand Canyon and Pine Nut pipes, however, indicate a distinctly older age of about 260 Ma. The clustering in ages for a variety of uranium deposits at about the age of the lower part of the Chinle Formation (Late Triassic) suggests that uranium in these deposits may have been derived by leaching from volcanic ash in the Chinle and mobilized by ground-water movement. Pb isotope ratios of galenas in mineralized pipes are more radiogenic than those of sulfides from either uranium-poor pipes or occurrences away from pipes. Fluids which passed through the pipes had interacted with the Proterozoic basement, possibly through the vertical fractures which influenced the location and evolution of the pipes themselves. -from Authors

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.

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.

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

PubMed

Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

2016-12-01

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

The Permo-Triassic uranium deposits of Gondwanaland

NASA Astrophysics Data System (ADS)

le Roux, J. P.; Toens, P. D.

The world's uranium provinces are time bound and occur in five distinct periods ranging from the Proterozoic to the Recent. One of these periods embraces the time of Gondwana sedimentation and probably is related to the proliferation of land plants from the Devonian on-ward. Decaying vegetal matter produced reducing conditions that enhanced uranium precipitation. The association of uranium with molassic basins adjacent to uplifted granitic and volcanic arcs suggests that lithospheric plate subduction, leading to anatexis of basement rocks and andesitic volcanism, created favorable conditions for uranium mineralization. Uranium occurrences of Gondwana age are of four main types: sandstone-hosted, coal-hosted, pelite-hosted, and vein-type deposits. Sandstone-hosted deposits commonly occur in fluviodeltaic sediments and are related to the presence of organic matter. These deposits commonly are enriched in molybdenum and other base metal sulfides and have been found in South Africa, Zimbabwe, Zambia, Angola, Niger, Madagascar, India, Australia, Argentina, and Brazil. Coalhosted deposits contain large reserves of uranium but are of low grade. In Africa they are mostly within the Permian Ecca Group and its lateral equivalents, as in the Springbok Flats, Limpopo, Botswana, and Tanzania basins. Uraniferous black shales are present in the Gabon and Amazon basins but grades are low. Vein-type uranium is found in Argentina, where it occurs in clustered veins crosscutting sedimentary rocks and quartz porphyries.

The Gas Hills uranium district and some probable controls for ore deposition

USGS Publications Warehouse

Zeller, Howard Davis

1957-01-01

Uranium deposits occur in the upper coarse-grained facies of the Wind River formation of Eocene age in the Gas Hills district of the southern part of the Wind River Basin. Some of the principal deposits lie below the water table in the unoxidized zone and consist of uraninite and coffinite occurring as interstitial fillings in irregular blanket-like bodies. In the near-surface deposits that lie above the water table, the common yellow uranium minerals consist of uranium phosphates, silicates, and hydrous oxides. The black unoxidized uraninite -coffinite ores show enrichment of molybdenum, arsenic, and selenium when compared to the barren sandstone. Probable geologic controls for ore deposits include: 1) permeable sediments that allowed passage of ore-bearing solutions; 2) numerous faults that acted as impermeable barriers impounding the ore -bearing solutions; 3) locally abundant pyrite, carbonaceous material, and natuial gas containing hydrogen sulfide that might provide a favorable environment for precipitation of uranium. Field and laboratory evidence indicate that the uranium deposits in the Gas Hills district are very young and related to the post-Miocene to Pleistocene regional tilting to the south associated with the collapse of the Granite Mountains fault block. This may have stopped or reversed ground water movement from a northward (basinward) direction and alkaline ground water rich in carbonate could have carried the uranium into the favorable environment that induced precipitation.

Effect of metal sulfide pulp density on gene expression of electron transporters in Acidithiobacillus sp. FJ2.

PubMed

Fatemi, Faezeh; Miri, Saba; Jahani, Samaneh

2017-05-01

In Acidithiobacillus ferrooxidans, one of the most important bioleaching bacterial species, the proteins encoded by the rus operon are involved in the electron transfer from Fe 2+ to O 2 . To obtain further knowledge about the mechanism(s) involved in the adaptive responses of the bacteria to growth on the different uranium ore pulp densities, we analyzed the expression of the four genes from the rus operon by real-time PCR, when Acidithiobacillus sp. FJ2 was grown in the presence of different uranium concentrations. The uranium bioleaching results showed the inhibitory effects of the metal pulp densities on the oxidation activity of the bacteria which can affect Eh, pH, Fe oxidation and uranium extractions. Gene expression analysis indicated that Acidithiobacillus sp. FJ2 tries to survive in the stress with increasing in the expression levels of cyc2, cyc1, rus and coxB, but the metal toxicity has a negative effect on the gene expression in different pulp densities. These results indicated that Acidithiobacillus sp. FJ2 could leach the uranium even in high pulp density (50%) by modulation in rus operon gene responses.

Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

USGS Publications Warehouse

Cunningham, C.G.; Rasmussen, J.D.; Steven, T.A.; Rye, R.O.; Rowley, P.D.; Romberger, S.B.; Selverstone, J.

1998-01-01

Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS2, together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km2 area, above a cupola of a composite, recurrent, magma chamber at least 24 ?? 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, 'pull-apart' fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200??C, ??18OH2O ~ -1.5, ?? -1.5, ??DH2O ~ -130, log fO2 about -47 to -50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in precipitation of uranium minerals. At the deepest exposed levels, wall-rocks were altered to sericite; and uraninite, coffinite, jordisite, fluorite, molybdenite, quartz, and pyrite were deposited in the veins. The fluids were progressively oxidized and cooled at higher levels in the system by boiling and degassing; iron-bearing minerals in wall rocks were oxidized to hematite, and quartz, fluorite, minor siderite, and uraninite were deposited in the veins. Near the ground surface, the fluids were acidified by condensation of volatiles and oxidation of hydrogen sulfide in near-surface, steam-heated, ground waters; wall rocks were altered to kaolinite, and quartz fluorite, and uraninite were deposited in veins. Secondary uranium minerals, hematite, and gypsum formed during supergene alteration later in the Cenozoic when the upper part of the mineralized system was exposed by erosion.

Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

2014-12-01

The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may normally be controlled by other oxidative pathways in which oxygen plays an indirect role.

Radioactive mineral springs in Delta County, Colorado

USGS Publications Warehouse

Cadigan, Robert A.; Rosholt, John N.; Felmlee, J. Karen

1976-01-01

The system of springs in Delta County, Colo., contains geochemical clues to the nature and location of buried uranium-mineralized rock. The springs, which occur along the Gunnison River and a principal tributary between Delta and Paonia, are regarded as evidence of a still-functioning hydrothermal system. Associated with the springs are hydrogen sulfide and sulfur dioxide gas seeps, carbon dioxide gas-powered geysers, thick travertine deposits including radioactive travertine, and a flowing warm-water (41?C) radioactive well. Geochemical study of the springs is based on surface observations, on-site water-property measurements, and sampling of water, travertine, soft precipitates, and mud. The spring deposits are mostly carbonates, sulfates, sulfides, and chlorides that locally contain notable amounts of some elements, such as arsenic, barium, lithium, and radium. Samples from five localities have somewhat different trace element assemblages even though they are related to the same hydrothermal system. All the spring waters but one are dominated by sodium chloride or sodium bicarbonate. The exception is an acid sulfate water with a pH of 2.9, which contains high concentrations of aluminum and iron. Most of the detectable radioactivity is due to the presence of radium-226, a uranium daughter product, but at least one spring precipitate contains abundant radium-228, a thorium daughter product. The 5:1 ratio of radium-228 to radium-226 suggests the proximity of a vein-type deposit as a source for the radium. The proposed locus of a thorium-uranium mineral deposit is believed to lie in the vicinity of Paonia, Colo. Exact direction and depth are not determinable from data now available.

Hydrogeochemical and stream sediment detailed geochemical survey for Edgemont, South Dakota; Wyoming

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

Butz, T.R.; Dean, N.E.; Bard, C.S.

1980-05-31

Results of the Edgemont detailed geochemical survey are reported. Field and laboratory data are presented for 109 groundwater and 419 stream sediment samples. Statistical and areal distributions of uranium and possible uranium-related variables are given. A generalized geologic map of the survey area is provided, and pertinent geologic factors which may be of significance in evaluating the potential for uranium mineralization are briefly discussed. Groundwaters containing greater than or equal to 7.35 ppB uranium are present in scattered clusters throughout the area sampled. Most of these groundwaters are from wells drilled where the Inyan Kara Group is exposed at themore » surface. The exceptions are a group of samples in the northwestern part of the area sampled and south of the Dewey Terrace. These groundwaters are also produced from the Inyan Kara Group where it is overlain by the Graneros Group and alluvium. The high uranium groundwaters along and to the south of the terrace are characterized by high molybdenum, uranium/specific conductance, and uranium/sulfate values. Many of the groundwaters sampled along the outcrop of the Inyan Kara Group are near uranium mines. Groundwaters have high amounts of uranium and molybdenum. Samples taken downdip are sulfide waters with low values of uranium and high values of arsenic, molybdenum, selenium, and vanadium. Stream sediments containing greater than or equal to 5.50 ppM soluble uranium are concentrated in basins draining the Graneros and Inyan Kara Groups. These values are associated with high values for arsenic, selenium, and vanadium in samples from both groups. Anomalous values for these elements in the Graneros Group may be caused by bentonite beds contained in the rock units. As shown on the geochemical distribution plot, high uranium values that are located in the Inyan Kara Group are almost exclusively draining open-pit uranium mines.« less

Application of Biostimulation for Remediation of Sulfate-Contaminated Groundwater at a Mining Site

NASA Astrophysics Data System (ADS)

Miao, Z.; Carroll, K. C.; Carreon, C.; Brusseau, M. L.

2011-12-01

There is growing concern regarding sulfate contamination of groundwater. One innovative in-situ remediation option under investigation is biostimulation through addition of electron-donor amendments to enhance sulfate reduction. Two pilot-scale ethanol-injection tests were conducted at a former uranium mining site that is contaminated with sulfate and nitrate (with a lack of heavy metals), and for which there appears to be minimal natural attenuation of sulfate. The first test was a push-pull test that had a limited zone of influence, while the second test was a single-well injection test in which additional downgradient wells were monitored. For both tests, sulfate concentrations began to decline within a few weeks of injection, after nitrate concentrations were significantly reduced. Concomitantly, aqueous concentrations of manganese, iron, and hydrogen sulfide increased from background. Monitoring over many months revealed that the declines in sulfate concentration conformed to exponential decay, with first-order decay rates of approximately 0.01 /d. Analysis of sulfur stable isotope data indicated that the decrease in sulfate concentrations was microbially mediated. The results also indicated that sulfides formed during sulfate reduction may have undergone partial re-oxidation. This study illustrates the feasibility of using ethanol injection for remediation of sulfate-contaminated groundwater. However, re-oxidation of sulfides (both metal sulfide precipitates and hydrogen sulfide gas) is a potential issue of significance that would need to be addressed.

Distribution of uranium in the Bisbee district, Cochise County, Arizona

USGS Publications Warehouse

Wallace, Stewart R.

1956-01-01

The Bisbee district has been an important source of copper for many years, and substantial amounts of lead and zinc ore and minor amounts of manganese ore have been mined during certain periods. The copper deposits occur both as low-grade disseminated ore in the Sacramento Hill stock and as massive sulfide (and secondary oxide and carbonate) replacement bodies in Paleozoic limestones that are intruded by the stock and related igneous bodies. The lead-zinc production has come almost entirely from limestone replacement bodies. The disseminated ore exhibits no anomalous radioactivity, and samples from the Lavender pit contain from 0.002 to less than 0.001 percent equivalent uranium. The limestone replacement ores are distinctly radioactive and stoping areas can be readily distinguished from from unmineralized ground on the basis of radioactivity alone. The equivalent uranium content of the copper replacement ores ranges from 0.002 to 0.014 percent and averages about 0.005 percent; the lead-zinc replacement ores average more than 0.007 percent equivalent uranium. Most of the uranium in the copper ores of the district is retained in the smelter slag of a residual concentrate; the slag contains about 0.009 percent equivalent uranium. Uranium carried off each day by acid mine drainage is roughly equal to 1 percent of that being added to the slag dump. Although the total amount of uranium in the district is large, no minable concentrations of ore-grade material are known; samples of relatively high-grade material represent only small fractions of tons at any one locality.

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

The impact of biostimulation on the fate of sulfate and associated sulfur dynamics in groundwater

NASA Astrophysics Data System (ADS)

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-08-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides within the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction.

THE IMPACT OF BIOSTIMULATION ON THE FATE OF SULFATE AND ASSOCIATED SULFUR DYNAMICS IN GROUNDWATER

PubMed Central

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-01-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides associated with the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction. PMID:25016586

Geology of the area adjacent to the Free Enterprise uranium-silver Mine, Boulder District, Jefferson County, Montana

USGS Publications Warehouse

Roberts, W.A.; Gude, A.J.

1952-01-01

Uranium minerals.occur in pods associated with cryptocrystalline silica, silver minerals, and scattered sulfide mineral grains in a hydrothermal vein that cuts quartz monzonite and alaskite at the Free Enterprise mine, 2 miles west of Boulder, Mont. The Free Enterprise vein is one of many silicified reef-like structures in this area, most of which trend about N. 60° E. The cryptocrystalline silica zones of the area are lenticular and are bordered by an altered zone where quartz monzonite is the wall rock. No alteration was noticed where alaskite is adjacent to silica zones. No uranium minerals were observed at the surface, but radioactivity anomalies were noted at 57 outcrops. Underground mining has shown that leaching by downward percolating waters has removed most of the uranium from the near-surface part of the Free Enterprise vein and probably has enriched slightly, parts of the vein and the adjacent wall rock from the bottom of the leached zone to the ground-water level. It is possible that other veins that show low to moderate radioactivity at the surface may contain significant concentrations of uranium minerals at relatively shallow depth. The quartz monzonite appears to be a more favorable host rock for the cryptocrystalline silica and associated uranium minerals than the alaskite. The alaskite occurs as vertical_dikes plug-like masses, and as irregularly shaped, gently dipping masses that are believed to have been intruded into open fractures formed during the cooling of the quartz monzonite.

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.

Radium and uranium concentrations and associated hydrogeochemistry in ground water in southwestern Pueblo County, Colorado

USGS Publications Warehouse

Felmlee, J. Karen; Cadigan, Robert Allen

1979-01-01

Radium and uranium concentrations in water from 37 wells tapping the aquifer system of the Dakota Sandstone and Purgatoire Formation in southwestern Pueblo County, Colorado, have a wide range of values and define several areas of high radioactivity in the ground water. Radium ranges from 0.3 to 420 picocuries per liter and has a median value of 8.8, and uranium ranges from 0.02 to 180 micrograms per liter and has a median value of 2.4. Radon concentrations, measured in 32 of the 37 wells, range from less than 100 picocuries per liter to as much as 27,000 and have a median value of 580. Relationships among the radioactive elements and 28 other geochemical parameters were studied by using correlation coefficients and R-mode factor analysis. Five factor groups were determined to represent major influences on water chemistry: (1) short-term solution reactions, (2) oxidation reactions, (3) hydrolysis reactions, (4) uranium distribution, and (5) long-term solution reactions. Uranium concentrations are most strongly influenced by oxidation reactions but also are affected by solution reactions and distribution of uranium in the rocks of the aquifer system. Radon and radium concentrations are mostly controlled by uranium distribution; radium also shows a moderate negative relationship with oxidation. To explain the statistical and spatial relationships among the parameters, a model was developed involving the selective leaching of uranium-bearing phases and metal sulfides which occur in discontinuous zones in sandstone and shale. When reducing conditions prevail, uranium is immobile, but radium can be taken into solution. When faults and associated fractured rocks allow oxidizing conditions to dominate, uranium can be taken into solution; radium can also be taken into solution, or it may become immobilized by coprecipitation with iron and manganese oxides or with barite. Several areas within the study area are discussed in terms of the model.

Analysis of borehole geophysical information across a uranium deposit in the Jackson Group, Karnes County, Texas

USGS Publications Warehouse

Daniels, Jeffrey J.; Scott, James Henry; Smith, Bruce D.

1979-01-01

Borehole geophysical studies across a uranium deposit in the Jackson Group, South Texas, show the three geochemical environments often associated with uranium roll-type deposits: an altered (oxidized) zone, an ore zone, and an unaltered (reduced) zone. Mineralogic analysis of the total sulfides contained in the drill core shows only slight changes in the total sulfide content among the three geochemical regimes. However, induced polarization measurements on the core samples indicate that samples obtained from the reduced side of the ore zone are more electrically polarizable than those from the oxidized side of the ore zone, and therefore probably contain more pyrite. Analysis of the clay-size fraction in core samples indicates that montmorillonite is the dominant clay mineral. High resistivity values within the ore zone indicate the presence of calcite cement concentrations that are higher than those seen outside of the ore zone. Between-hole resistivity and induced polarization measurements show the presence of an extensive zone of calcite cement within the ore zone, and electrical polarizable material (such as pyrite) within and on the reduced side of the ore zone. A quantitative analysis of the between-hole resistivity data, using a layered-earth model, and a qualitative analysis of the between-hole induced polarization measurements showed that mineralogic variations among the three geochemical environments were more pronounced than were indicated by the geophysical and geologic well logs. Uranium exploration in the South Texas Coastal Plain area has focused chiefly in three geologic units: the Oakville Sandstone, the Catahoula Tuff, and the Jackson Group. The Oakville Sandstone and the Catahoula Tuff are of Miocene age, and the Jackson Group is of Eocene age (Eargle and others, 1971). Most of the uranium mineralization in these formations is low grade (often less than 0.02 percent U3O8) and occurs in shallow deposits that are found by concentrated exploratory drilling programs. The sporadic occurrence of these deposits makes it desirable to develop borehole geophysical techniques that will help to define the depositional environments of the uranium ore, which is characterized by geochemical changes near the uranium deposits. Geochemical changes are accompanied by changes in the physical characteristics of the rocks that can be detected with borehole geophysical tools. This study is concerned with a uranium deposit within the Jackson Group that is located just east of Karnes City, Tex. Five holes were drilled on this property to obtain borehole geophysical data and cores. The cores were analyzed for mineralogic and electrical properties. The borehole geophysical information at this property included induced polarization, resistivity, gamma-gamma density, neutron-neutron, gamma-ray, caliper, and single-point-resistance logs. Between-hole resistivity and induced polarization measurements were made between hole pairs across the ore deposit and off the ore deposit.

Preliminary report on the White Canyon area, San Juan county, Utah

USGS Publications Warehouse

Benson, William E.; Trites, Albert F.; Beroni, Ernest P.; Feeger, John A.

1952-01-01

The White Canyon area, in the central part of San Juan County, Utah, consists of approximately two 15-minute quadrangles. Approximately 75 square miles have been mapped by the Geological Survey on a scale of 1 inch equals 1 mile, using a combined aerial photography-plane table method. Structure contours were drawn on top of the Organ Rock member of the Cutler formation. Parts of the Gonway and North Point claims, 1/4 mile east of the Happy Jack mine, were mapped in detail. The principal objectives of the investigations were: (1) to establish ore guides; (2) to select areas favorable for exploration; and (3) to map the general geology and to determine the regional relationships of the uranium deposits. The White Canyon area is comprised of sedimentary rocks of Carboniferous to Jurassic age, more than 2,000 feet thick, having a regional dip of 1° to 2° SW. The nearest igneous rocks are in the Henry Mountains about 7 miles west of the northern part of the area; The Shinarump conglomerate of the late Triassic age, the principal ore horizon in the White Canyon area, consists of lenticular beds of sandstone, conglomeratic sandstone, conglomerate, clay, and siltstone. The Shinarump conglomerate, absent in places, is as much as 75 feet thick. The sandstones locally contain molds of logs and fragments of altered volcanic ash. Some of the logs have been replaced by copper and uranium minerals and iron oxides. The clay and siltstone underlie and are interbedded with the sandstone, and are most common in channels that cut into the underlying Moenkopi formation. The Shinarump conglomerate contains reworked Moenkopi siltstone fragments, clay balls, carbonized wood, and pebbles of quarts, quartzite, and chert. Jointing is prominent in the Western part of the mapped area. The three most prominent joint trends are due east, N. 65°-75° W., and N. 65°-75° E. All joints have vertical dips. The red beds are bleached along some joints, especially those that trend N. 65°-75° W. All uranium ore produced has been from the lower part of the Shinarump conglomerate, where it commonly occurs with copper as disseminations and fracture coatings in sandstone. Uranium and copper minerals also occur in low-grade disseminated deposits in the lower Chinle and in the Moenkopi formation and in veins cutting these formations. Although some uranium deposits occur in Chinarump channels and scours, copper and uranium minerals along fractures suggest that channel control may be secondary. Logs and clay balls apparently have exerted some chemical influences for deposition. The uranium occurs as the oxide in some deposits, and as secondary hydrous sulfates, phosphates, oxides, and silicates in these and several other deposits. Charcoal, iron and manganese oxides, and veinlets of hydrocarbon are abnormally radioactive in most of the deposits. Base-metal sulfides are commonly found inside the oxidized zone. Secondary copper minerals include the hydrous sulfates and carbonate. Gangue minerals include quarts, clay minerals, and manganese oxides, dickite (?), calcite, gypsum, pyrite, and chalcedony (?). Principal wall-rock alteration appears to have been silicification, clay alteration, and bleaching. Most of the shipped ore has contained more than 0.3 percent uranium. The ore also contains copper, commonly in grades lower than 1.0 percent. Criteria believed to be most useful for prospecting for concealed uranium deposits are (1) visible uranium minerals; (2) sulfide minerals; (3) secondary copper minerals; (4) dickite (?); (5) hydrocarbons; and (6) bleaching and alteration of the Moenkopi formation.

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

Microbial Links between Sulfate Reduction and Metal Retention in Uranium- and Heavy Metal-Contaminated Soil▿

PubMed Central

Sitte, Jana; Akob, Denise M.; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E.; Scheinost, Andreas C.; Büchel, Georg; Küsel, Kirsten

2010-01-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the 35SO42− radiotracer method, was restricted to reduced soil horizons with rates of ≤142 ± 20 nmol cm−3 day−1. Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that ∼80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [13C]acetate- and [13C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined ≤100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching ≤1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems. PMID:20363796

Quantitative radiochemical method for determination of major sources of natural radioactivity in ores and minerals

USGS Publications Warehouse

Rosholt, J.N.

1954-01-01

When an ore sample contains radioactivity other than that attributable to the uranium series in equilibrium, a quantitative analysis of the other emitters must be made in order to determine the source of this activity. Thorium-232, radon-222, and lead-210 have been determined by isolation and subsequent activity analysis of some of their short-lived daughter products. The sulfides of bismuth and polonium are precipitated out of solutions of thorium or uranium ores, and the ??-particle activity of polonium-214, polonium-212, and polonium-210 is determined by scintillation-counting techniques. Polonium-214 activity is used to determine radon-222, polonium-212 activity for thorium-232, and polonium-210 for lead-210. The development of these methods of radiochemical analysis will facilitate the rapid determination of some of the major sources of natural radioactivity.

An Evaluation of a Networked Radiation Detection System

DTIC Science & Technology

2010-03-01

conducted at the site using RAT (Cooper, 2008a): “Beginning in the 1940’ s , widespread mining and milling of uranium ore for national defense and energy...contamination…” in order to determine future sampling points (Cooper, 2007). 2. 4 May 2005, conducted mobile air monitoring during the removal of 30...provide site-wide estimates of emissions…” at Warren (OH) Recycling Inc.®’ s 85 acre landfill emitting hydrogen sulfide (H2S) (Cooper, 2007). 4. 7 July

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.

Hydrogen sulfide (H2S) attenuates uranium-induced acute nephrotoxicity through oxidative stress and inflammatory response via Nrf2-NF-κB pathways.

PubMed

Zheng, Jifang; Zhao, Tingting; Yuan, Yan; Hu, Nan; Tang, Xiaoqing

2015-12-05

As an endogenous gaseous mediator, H2S exerts anti-oxidative, anti-inflammatory and cytoprotective effects in kidneys. This study was designed to investigate the protective effect of H2S against uranium-induced nephrotoxicity in adult SD male rats after in vivo effect of uranium on endogenous H2S formation was explored in kidneys. The levels of endogenous H2S and H2S-producing enzymes (CBS and CSE) were measured in renal homogenates from rats intoxicated by an intraperitoneally (i.p.) injection of uranyl acetate at a single dose of 2.5, 5 or 10 mg/kg. In rats injected i.p. with uranyl acetate (5 mg/kg) or NaHS (an H2S donor, 28 or 56 μmol/kg) alone or in combination, we determined biochemical parameters and histopathological alteration to assess kidney function, examined oxidative stress markers, and investigated Nrf2 and NF-κB pathways in kidney homogenates. The results suggest that uranium intoxication in rats decreased endogenous H2S generation as well as CBS and CSE protein expression. NaHS administration in uranium-intoxicated rats ameliorated the renal biochemical indices and histopathological effects, lowered MDA accumulation, and restored GSH level and anti-oxidative enzymes activities like SOD, CAT, GPx and GST. NaHS treatment in uranium-intoxicated rats activated uranium-inhibited protein expression and nuclear translocation of transcription factor Nrf2, which increased protein expression of downstream target-Nrf2 genes HO-1, NQO-1, GCLC, and TXNRD-1. NaHS administration in uranium-intoxicated rats inhibited uranium-induced nuclear translocation and phosphorylation of transcription factor κB/p65, which decreased protein expression of target-p65 inflammatory genes TNF-α, iNOS, and COX-2. Taken together, these data implicate that H2S can afford protection to rat kidneys against uranium-induced adverse effects through induction of antioxidant defense by activating Nrf2 pathway and reduction of inflammatory response by suppressing NF-κB pathway. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Uranium, thorium and REE partitioning into sulfide liquids at high pressure and high temperature: Implications for reduced, S-rich planetary bodies

NASA Astrophysics Data System (ADS)

Wohlers, A.; Wood, B. J.

2017-12-01

Based on models of the young solar nebula it is likely that the inner planets went through an early reduced phase of accretion with high metal/silicate ratio and low volatile element contents. Mercury is an existing example of a large planetary embryo with these characteristics but also with a very high S content. In order to investigate the geochemical evolution of Mercury-like bodies we experimentally determined the partitioning of lithophile elements (U, Th, Eu, Sm, Nd, Zr, La, Ce, Yb) between sulfide liquid, low-S metals and silicate melt at 1.5 GPa and 1400-2100˚C. Our results, when combined with those of Wohlers and Wood (2015) show that under highly reducing conditions (FeOsilicate<1wt%) U, Sm, Nd and other lithophile elements partition strongly into FeS liquids relative to silicate melts. The dependences of D's on the FeS contents of the metal and FeO contents of the silicate may be understood in terms of exchange reactions: UO2 + 2FeS = 2FeO + US2silicate sulfide silicate sulfideHigh concentrations of FeSmetal and low FeO contents of the silicate melts drive the reaction to the right, yielding high US2 in the sulfide and high DU. A second effect which raises DU (and other lithophile D's) is the S content of the silicate melt. The latter increases rapidly at low FeO contents and reaches 11wt %. This greatly reduces the activity coefficient of FeO, displacing the reaction further to the right. At 1.5GPa and 1400˚C we obtain sulfide-silicate partitioning with DNd/DSm 1.4 and DTh 0.1DU. As temperature increases to 2100˚C, DNd/DSm declines to 1.0 and DTh/DU increases to 0.3. We estimated the effects of accreting a reduced sulfur-rich component (with FeS core) added to early Earth. The results at 1400˚C imply the possibility of a significant ( 11ppm) 142Nd anomaly in silicate Earth and the addition of >8 ppb U to the core, but require an unreasonably high Th/U of silicate Earth (4.54). Results at 2100˚C lead to a 142Nd anomaly of 0 but addition of such a reduced sulfur-rich body could add up to 10 ppb of U to the core, together with 21 ppb Th. This combination would generate 3 TW of the energy required for the geodynamo. In this case, the Th/U ratio of silicate Earth would be 4.3, within the range of some estimates. Wohlers A. & Wood B.J. (2015) A Mercury-like component of early Earth yield uranium in the core and high mantle Nd142. Nature 520, 337-340

Uranium in Surface Waters and Sediments Affected by Historical Mining in the Denver West 1:100,000 Quadrangle, Colorado

USGS Publications Warehouse

Zielinski, Robert A.; Otton, James K.; Schumann, R. Randall; Wirt, Laurie

2008-01-01

Geochemical sampling of 82 stream waters and 87 stream sediments within mountainous areas immediately west of Denver, Colorado, was conducted by the U.S. Geological Survey in October 1994. The primary purpose was to evaluate regionally the effects of geology and past mining on the concentration and distribution of uranium. The study area contains uranium- and thorium-rich bedrock, numerous noneconomic occurrences of uranium minerals, and several uranium deposits of variable size and production history. During the sampling period, local streams had low discharge and were more susceptible to uranium-bearing acid drainage originating from historical mines of base- and precious-metal sulfides. Results indicated that the spatial distribution of Precambrian granites and metamorphic rocks strongly influences the concentration of uranium in stream sediments. Within-stream transport increases the dispersion of uranium- and thorium rich mineral grains derived primarily from granitic source rocks. Dissolved uranium occurs predominantly as uranyl carbonate complexes, and concentrations ranged from less than 1 to 65 micrograms per liter. Most values were less than 5 micrograms per liter, which is less than the current drinking water standard of 30 micrograms per liter and much less than locally applied aquatic-life toxicity standards of several hundred micrograms per liter. In local streams that are affected by uranium-bearing acid mine drainage, dissolved uranium is moderated by dilution and sorptive uptake by stream sediments. Sorbents include mineral alteration products and chemical precipitates of iron- and aluminum-oxyhydroxides, which form where acid drainage enters streams and is neutralized. Suspended uranium is relatively abundant in some stream segments affected by nearby acid drainage, which likely represents mobilization of these chemical precipitates. The 234U/238U activity ratio of acid drainage (0.95-1.0) is distinct from that of local surface waters (more than 1.05), and this distinctive isotopic composition may be preserved in iron-oxyhydroxide precipitates of acid drainage origin. The study area includes a particularly large vein-type uranium deposit (Schwartzwalder mine) with past uranium production. Stream water and sediment collected downstream from the mine's surface operations have locally anomalous concentrations of uranium. Fine-grained sediments downstream from the mine contain rare minute particles (10-20 micrometers) of uraninite, which is unstable in a stream environment and thus probably of recent origin related to mining. Additional rare particles of very fine grained (less than 5 micrometer) barite likely entered the stream as discharge from settling ponds in which barite precipitation was formerly used to scavenge dissolved radium from mine effluent.

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

NASA Astrophysics Data System (ADS)

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

2011-08-01

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

Biomining: metal recovery from ores with microorganisms.

PubMed

Schippers, Axel; Hedrich, Sabrina; Vasters, Jürgen; Drobe, Malte; Sand, Wolfgang; Willscher, Sabine

2014-01-01

Biomining is an increasingly applied biotechnological procedure for processing of ores in the mining industry (biohydrometallurgy). Nowadays the production of copper from low-grade ores is the most important industrial application and a significant part of world copper production already originates from heap or dump/stockpile bioleaching. Conceptual differences exist between the industrial processes of bioleaching and biooxidation. Bioleaching is a conversion of an insoluble valuable metal into a soluble form by means of microorganisms. In biooxidation, on the other hand, gold is predominantly unlocked from refractory ores in large-scale stirred-tank biooxidation arrangements for further processing steps. In addition to copper and gold production, biomining is also used to produce cobalt, nickel, zinc, and uranium. Up to now, biomining has merely been used as a procedure in the processing of sulfide ores and uranium ore, but laboratory and pilot procedures already exist for the processing of silicate and oxide ores (e.g., laterites), for leaching of processing residues or mine waste dumps (mine tailings), as well as for the extraction of metals from industrial residues and waste (recycling). This chapter estimates the world production of copper, gold, and other metals by means of biomining and chemical leaching (bio-/hydrometallurgy) compared with metal production by pyrometallurgical procedures, and describes new developments in biomining. In addition, an overview is given about metal sulfide oxidizing microorganisms, fundamentals of biomining including bioleaching mechanisms and interface processes, as well as anaerobic bioleaching and bioleaching with heterotrophic microorganisms.

Reduction of acid rock drainage using steel slag in cover systems over sulfide rock waste piles.

PubMed

de Almeida, Rodrigo Pereira; Leite, Adilson do Lago; Borghetti Soares, Anderson

2015-04-01

The extraction of gold, coal, nickel, uranium, copper and other earth-moving activities almost always leads to environmental damage. In metal and coal extraction, exposure of sulfide minerals to the atmosphere leads to generation of acid rock drainage (ARD) and in underground mining to acid mine drainage (AMD) due to contamination of infiltrating groundwater. This study proposes to develop a reactive cover system that inhibits infiltration of oxygen and also releases alkalinity to increase the pH of generated ARD and attenuate metal contaminants at the same time. The reactive cover system is constructed using steel slag, a waste product generated from steel industries. This study shows that this type of cover system has the potential to reduce some of the adverse effects of sulfide mine waste disposal on land. Geochemical and geotechnical characterization tests were carried out. Different proportions of sulfide mine waste and steel slag were studied in leachate extraction tests. The best proportion was 33% of steel slag in dry weight. Other tests were conducted as follows: soil consolidation, saturated permeability and soil water characteristic curve. The cover system was numerically modeled through unsaturated flux analysis using Vadose/w. The solution proposed is an oxygen transport barrier that allows rain water percolation to treat the ARD in the waste rock pile. The results showed that the waste pile slope is an important factor and the cover system must have 5 m thickness to achieve an acceptable effectiveness. © The Author(s) 2015.

RELATIONSHIP OF URANIUM ORE DEPOSITS TO PETROLEUM AND GAS-BEARING STRUCTURES

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

Russell, R.T.

eposits are located on producing or breached oil and gas structures, or in the immediate vicinity of such structures. Individual deposits associated with these structures contain ore reserves which may exceed one million tons. Data derived from a study of the known deposits should be useful in evaluating the potentiality of other areas where similar structural relations and abnormal radioactivity are known to exist. Uranium deposits located in producing oil or gas fields include a deposit of more than one million tons of uranium ore on a single salt dome in Texas, and uranium deposits in the Poison Basin, Wyoming,more » which are situated over a producing naturalgas structure, having a potential of 100,000 to 200,000 tons. Important uranium mining districts are also located near producing oil fields or near structures which may have contained oil at some time in the past. The Gas Hills district to Wyoming is on the flanks of a breached anticline and within one mile of natural-gas seeps. Deposits in the Brown's Park formation near Maybell, Colorado, are witin 10 miles of producing oil wells and natural-gas seeps are known within one mile of some of the uranium mines; and at Morrison, Colorado, uranium ore is associated with tar seeps. On th Colorado Plateau, large ore bodies with total reserves of at least 30 million tons of 0.3% U/sub 3/O/sub 8/ ore in the Ambrosia Lake district near Grants, New Mexico, and produce ore associated with asphaltite.'' The uraniferous asphaltite'' ore at Temple Mountain, Utah has been known for nearly 50 years. At both Circle Cliffs and the Inter- River area in Utah, uranium ore is associated with asphaltic material on anticlinal structures. Many other deposits are on breached strucIn Wyoming, uranium deposits in Tertiary sandstone and arkose generally lack carbon trash, but are located near oil or gas structures that contain hydrocarbons and natural gases capable of precititating uranium. Also, many uranium deposits on the Colorado Plateau have insufficient plant remains present to be the fixing agent for uranium, but petroleum and/or natural gas are proposed as possible extractants. The hydrogen sulfide contaned in natural gas or dissolved in oil-field water has been a factor in the formation of some uranium deposits. Oil-type structural traps must have been effective in localizing both petroleum and uranium ore in some districts. Although petroleum may contain small amounts of uranium, it is doubtful if either oil or natural gas are important transporting agents for uranium. Careful consideration of these various factors will provide a basis upon which to evaluate more effectively many ore producing areas. (auth)« less

Geology of uranium in the Chadron area, Nebraska and South Dakota

USGS Publications Warehouse

Dunham, Robert Jacob

1961-01-01

The Chadron area covers 375 square miles about 25 miles southeast of the Black Hills. Recurrent mild tectonic activity and erosion on the Chadron arch, a compound anticlinal uplift of regional extent, exposed 1900 feet of Upper Cretaceous rocks, mostly marine shale containing pyrite and organic matter, and 600 feet of Oligocene and Miocene rocks, mostly terrestrial fine-grained sediment containing volcanic ash. Each Cretaceous formation truncated by the sub-Oligocene unconformity is stained yellow and red, leached, kaolinized, and otherwise altered to depths as great as 55 feet. The composition and profile of the altered material indicate lateritic soil; indirect evidence indicates Eocene(?) age. In a belt through the central part of the area, the Brule formation of Oligocene age is a sequence of bedded gypsum, clay, dolomite, and limestone more than 300 feet thick. Uranium in Cretaceous shale in 58 samples averages 0.002 percent, ten times the average for the earths crust. Association with pyrite and organic matter indicates low valency. The uranium probably is syngenetic or nearly so. Uranium in Eocene(?) soil in 43 samples averages 0.054 percent, ranging up to 1.12 percent. The upper part of the soil is depleted in uranium; enriched masses in the basal part of the soil consist of remnants of bedrock shale and are restricted to the highest reaches of the ancient oxidation-reduction interface. The uranium is probably in the from of a low-valent mineral, perhaps uraninite. Modern weathering of Cretaceous shale is capable of releasing as much as 0.780 ppm uranium to water. Eocene(?) weathering probably caused enrichment of the ancient soil through 1) leaching of Cretaceous shale, 2) downward migration of uranyl complex ions, and 3) reduction of hydrogen sulfide at the water table. Uranium minerals occur in the basal 25 feet of the gypsum facies of the Brule formation at the two localities where the gypsum is carbonaceous; 16 samples average 0.066 percent uranium and range up to 0.43 percent. Elsewhere uranium in dolomite and limestone in the basal 25 feet of the gypsum facies in 10 samples averages 0.007 percent, ranging up to 0.12 percent. Localization of the uranium at the base of the gypsum facies suggests downward moving waters; indirect evidence that the water from which the gypsum was deposited was highly alkaline suggests that the uranium was leached from volcanic ash in Oligocene time.

Time-Series Radiocarbon Measurements Indicate Carbon Turnover Across Soil Fractions is Correlated With Productivity in a Long-Term Agricultural Experiment

NASA Astrophysics Data System (ADS)

Sanderman, J.; Baisden, W. T.; Creamer, C.; Farrell, M.; Fallon, S.

2016-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are linked to the presence of Th and U, although mineral hosts for these elements are moderately unreactive in the environment. Both deposit types can have mill tailings that exceed residential soil criteria for U. Uranium can be recovered as a byproduct to mitigate its environmental effects, but Th remains a waste product that requires management.

Environmental Characteristics of Carbonatite and Alkaline Intrusion-related Rare Earth Element (REE) Deposits

NASA Astrophysics Data System (ADS)

Seal, R. R., II; Piatak, N. M.

2017-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are linked to the presence of Th and U, although mineral hosts for these elements are moderately unreactive in the environment. Both deposit types can have mill tailings that exceed residential soil criteria for U. Uranium can be recovered as a byproduct to mitigate its environmental effects, but Th remains a waste product that requires management.

Geologic report on the Sand Wash Drilling Project, Moffat and Routt Counties, Colorado

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

Carter, T.E.; Wayland, T.E.

1981-09-01

The Sand Wash Basin Drilling Project comprises twenty-seven (27) drill holes located in Moffat and Routt Counties, northwest Colorado, having an aggregate depth of 26,107.5 feet (7957.6 m). The holes penetrate the Browns Park Formation of Miocene age, which is a tuffaceous continental sandstone deposited in fluvial, eolian, and lacustrine environments. Partly based on project drilling results, uranium potential resource estimates for this formation in the $50/lb U/sub 3/O/sub 8/ forward-cost category have been increased by 34,476 tons U/sub 3/O/sub 8/ (35,036 metric tons). Three areas between Maybell and Craig, Colorado, considered favorable for uranium occurrences were verified as favorablemore » by project drilling, and a fourth favorable area northwest of Maybell has been expanded. In addition, project drilling results indicate two new favorable areas, one north and northwest and one south of Steamboat Springs, Colorado. Anomalous radioactivity was detected in drill holes in all six study areas of the project. The most important factor in concentrating significant amounts of uranium in the target formation appears to be the availability of gaseous or liquid hydrocarbons and/or hydrogen sulfide gas as reductants. Where subjacent formations supply these reductants to the Browns Park Formation, project drilling encountered 0.05 percent to 0.01 percent uranium concentrations. Potential, though unproven, sources of these reductants are believed to underlie parts of all six project study areas.« less

Metal-organic framework templated synthesis of porous inorganic materials as novel sorbents

DOEpatents

Taylor-Pashow, Kathryn M. L.; Lin, Wenbin; Abney, Carter W.

2017-03-21

A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

NASA Astrophysics Data System (ADS)

Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

2016-12-01

Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

Progress in understanding uranium(IV) speciation and dynamics in biologically reduced sediments: Research at molecular to centimeter scales by the SLAC SFA program

NASA Astrophysics Data System (ADS)

Bargar, J.; Williams, K. H.; Campbell, K. M.; Stubbs, J. E.; Suvorova, E.; Lezama-Pacheco, J. S.; Alessi, D.; Stylo, M.; Handley, K. M.; Bernier-Latmani, R.; Cerrato, J.; Davis, J. A.; Fox, P. M.; Giammar, D.; Long, P. E.

2011-12-01

The chemical and physical forms of U(IV) in reduced sediments, as well as the biogeochemical processes by which they form and transform, profoundly influence the stability of reduced U(IV) species and the behavior of uranium in biostimulated aquifers. Obtaining such information in field sediments is important because biogeochemical field conditions and their time dependence are difficult to replicate in the laboratory. The majority of contaminated aquifers in which bioremediation is of potential interest, including the Old Rifle, CO IFRC site, exhibit relatively low uranium sediment concentrations, i.e., < 10 ppm, presenting a formidable challenge to the use of spectroscopy and microscopy techniques that typically require 10-fold or higher uranium loadings. We have developed an in-situ column technique to study U(IV) species and evolving microbial communities in the Old Rifle aquifer and to correlate them with changes in trace and major ion groundwater composition during biostimulation treatments. Sediments were examined using x-ray and electron microscopy, x-ray absorption spectroscopy (XAS), and chemical extractions. XAS analysis showed that U(IV) occurred predominantly or exclusively as monomeric U(IV) complexes coordinated to oxo (or similar N/C) neighbors, and is associated with biomass or Fe sulfides. Even in the latter case, U(IV) was not coordinated directly to S neighbors. Sediment-hosted monomeric U(IV) complexes were found to partially transform into uraninite in the aquifer over a subsequent 12 month period. This work establishes the importance of monomeric U(IV) complexes in subsurface sediments at the Old Rifle site and provides a conceptual framework in which previously observed U(IV) reduction products can be related. These experiments also establish that U(IV) species are dynamic in aquifers and can undergo non-oxidative transformation reactions. These new results have important implications for uranium reactive transport models, long-term assessment of remediation technologies, and understanding natural uranium reduction in aquifers.

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

PubMed

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Progress report on geologic studies of the Ranger orebodies, Northern Territory, Australia

USGS Publications Warehouse

Nash, J.T.; Frishman, David

1982-01-01

The Ranger No. 1 and No. 3 orebodies contain about 124,000 tonnes U3O8 in highly chloritized metasediments of the lower Proterozoic Cahill Formation within about 500 m of the projected sub-Kombolgie Formation unconformity. In both orebodies, oxidized and reduced uranium minerals occur chiefly in quartzose schists that have highly variable amounts of muscovite, sericite, and chlorite. The effects of several periods of alteration are pervasive in the vicinity of orebodies where biotite and garnet are altered to chlorite, and feldspars to white mica or chlorite. Oxidized uranium minerals, associated with earthy iron oxides, occur from the surface to a depth of about 60 m. Below the oxidized zone, uranium occurs chiefly as uraninite and pitchblende disseminated through thick sections of quartz-chlorite-muscovite schist and has no apparent association with graphite or sulfides. In fact, graphite is rare and sulfides are generally low in abundance (<0.5 percent). Higher ore grades occur in disrupted zones a few centimeters thick and in some quartz-chlorite vein-like zones of uncertain origin. Uranium correlates strongly with chlorite, but not all of the many ages of chlorite have associated uranium. At least five textural varieties of chlorite are present and represent at least 3 ages. Preliminary microprobe analyses suggest that Mg-Fe-Al contents are relatively uniform. Apatite commonly occurs with chlorite. Uranium is not common in carbonate rocks and seems to occur only in disrupted zones that have chlorite alteration. Chloritization and silicification are more widespread and intense in the No. 1 orebody than in the No. 3. In both orebodies, hematite occurs tens to hundreds of meters below the weathered zone, in both altered and largely unaltered rocks, with and without uranium. The structure of the orebodies is outwardly simple, particularly in No. 3; dips are less than 40? on most lithologic contacts. The No. 1 orebody is in a basin-like structure about 400 m wide that probably formed in part by progressive removal of carbonate rocks that are as much as 200 m thick adjacent to the No. 1 orebody and below the No. 3 orebody. Quartz-chlorite breccias have formed in the zone of carbonate thinning; uranium is spotty and low grade in these breccias. Chloritized and uraniferous broken and sheared zones, a few centimeters to a few meters thick, have an unknown attitude but must have small displacement. Blocks of altered Kombolgie sandstone are downfaulted into the No. 3 orebody and locally contain reduced uranium minerals. One or more shear zones 5-30 m thick of crushed and smeared fine to coarse rock fragments occur below the orebodies, and other low-angle shears probably occur in the orebodies. The shear zone dips about 40 o and displacement on it is not known. The footwall rocks generally are less retrograded than those in the hanging wall (orebody) and consist of quartz-biotite-feldspar schists and gneisses flanking the Nanambu Complex. A few scattered fractures in the footwall sequence contain pitchblende of unknown age and origin. Major element chemical analyses confirm the lithologic observations of large changes in composition during multiple stages of alteration. Granitic dikes and pelitic schists have gained Fe and Mg and lost Si, Ca, Na, and K during chloritization. Marbles have gained Si, Al, Fe, and P, and lost Mg, Ca, and K during jasperoid-chlorite alteration. Total net chemical gains and losses in the Ranger No. 1 orebody were huge: equal to about 37 percent of the mass of the ore-bearing rock that will be mined. There were net gains in Si and P and net losses in Al, Fe, Mg, Ca, K, and Na. The geologic age(s) of uranium emplacement are obscure because there are few age criteria. Reduced uranium minerals are younger than 1.8-b.y.-old granite dikes, and some occur locally in 1.65-b.y.-old Kombolgie Formation. Diabase dikes (age not known) are thoroughly chloritized and contain sparse ore minerals. Oxidized ura

Immobilization of uranium in biofilm microorganisms exposed to groundwater seeps over granitic rock tunnel walls in Olkiluoto, Finland

NASA Astrophysics Data System (ADS)

Krawczyk-Bärsch, Evelyn; Lünsdorf, Heinrich; Pedersen, Karsten; Arnold, Thuro; Bok, Frank; Steudtner, Robin; Lehtinen, Anne; Brendler, Vinzenz

2012-11-01

In an underground rock characterization facility, the ONKALO tunnel in Finland, massive 5-10-mm thick biofilms were observed attached to tunnel walls where groundwater was seeping from bedrock fractures at a depth of 70 m. In laboratory experiments performed in a flow cell with detached biofilms to study the effect of uranium on the biofilm, uranium was added to the circulating groundwater (CGW) obtained from the fracture feeding the biofilm. The final uranium concentration in the CGW was adjusted to 4.25 × 10-5 M, in the range expected from a leaking spent nuclear fuel (SNF) canister in a future underground repository. The effects were investigated using microelectrodes to measure pH and Eh, time-resolved laser fluorescence spectroscopy (TRLFS), energy-filtered transmission electron microscopy (EF-TEM), and electron energy-loss spectroscopy (EELS) studies and thermodynamic calculations were utilized as well. The results indicated that the studied biofilms constituted their own microenvironments, which differed significantly from that of the CGW. A pH of 5.37 was recorded inside the biofilm, approximately 3.5 units lower than the pH observed in the CGW, due to sulfide oxidation to sulfuric acid in the biofilm. Similarly, the Eh of +73 mV inside the biofilm was approximately 420 mV lower than the Eh measured in the CGW. Adding uranium increased the pH in the biofilm to 7.27 and reduced the Eh to -164 mV. The changes of Eh and pH influenced the bioavailability of uranium, since microbial metabolic processes are sensitive to metals and their speciation. EF-TEM investigations indicated that uranium in the biofilm was immobilized intracellularly in microorganisms by the formation of metabolically mediated uranyl phosphate, similar to needle-shaped autunite (Ca[UO2]2[PO4]2·2-6H2O) or meta-autunite (Ca[UO2]2[PO4]2·10-12H2O). In contrast, TRLFS studies of the contaminated CGW identified aqueous uranium carbonate species, likely (Ca2UO2[CO3]3), formed due to the high concentration of carbonate in the CGW. The results agreed with thermodynamic calculations of the theoretically predominant field of uranium species, formed in the uranium-contaminated CGW at the measured geochemical parameters. This investigation clearly demonstrated that biological systems must be considered as a part of natural systems that can significantly influence radionuclide behavior. The results improve our understanding of the mechanisms of biofilm response to radionuclides in relation to safety assessments of SNF repositories.

Uranium occurrences in the Golden Gate Canyon and Ralston Creek areas, Jefferson County, Colorado

USGS Publications Warehouse

Adams, John Wagstaff; Gude, A.J.; Beroni, E.P.

1953-01-01

Pitchblende, associated with base-metal sulfides, has been found at nine localities in the northern part of Jefferson County, Colo., in shear zones that cut pre-Cambrian metamorphic and igneous rocks, chiefly hornblende gneiss, biotite schist, and granite pegmatite. The known deposits are in the vicinity of Halston Creek and Golden Gate Canyon, in the foothills of the Colorado Front Range and about 15 miles east of the pitchblende-producing area of the Central City district. Two of the pitchblende occurrences were found by a local prospector in 1949; the seven other deposits were found by Geological Survey. personnel in 1951-52. The pitchblende deposits, with one exception, are in major shear zones that contain veinlike bodies of carbonate-rich breccia that ranges from 1 to 5 feet in thickness. The breccias probably are related to the Laramide faults, or 'breccia reefs' of similar trend, mapped by Loverinq and Goddard (1950). The breccias are composed of fragments of bleached and iron-stained wall rock, usually hornblende gneiss, that have been cut by veins and cemented by carbonate minerals, quartz, and orthoclase(?). Pitchblende and associated ore minerals, chiefly copper sulfides, occur in and along the margins of the breccias and apparently were introduced at a late stage of the carbonate deposition. At one deposit, the Buckman, the pitchblende is in narrow shear zones not closely related to any large breccia bodies. Secondary uranium minerals are subordinate except at the Schwartzwalder mine, where torbernite and metatorbernite are common. Some alteration of pitchblende to non-opaque materials, believed to be hydrated oxides, has been noted in ore from two of the deposits.

ASTER, ALI and Hyperion sensors data for lithological mapping and ore minerals exploration.

PubMed

Beiranvand Pour, Amin; Hashim, Mazlan

2014-01-01

This paper provides a review of the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER), Advanced Land Imager (ALI), and Hyperion data and applications of the data as a tool for ore minerals exploration, lithological and structural mapping. Spectral information extraction from ASTER, ALI, and Hyperion data has great ability to assist geologists in all disciplines to map the distribution and detect the rock units exposed at the earth's surface. The near coincidence of Earth Observing System (EOS)/Terra and Earth Observing One (EO-1) platforms allows acquiring ASTER, ALI, and Hyperion imagery of the same ground areas, resulting accurate information for geological mapping applications especially in the reconnaissance stages of hydrothermal copper and gold exploration, chromite, magnetite, massive sulfide and uranium ore deposits, mineral components of soils and structural interpretation at both regional and district scales. Shortwave length infrared and thermal infrared bands of ASTER have sufficient spectral resolution to map fundamental absorptions of hydroxyl mineral groups and silica and carbonate minerals for regional mapping purposes. Ferric-iron bearing minerals can be discriminated using six unique wavelength bands of ALI spanning the visible and near infrared. Hyperion visible and near infrared bands (0.4 to 1.0 μm) and shortwave infrared bands (0.9 to 2.5 μm) allowed to produce image maps of iron oxide minerals, hydroxyl-bearing minerals, sulfates and carbonates in association with hydrothermal alteration assemblages, respectively. The techniques and achievements reviewed in the present paper can further introduce the efficacy of ASTER, ALI, and Hyperion data for future mineral and lithological mapping and exploration of the porphyry copper, epithermal gold, chromite, magnetite, massive sulfide and uranium ore deposits especially in arid and semi-arid territory.

Geochemical Characterization of the Upper and Middle Floridan Aquifer System, South Florida

NASA Astrophysics Data System (ADS)

Mirecki, J.; Richardson, E.; Bennett, M.; Hendel, J.

2008-05-01

Our study focus is to characterize the water quality and geochemical environment of the Floridan Aquifer System (FAS) throughout the regional flowpath. A synoptic survey of 21 wells (n=15, upper FAS; n=6 middle FAS) was supplemented by additional samples (n=11) obtained during exploratory well development at 4 aquifer storage recovery (ASR) pilot sites. Synoptic survey samples were analyzed intensively, yielding a dataset that consists of major and trace dissolved constituents (including metals), stable isotopes (δ18O, δ13C, δD, δ34S in sulfate and sulfide), carbon species (carbonate alkalinity and organic carbon), uranium-series radionuclides, nutrients, and selected microbes and pathogens. The objectives of this study are three-fold: 1) to provide baseline water-quality and geochemical information prior to initiation of ASR activities that are part of the Comprehensive Everglades Restoration Plan; 2) to quantify the major controls on geochemical evolution along upper and middle FAS flowpaths using geochemical modeling methods; and 3) to identify areas where water- quality may limit the feasibility of ASR methods in the FAS. Preliminary interpretations water quality changes along the regional FAS flowpath can be summarized as follows. Concentrations of dissolved constituents increase from north to south along the flow path; generally, the upper FAS has lower total dissolved solids than the middle FAS at locations where well pairs were analyzed. The redox environment changes from oxic to strongly anoxic, very close to the recharge area. Redox measurements, dissolved iron, sulfide, and sulfur isotope data are consistent with sulfate-reducing conditions. Uranium-series isotope concentrations and activities generally are below regulatory criteria, with few exceptions in both the upper and middle FAS. Areas with greater radionuclide activity occur primarily at distal flowpath locations or at the coast.

Geology of the Midnite uranium mine area, Washington: maps, description, and interpretation

USGS Publications Warehouse

Nash, J. Thomas

1977-01-01

Bedrock geology of about 12 km2 near the Midnite mine has been mapped at the surface, in mine exposures, and from drilling, at scales from 1:600 to 1:12,000 and is presented here at 1:12,000 to provide description of the setting of uranium deposits. Oldest rocks in the area are metapelitic and metacarbonate rocks of the Precambrian (Y) Togo Formation. The chief host for uranium deposits is graphitic and pyritic mica phyllite and muscovite schist. Ore also occurs in calc-silicate hornfels and marble at the western edge of a calcareous section about 1,150 m thick. Calcareous rocks of the Togo are probably older than the pelitic as they are interpreted to be near the axis of a broad anticline. The composition and structural position of the calcareous unit suggests correlation with less metamorphosed carbonate-bearing rocks of the Lower Wallace Formation, Belt Supergroup, about 200 km to the east. Basic sills intrusive into the Togo have been metamorphosed to amphibolite. Unmetamorphosed rocks in the mine area are Cretaceous(?) and Eocene igneous rocks. Porphyritic quartz monzonite of Cretaceous age, part of the Loon Lake batholith, is exposed over one third of the mine area. It underlies the roof pendant of Precambrian rocks in which the Midnite mine occurs at depths of generally less than 300 m. The pluton is a two-mica granite and exhibits pegmatitic and aplitic textural features indicative of water saturation and pressure quenching. Eocene intrusive and extrusive rocks in the area provide evidence that the Eocene surface was only a short distance above the present uranium deposits. Speculative hypotheses are presented for penesyngenetic, hydrothermal, and supergene modes of uranium emplacement. The Precambrian Stratigraphy, similar in age and pre-metamorphic lithology to that of rocks hosting large uranium deposits in Saskatchewan and Northern Territory, Australia, suggests the possibility of uranium accumulation along with diagenetic pyrite in carbonaceous muds in a marine shelf environment. This hypothesis is not favored by the author because there is no evidence for stratabound uranium such as high regional radioactivity in the Togo. A hydrothermal mode of uranium emplacement is supported by the close apparent ages of mineralization and plutonism, and by petrology of the pluton. I speculate that uranium may have become enriched in postmagmatic fluids at the top of the pluton, possibly by hydrothermal leaching of soluble uranium associated with magnetite, and diffused outward into metasedimentary wall rocks to create an aureole about 100 m thick containing about 100 ppm uranium. Chemistry of the hydrothermal process is not understood, but uranium does not appear to have been transported by an oxidizing fluid, and the fluid did not produce veining and alteration comparable to that of base-metal sulfide deposits. Uranium in the low-grade protore is believed to have been redistributed into permeable zones in the Tertiary to create ore grades. Geologic and isotopic ages of uranium mineralization, and the small volume of porphyritic quartz monzonite available for leaching, are not supportive of supergene emplacement of uranium.

Using complex resistivity imaging to infer biogeochemical processes associated with bioremediation of an uranium-contaminated aquifer

NASA Astrophysics Data System (ADS)

Flores Orozco, AdriáN.; Williams, Kenneth H.; Long, Philip E.; Hubbard, Susan S.; Kemna, Andreas

2011-09-01

Experiments at the Department of Energy's Integrated Field Research Challenge (IFRC) site near Rifle, Colorado, have demonstrated the ability to remove uranium from groundwater by stimulating the growth and activity of Geobacter species through acetate amendment. Prolonging the activity of these strains in order to optimize uranium bioremediation has prompted the development of minimally invasive and spatially extensive monitoring methods diagnostic of their in situ activity and the end products of their metabolism. Here we demonstrate the use of complex resistivity imaging for monitoring biogeochemical changes accompanying stimulation of indigenous aquifer microorganisms during and after a prolonged period (100+ days) of acetate injection. A thorough raw data statistical analysis of discrepancies between normal and reciprocal measurements and incorporation of a new power law phase-error model in the inversion were used to significantly improve the quality of the resistivity phase images over those obtained during previous monitoring experiments at the Rifle IFRC site. The imaging results reveal spatiotemporal changes in the phase response of aquifer sediments, which correlate with increases in Fe(II) and precipitation of metal sulfides (e.g., FeS) following the iterative stimulation of iron and sulfate-reducing microorganisms. Only modest changes in resistivity magnitude were observed over the monitoring period. The largest phase anomalies (>40 mrad) were observed hundreds of days after halting acetate injection, in conjunction with accumulation of Fe(II) in the presence of residual FeS minerals, reflecting preservation of geochemically reduced conditions in the aquifer, a prerequisite for ensuring the long-term stability of immobilized, redox-sensitive contaminants such as uranium.

Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

NASA Astrophysics Data System (ADS)

Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

2015-12-01

The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table. Seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may also be controlled by other oxidative pathways in which oxygen plays an indirect role.

Radioactive deposits in California

USGS Publications Warehouse

Walker, George W.; Lovering, Tom G.

1954-01-01

Reconnaissance examination by Government geologists of many areas, mine properties, and prospects in California during the period between 1948 and 1953 has confirmed the presence of radioactive materials in place at more than 40 localities. Abnormal radioactivity at these localities is due to concentrations of primary and secondary uranium minerals, to radon gas, radium (?), and to thorium minerals. Of the known occurrences only three were thought to contain uranium oxide (uranitite or pitchblende), 4 contained uranium-bearing columbate, tantalate, or titanate minerals, 12 contained secondary uranium minerals, such as autunite, carnotite, and torbernite, one contained radon gas, 7 contained thorium minerals, and, at the remaining 16 localities, the source of the anomalous radiation was not positively determined. The occurrences in which uranium oxide has been tentatively identified include the Rathgeb mine (Calaveras County), the Yerih group of claims (San Bernardino County), and the Rainbow claim (Madera County). Occurrences of secondary uranium minerals are largely confined to the arid desert regions of south-eastern California including deposits in San Bernardino, Kern, Inyo, and Imperial Counties. Uranium-bearing columbate, tantalate, or titanate minerals have been reported from pegmatite and granitic rock in southeastern and eastern California. Thorium minerals have been found in vein deposits in eastern San Bernardino County and from pegmatites and granitic rocks in various parts of southeastern California; placer concentrations of thorium minerals are known from nearly all areas in the State that are underlain, in part, by plutonic crystalline rocks. The primary uranium minerals occur principally as minute accessory crystals in pegmatite or granitic rock, or with base-metal sulfide minerals in veins. Thorium minerals also occur as accessory crystals in pegmatite or granitic rock, in placer deposits derived from such rock, and, at Mountain Pass, in veins containing rare earths. Secondary uranium minerals have been found as fracture coatings and as disseminations in various types of wall rock, although they are largely confined to areas of Tertiary volcanic rocks. Probably the uranium in the uraniferous deposits in California is related genetically to felsic crystalline rocks and felsic volcanic rocks; the present distribution of the secondary uranium minerals has been controlled, in part, by circulating ground waters and probably, in part, by magmatic waters related to the Tertiary volcanic activity. The thorium minerals are genetically related to the intrusion of pegmatite and plutonic crystalline rocks. None of the known deposits of radioactive minerals in California contain marketable reserves of uranium or thorium ore under economic conditions existing in 1952. With a favorable local market small lots of uranium ore may be available in the following places: the Rosamund prospect, the Rafferty and Chilson properties, the Lucky Star claim, and the Yerih group. The commercial production of thorium minerals will be possible, in the near future, only if these minerals can be recovered cheaply as a byproduct either from the mining of rare earths minerals at Mountain Pass or as a byproduct of placer mining for gold.

A deposit model for carbonatite and peralkaline intrusion-related rare earth element deposits: Chapter J in Mineral deposit models for resource assessment

USGS Publications Warehouse

Verplanck, Philip L.; Van Gosen, Bradley S.; Seal, Robert R.; McCafferty, Anne E.

2014-01-01

The greatest environmental challenges associated with carbonatite and peralkaline intrusion-related rare earth element deposits center on the associated uranium and thorium. Considerable uncertainty exists around the toxicity of rare earth elements and warrants further investigation. The acid-generating potential of carbonatites and peralkaline intrusion-related deposits is low due to the dominance of carbonate minerals in carbonatite deposits, the presence of feldspars and minor calcite within the alkaline intrusion deposits, and only minor quantities of potentially acid-generating sulfides. Therefore, acid-drainage issues are not likely to be a major concern associated with these deposits. Uranium has the potential to be recovered as a byproduct, which would mitigate some of its environmental effects. However, thorium will likely remain a waste-stream product that will require management since progress is not being made towards the development of thorium-based nuclear reactors in the United States or other large scale commercial uses. Because some deposits are rich in fluorine and beryllium, these elements may be of environmental concern in certain locations.

Using complex resistivity imaging to infer biogeochemical processes associated with bioremediation of a uranium-contaminated aquifer

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

Flores-Orozco, Adrian; Williams, Kenneth H.; Long, Philip E.

2011-07-07

Experiments at the Department of Energy’s Rifle Integrated Field Research Challenge (IFRC) site near Rifle, Colorado (USA) have demonstrated the ability to remove uranium from groundwater by stimulating the growth and activity of Geobacter species through acetate amendment. Prolonging the activity of these strains in order to optimize uranium bioremediation has prompted the development of minimally-invasive and spatially-extensive monitoring methods diagnostic of their in situ activity and the end products of their metabolism. Here we demonstrate the use of complex resistivity imaging for monitoring biogeochemical changes accompanying stimulation of indigenous aquifer microorganisms during and after a prolonged period (100+ days)more » of acetate injection. A thorough raw-data statistical analysis of discrepancies between normal and reciprocal measurements and incorporation of a new power-law phase-error model in the inversion were used to significantly improve the quality of the resistivity phase images over those obtained during previous monitoring experiments at the Rifle IRFC site. The imaging results reveal spatiotemporal changes in the phase response of aquifer sediments, which correlate with increases in Fe(II) and precipitation of metal sulfides (e.g., FeS) following the iterative stimulation of iron and sulfate reducing microorganism. Only modest changes in resistivity magnitude were observed over the monitoring period. The largest phase anomalies (>40 mrad) were observed hundreds of days after halting acetate injection, in conjunction with accumulation of Fe(II) in the presence of residual FeS minerals, reflecting preservation of geochemically reduced conditions in the aquifer – a prerequisite for ensuring the long-term stability of immobilized, redox-sensitive contaminants, such as uranium.« less

Using complex resistivity imaging to infer biogeochemical processes associated with bioremediation of a uranium-contaminated aquifer

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

Orozco, A. Flores; Williams, K.H.; Long, P.E.

2011-04-01

Experiments at the Department of Energy's Rifle Integrated Field Research Challenge (IFRC) site near Rifle, Colorado (USA) have demonstrated the ability to remove uranium from groundwater by stimulating the growth and activity of Geobacter species through acetate amendment. Prolonging the activity of these strains in order to optimize uranium bioremediation has prompted the development of minimally-invasive and spatially-extensive monitoring methods diagnostic of their in situ activity and the end products of their metabolism. Here we demonstrate the use of complex resistivity imaging for monitoring biogeochemical changes accompanying stimulation of indigenous aquifer microorganisms during and after a prolonged period (100+ days)more » of acetate injection. A thorough raw-data statistical analysis of discrepancies between normal and reciprocal measurements and incorporation of a new power-law phase-error model in the inversion were used to significantly improve the quality of the resistivity phase images over those obtained during previous monitoring experiments at the Rifle IRFC site. The imaging results reveal spatiotemporal changes in the phase response of aquifer sediments, which correlate with increases in Fe(II) and precipitation of metal sulfides (e.g., FeS) following the iterative stimulation of iron and sulfate reducing microorganism. Only modest changes in resistivity magnitude were observed over the monitoring period. The largest phase anomalies (>40 mrad) were observed hundreds of days after halting acetate injection, in conjunction with accumulation of Fe(II) in the presence of residual FeS minerals, reflecting preservation of geochemically reduced conditions in the aquifer - a prerequisite for ensuring the long-term stability of immobilized, redox-sensitive contaminants, such as uranium.« less

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

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

Hayes, Kim F.; Bi, Yuqiang; Carpenter, Julian

2013-12-31

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic andmore » environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe 1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe 3S 4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe 2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe 3(PO 4) 2•8(H 2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO 2 produced in presence of ferrous iron was poorly crystalline. At UM, laboratory-scale reactor studies were performed to assess the potential for the predominant abiotic reductants formed under sulfate reducing conditions (SRCs) to: (1) reduce U(VI) in contaminated groundwater sediments), and (2) inhibit the re-oxidation of U(IV) species, and in particular, uraninite (UO 2(s)). Under SRCs, mackinawite and aqueous sulfide are the key reductants expected to form. To assess their potential for abiotic reduction of U(VI) species, a series of experiments were performed in which either FeS or S(-II) was added to solutions of U(VI), with the rates of conversion to U(IV) solids monitored as a function of pH, and carbonate and calcium concentration. In the presence of FeS and absence of oxygen or carbonate, U(IV) was completely reduced uraninite. S(-II) was also found to be an effective reductant of aqueous phase U(VI) species and produced uraninite, with the kinetics and extent of reduction depending on geochemical conditions. U(VI) reduction to uraninite was faster under higher S(-II) concentrations but was slowed by an increase in the dissolved Ca or carbonate concentration. Rapid reduction of U(VI) occurred at circumneutral pH but virtually no reduction occurred at pH 10.7. In general, dissolved Ca and carbonate slowed abiotic U(VI) reduction by forming stable Ca-U(VI)-carbonate soluble complexes that are resistant to reaction with aqueous sulfide. To investigate the stability of U(IV) against re-oxidation in the presence of iron sulfides by oxidants in simulated groundwater environments, and to develop a mechanistic understanding the controlling redox processes, continuously-mixed batch reactor (CMBR) and flow-through reactor (CMFR) studies were performed at UM. In these studies a series of experiments were conducted under various oxic groundwater conditions to examine the effectiveness of FeS as an oxygen scavenger to retard UO 2 dissolution. The results indicate that FeS is an effective oxygen scavenger, and can lower the rate of oxidative dissolution of UO 2 by over an order of magnitude compared to the absence of FeS, depending on pH, FeS content, and DO concentrations. Column reactor studies were performed at UM to assess the impact of mackinawite on uraninite oxidation under hydrodynamic flow conditions more representative of packed porous media at contaminated groundwater sites. In these studies, Rifle sediments were packed in the two columns which were subjected to different bioreduction steps and then run in parallel. The first column was bioreduced under SRCs (i.e., with sulfate in the influent) to generate mackinawite, mixed with uraninite, gamma-sterilized to inhibit subsequent microbiological activity, and then subjected to groundwater influent containing first nitrite and then oxygen. The second column was bioreduced (but in absence of sulfate in the influent) so that no iron sulfides would form, and then subjected to identical steps and influent as the first column. When nitrite was introduced in the influent of both columns, no significant release of U(VI) relative to the anoxic flow prior to nitrite addition occurred. However, when oxygen was introduced, the column which had undergone sulfate reduction (and had produced mackinawite as later verified by XAS) significantly lowered the peak U(VI) effluent concentrations, and in general, slowed U(VI) release considerably compared to the column with no FeS. Overall, these studies demonstrated that the presence of mackinawite can be a significant scavenger of oxygen and inhibit the oxidation of uraninite by oxygen, whereas nitrite had little impact on uraninite oxidation either in the presence or absence of FeS.« less

CHARLES SHELDON ANTELOPE RANGE AND SHELDON NATIONAL ANTELOPE REFUGE, NEVADA AND OREGON.

USGS Publications Warehouse

Cathrall, J.B.; Tuchek, E.T.

1984-01-01

A mineral survey of the Charles Sheldon Antelope Range and Sheldon National Antelope Refuge, in Humboldt and Washoe Counties, Nevada, and Lake and Harney Counties, Oregon, was conducted. The investigation identified areas of mineral-resource potential within the range and refuge. The range and refuge have areas of substantiated resource potential for precious opal and uranium, a demonstrated resource of decorative building stone, and areas with probable resource potential for mercury and for base- and precious-metal sulfide deposits. Reservoir temperatures, estimated from the analysis of thermal springs, indicate that a probable potential for geothermal resources exists in two areas in the range. No other energy resources were identitied in the area.

Geology of the Ralston Buttes district, Jefferson County, Colorado: a preliminary report

USGS Publications Warehouse

Sheridan, Douglas M.; Maxwell, Charles H.; Albee, Arden L.; Van Horn, Richard

1956-01-01

The Ralston Buttes district in Jefferson County is one of the most significant new uranium districts located east of the Continental Divide in Colorado. The district is east of the Colorado Front Range mineral belt, along the east front of the range. From November 1953 through October 1956, about 10,000 tons of uranium ore, much of which was high-grade pitchblende-bearing vein material, was shipped from the district. The ore occurs in deposits that range in size from bodies containing less than 50 tons to ore shoots containing over 1,000 tons. The only other mining activity in the area has been a sporadic production of beryl, feldspar, and scrap mica from Precambrian pegmatites, and quarrying of dimension stone, limestone, and clay from sedimentary rocks. Most of the Ralston Buttes district consists of complexly folded Precambrian metamorphic and igneous rocks - gneiss, schist, quartzite, amphibolite, and granodiorite. Paleozoic and Mesozoic sedimentary rocks crop out in the northeastern part of the district. These rocks are cut by northwesterly-trending fault systems of Laramide age and by small bodies of intrusive rocks that are Tertiary in age. The typical uranium deposits in the district are hydrothermal veins occupying openings in Laramide fault breccias or related fractures that cut the Precambrian rocks. Pitchblende and lesser amounts of secondary uranium minerals are associated with sparse base-mental sulfides in a gangue of carbonate minerals, potash feldspar, and, more rarely, quartz. Less common types of deposits consist of pitchblende and secondary uranium minerals that occupy fractures cutting pegmatites and quartz veins. The uranium deposits are concentrated in two areas, the Ralston Creek area and the Golden Gate Canyon area. The deposits in the Ralston Creek area are located along the Rogers fault system, and the deposits in the Golden Gate Canyon area are along the Hurricane Hill fault system. Two geologic factors were important to the localization of the uranium deposits: (1) favorable structural environment and (2) favorable host rocks. The deposits in each of the two major areas are located where a northwesterly-trending Laramide fault system splits into a complex network of faults. Also, most of the deposits appear to be localized where the faults cut Precambrian rocks rich in hornblende, biotite, or garnet and biotite. The ore controls recognized in this relatively new uranium district may have wider application in areas of similar geology elsewhere in the Front Range.

Progress report on the Happy Jack mine, Which Canyon area, San Juan county, Utah

USGS Publications Warehouse

Trites, Albert F.; Chew, Randall T.

1954-01-01

The Happy Jack mine is in the White Canyon area, San Juan county, Utah. Production is from high-grade uranium deposits in the Shinarump conglomerate of the Triassic age. In this area the Shinarump beds range from about 16 to 40 feet in thickness and the lower part of these beds fills an east-trending channel this is note than 750 feet wide and 10 feet deep. The Shinarump conglomerate consists of beds of coarse- to fine-grained quartzose sandstone, conglomerate, siltstone, and claystone. Carbonized wood is abundant in these beds, and in the field it was classified as mineral charcoal and coal. Intra-Shinarump channels, cross-stratification, current lineation, and slumping and compaction structures have been recognized in the mine. Steeply dipping fractures have dominant trends in four directions -- N 65°W, N 60°E, N 85°E, and due north. Uranium occurs as bedded deposits, as replacement bodies in accumulations of "trash", and as replacements of larger fragments of wood. An "ore shoot" is formed where the three types of uranium deposits occur together; these ore shoots appear to be elongate masses with sharp boundaries. Uranium minerals include uraninite, sooty pitchblende(?), and the sulfate--betazippeite, johannite, and uranopilite. Associated with the uraninite are the sulfide minerals covellite, bornite, chalcopyritw, and pyrite. Galena and sphalerite have been found in close association with uranium minerals. The gaunge minerals include: limonite and hematite present in most of the sandstone beds throughout the deposit, jarosite that impregnates much of the sandstone in the outer parts of the mine workings, gypsum that fills many of the fractures, and barite that impregnates the sandstone in at least one part of the mine. Secondary copper minerals, mainly copper sulfates, occur throughout the mine, but most abundant near the adits in the outermost 30 feet of the workings. The minerals comprising the bulk of the country rock include quartz, feldspar, and clay minerals. The amount of uranium minerals deposited in a sandstone bed is believed to have been determined by the position of the bed in the channel, the permeability of the sandstone in the bed, and the amount of carbonized wood and plant remains within the bed. The beds considered most favorable for uranium deposition contain an abundance of claystone and siltstone both as matrix filling and as fragments and pebbles. Suggested exploration guides from uranium ore bodies include the following: (1) interbedded siltstone lenses, (2) claystone and siltstone cement and pabbles, (3) concentrations of "trash", (4) covelllite and bornite, (5) chalcopyrite, and (6) carbonized wood.

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

Understanding controls on redox processes in floodplain sediments of the Upper Colorado River Basin

DOE PAGES

Noël, Vincent; Boye, Kristin; Kukkadapu, Ravi K.; ...

2017-12-15

Floodplains, heavily used for water supplies, housing, agriculture, mining, and industry, are important repositories of organic carbon, nutrients, and metal contaminants. The accumulation and release of these species is often mediated by redox processes. By understanding the physicochemical, hydrological, and biogeochemical controls on the distribution and variability of sediment redox conditions we can develop conceptual and numerical models of contaminant transport within floodplains. The Upper Colorado River Basin (UCRB) is impacted by former uranium and vanadium ore processing, resulting in contamination by V, Cr, Mn, As, Se, Mo and U. Previous authors have suggested that sediment redox activity occurring withinmore » organic carbon-enriched bodies located below the groundwater level may be regionally important to the maintenance and release of contaminant inventories, particularly uranium. To help assess this hypothesis, vertical distributions of Fe and S redox states and sulfide mineralogy were assessed in sediment cores from three floodplain sites spanning a 250 km transect of the central UCRB. Our results support the hypothesis that organic-enriched reduced sediments are important zones of biogeochemical activity within UCRB floodplains. Furthermore, we found that the presence of organic carbon, together with pore saturation, are the key requirements for maintaining reducing conditions, which were dominated by sulfate-reduction products. Sediment texture was found to be of secondary importance and to moderate the response of the system to external forcing, such as oxidant diffusion. Consequently, fine-grain sediments are relatively resistant to oxidation in comparison to coarser-grained sediments. Exposure to oxidants consumes precipitated sulfides, with a disproportionate loss of mackinawite (FeS) as compared to the more stable pyrite. The accompanying loss of redox buffering capacity creates the potential for release of sequestered radionuclides and metals. Because of their redox reactivity and stores of metals, C, and N, organic-enriched sediments are likely to be important to nutrient and contaminant mobility within UCRB floodplain aquifers.« less

Understanding controls on redox processes in floodplain sediments of the Upper Colorado River Basin

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

Noël, Vincent; Boye, Kristin; Kukkadapu, Ravi K.

Floodplains, heavily used for water supplies, housing, agriculture, mining, and industry, are important repositories of organic carbon, nutrients, and metal contaminants. The accumulation and release of these species is often mediated by redox processes. By understanding the physicochemical, hydrological, and biogeochemical controls on the distribution and variability of sediment redox conditions we can develop conceptual and numerical models of contaminant transport within floodplains. The Upper Colorado River Basin (UCRB) is impacted by former uranium and vanadium ore processing, resulting in contamination by V, Cr, Mn, As, Se, Mo and U. Previous authors have suggested that sediment redox activity occurring withinmore » organic carbon-enriched bodies located below the groundwater level may be regionally important to the maintenance and release of contaminant inventories, particularly uranium. To help assess this hypothesis, vertical distributions of Fe and S redox states and sulfide mineralogy were assessed in sediment cores from three floodplain sites spanning a 250 km transect of the central UCRB. Our results support the hypothesis that organic-enriched reduced sediments are important zones of biogeochemical activity within UCRB floodplains. Furthermore, we found that the presence of organic carbon, together with pore saturation, are the key requirements for maintaining reducing conditions, which were dominated by sulfate-reduction products. Sediment texture was found to be of secondary importance and to moderate the response of the system to external forcing, such as oxidant diffusion. Consequently, fine-grain sediments are relatively resistant to oxidation in comparison to coarser-grained sediments. Exposure to oxidants consumes precipitated sulfides, with a disproportionate loss of mackinawite (FeS) as compared to the more stable pyrite. The accompanying loss of redox buffering capacity creates the potential for release of sequestered radionuclides and metals. Because of their redox reactivity and stores of metals, C, and N, organic-enriched sediments are likely to be important to nutrient and contaminant mobility within UCRB floodplain aquifers.« less

Seasonal Hydrologic Controls on Uranium and Iron Biogeochemistry in a Riparian Aquifer

NASA Astrophysics Data System (ADS)

Wilkins, M.; Williams, K. H.; Danczak, R. E.; Yabusaki, S.; Fang, Y.; Hobson, C.

2015-12-01

The maintenance of geochemically reducing conditions is generally optimal for the formation and preservation of reduced metals and mineral phases that can limit contaminant fate and transport. At a riparian aquifer near Rifle, CO, we tracked over six months the biogeochemical response within the aquifer to an annual pulse of dissolved oxygen (DO) that results from snowmelt-driven changes in Colorado River stage. In reduced portions of the aquifer (naturally reduced zones; NRZs) the re-oxidation of abundant iron sulfide minerals was the dominant oxygen-consuming process, and resulted in little DO intrusion into the deeper aquifer. In less reduced areas, DO intruded through the entire vertical profile of the aquifer. Across both regions, these perturbations resulted in changes to the microbial community structure, and aqueous metal pools. Two potentially different mechanisms of uranium mobilization were observed; (1) re-oxidation of reduced U(IV) phases in response to DO intrusion, and (2) mobilization of U(VI) from the vadose zone during water table rise. This high-resolution, long-term monitoring of aquifer biogeochemistry at the Rifle site has revealed dynamic microbial and geochemical responses to predictable, annual hydrologic perturbations, and offers an opportunity to further refine modeling approaches for such regions.

Advances in soil gas geochemical exploration for natural resources: Some current examples and practices

NASA Astrophysics Data System (ADS)

McCarthy, J. Howard, Jr.; Reimer, G. Michael

1986-11-01

Field studies have demonstrated that gas anomalies are found over buried mineral deposits. Abnormally high concentrations of sulfur gases and carbon dioxide and abnormally low concentrations of oxygen are commonly found over sulfide ore deposits. Helium anomalies are commonly associated with uranium deposits and geothermal areas. Helium and hydrocarbon gas anomalies have been detected over oil and gas deposits. Gases are sampled by extracting them from the pore space of soil, by degassing soil or rock, or by adsorbing them on artificial collectors. The two most widely used techniques for gas analysis are gas chromatography and mass spectrometry. The detection of gas anomalies at or near the surface may be an effective method to locate buried mineral deposits.

Pilot Study to Evaluate Hydrogen Injection for Stimulating Reduction and Immobilization of Uranium in Groundwater at an ISR Mining Site

NASA Astrophysics Data System (ADS)

Clapp, L. W.; Cabezas, J.; Gamboa, Y.; Fernandez, W.

2011-12-01

State and federal regulations require that groundwater at in-situ recovery (ISR) uranium mining operations be restored to pre-mining conditions. Reverse osmosis (RO) filtration of several pore volumes of the post-leached groundwater and reinjection of the clean permeate is the most common technology currently used for restoring groundwater at uranium ISR sites. However, this approach does not revert the formation back to its initial reducing conditions, which can potentially impede timely groundwater restoration. In-situ biostimulation of indigenous iron- and sulfate reducing bacteria by injection of organic electron donors (e.g., ethanol, acetate, and lactate) to promote soluble uranium reduction and immobilization has been the subject of previous studies. However, injection of organic substrates has been observed to cause aquifer clogging near the injection point. In addition, U(VI) solubility may be enhanced through complexation with carbonate generated by organic carbon oxidation. An alternative approach that may overcome these problems involves the use of hydrogen as a reductant to promote microbial reduction and immobilization of U(VI) in situ. To test this approach, approximately 100,000 scf of compressed hydrogen gas was injected into a leached unconsolidated sand zone over two months at an ISR mining site. During this time groundwater was recirculated between injection and extraction wells (separated by 130 ft) at a rate of about 40 gpm and bromide was coinjected as a conservative tracer. A well monitoring program has been executed since June 2009 to evaluate the performance of the hydrogen injection. Current results show that U(VI) has been reduced from 4.2 to 0.05 ppm in the area surrounding the injection well and to 2.0 ± 0.3 ppm in the area surrounding the extraction well and two intermediate monitoring wells. Other water quality changes near the injection well include significant decreases in concentrations of Mo, sulfate, Fe, Mn, bicarbonate, Ca, and Eh, and increases in pH, methane, and sulfide. No significant rebound of soluble uranium concentrations was observed, but significant rebounds in molybdenum and sulfate have been observed. Ongoing studies are evaluating the effective zone of influence of the hydrogen injection.

Preliminary Report on the White Canyon Area, San Juan County, Utah

USGS Publications Warehouse

Benson, William Edward Barnes; Trites, A.F.; Beroni, E.P.; Feeger, J.A.

1952-01-01

The White Canyon area in San Juan County, Utah, contains known deposits of copper-uranium ore and is currently being mapped and studied by the Geological Survey. To date, approximately 75 square miles, or about 20 percent of the area, has been mapped on a scale 1 inch=1 mile. The White Canyon area is underlain by more than 2,000 feet of sedimentary rocks, Carboniferous to Jurassic(?) in age. The area is on the flank of the Elk Ridge anticline, and the strata have a regional dip of 1 deg to 2 deg SW. The Shinarump conglomerate of Late Triassic age is the principal ore-bearing formation. The Shinarump consists of lenticular beds of sandstone, conglomeratic sandstone, clay, and siltstone, and ranges in thickness from a feather edge to as much as 75 feet. Locally the sandstones contain silicified and carbonized wood and fragments of charcoal. These vegetal remains are especially common in channel-fill deposits. Jointing is prominent in the western part of the area, and apparently affects all formations. Adjacent to the joints some of the redbeds in the sequence are bleached. Deposits of copper-uranium minerals have been found in the Moenkopi, Shinarump, and Chinle formations, but the only production of ore has been from the Shinarump conglomerate. The largest concentration of these minerals is in the lower third of the Shinarump, and the deposits seem to be controlled in part by ancient channel fills and in part by fractures. Locally precipitation of the copper and uranium minerals apparently has been aided by charcoal and clays. Visible uranium minerals include both hard and soft pitchblende and secondary hydrosulfates, phosphates, and silicates. In addition, unidentified uranium compounds are present in carbonized wood and charcoal, and in veinlets of hydrocarbons. Base-metal sulfides have been identified in all prospects that extend beyond the oxidized zone. Secondary copper minerals in the oxidized zone include the hydrous sulfates and carbonates, and possibly chrysocolla. The principal gangue minerals are quartz, clay minerals, chlorite, oxides of iron and manganese, alunite, calcite, gypsum, pyrite, allophane, gibbsite, opal, and chalcedony. The origin of the copper-uranium ores has not been determined, but the association of many deposits with fractures, the mineralogic assemblage, and a lead-uranium age determination of 50 to 60 million years for the pitchblende in the Happy Jack mine favor the hypothesis that the ores are of hydrothermal origin and were deposited in early Tertiary time. Criteria believed to be the most useful in prospecting for new deposits are (1) visible uranium minerals; (2) visible copper minerals; (3) alunite; (4) hydrocarbons; and (5) bleaching of the underlying Moenkopi formation.

Exploratory Solid-State Synthesis of Uranium Chalcogenides and Mixed Anion Uranium Chalcogenides

NASA Astrophysics Data System (ADS)

Ward, Matthew David

Several uranium chalcogenides and mixed anion uranium chalcogenides have been synthesized by solid-state synthetic methods. Structural determinations were carried out via single-crystal X-ray diffraction. Some of these compounds have been further characterized by magnetic measurements, optical properties measurements, Raman spectroscopy, resistivity measurements, XANES and XPS. Eight compounds of the composition MU8Q17 were synthesized and characterized by single-crystal X-ray diffraction. All of these compounds crystallize in the CrU8S17 structure type. XANES measurements indicate that ScU8S17 contains Sc3+ and must be charge balanced with some amount of U 3+. Two compounds of the composition ATiU3Te9 crystallize as black rectangular plates. From single-crystal magnetic measurements, CsTiU 3Te9 is consistent with antiferromagnetic coupling between magnetic U atoms. The uranium chalcogenide compounds NiUS3 and Cr4US 8 were synthesized from reaction of the elements in various fluxes. NiUS3 crystallizes in the GdFeO3 structure type. Cr 4US8 crystallizes in the orthorhombic space group D - Pnma and its structure is related to that of Li4UF 8. The compounds Rh2U6S15, Cs 2Ti2U6Se15, and Cs2Cr 2U6Se15 crystallize as black prisms in the cubic space group O-Im3m. Magnetic measurements on Cs 2Cr2U6Se15 give a value for the Weiss temperature, θWeiss, of 57.59 K, indicative of ferromagnetic coupling. Black plates of CsScU(Se2)Se3 were synthesized from the reaction of the elements in a CsCl flux. CsScU(Se2)Se 3 crystallizes in the orthorhombic space group D- Cmcm . Magnetic susceptibility measurements on CsScU(Se2)Se 3 indicate three regions of magnetic response. The uranium double salt Cs5[U2(μ-S 2)2Cl8]I crystallizes as red plates. Cs 5[U2(μ-S2)2Cl 8]I displays optical anisotropy with band gap energies of 1.99 eV and 2.08 eV along the [001] and [100] polarizations. The uranium oxychalcogenides U7O2Se12 and Na2Ba2(UO2)S4 were synthesized by intentional oxygen contamination. The structure of U7O 2Se12 is related to the previously reported U7Q 12. Na2Ba2(UO2)S4 contains isolated uranyl polyhedra in which each uranium atom may be assigned an oxidation state of +6. The four uranium(IV) chlorophosphates, UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl 2), and U2Cl8(POCl3) were synthesized in an effort to synthesize new novel uranyl sulfides. All are unstable, but UCl4(POCl3) is the thermodynamically favorable phase.

Heavy metal mining using microbes.

PubMed

Rawlings, Douglas E

2002-01-01

The use of acidiphilic, chemolithotrophic iron- and sulfur-oxidizing microbes in processes to recover metals from certain types of copper, uranium, and gold-bearing minerals or mineral concentrates is now well established. During these processes insoluble metal sulfides are oxidized to soluble metal sulfates. Mineral decomposition is believed to be mostly due to chemical attack by ferric iron, with the main role of the microorganisms being to reoxidize the resultant ferrous iron back to ferric iron. Currently operating industrial biomining processes have used bacteria that grow optimally from ambient to 50 degrees C, but thermophilic microbes have been isolated that have the potential to enable mineral biooxidation to be carried out at temperatures of 80 degrees C or higher. The development of higher-temperature processes will extend the variety of minerals that can be commercially processed.

Early breakthrough of molybdenum and uranium in a permeable reactive barrier.

PubMed

Morrison, Stan J; Mushovic, Paul S; Niesen, Preston L

2006-03-15

A permeable reactive barrier (PRB) using zerovalent iron (ZVI) was installed at a site near Cañon City, CO, to treat molybdenum (Mo) and uranium (U) in groundwater. The PRB initially decreased Mo concentrations from about 4.8 to less than 0.1 mg/L; however, Mo concentrations in the ZVI increased to 2.0 mg/L after about 250 days and continued to increase until concentrations in the ZVI were about 4 times higherthan in the influent groundwater. Concentrations of U were reduced from 1.0 to less than 0.02 mg/L during the same period. Investigations of solid-phase samples indicate that (1) calcium carbonate, iron oxide, and sulfide minerals had precipitated in pores of the ZVI; (2) U and Mo were concentrated in the upgradient 5.1 cm of the ZVI; and (3) calcium was present throughout the ZVI accounting for up to 20.5% of the initial porosity. Results of a column test indicated that the ZVI from the PRB was still reactive for removing Mo and that removal rates were dependenton residence time and pH. The chemical evolution of the PRB is explained in four stages that present a progression from porous media flow through preferential flow and, finally, complete bypass of the ZVI.

PRIMARY MINERALIZATION OF URANIUM-BEARING "SILICEOUS REEF" VEINS IN THE BOULDER BATHOLITH, MONTANA. PART I. THE HOST ROCKS

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

Wright, H.D.; Bieler, B.H.

1960-01-01

Between 1952 and 1956 a study was made of some of the uranium-bearing hydrothermal veins in the northern part of the Boulder batholith, Montana. Three mines, the W. Wilson, G. Washington, and Free Enterprise, were investigated in detail. The veins are characterized by a microcrystalline quartz gangue containing sparsely scattered, very fine-grained sulfide minerals and uraninite. Above the present water table, secondary uranium minerals are abundant locally. Throughout the area the veins --called "siliceous reefs"--strike east to northeast, are of steep dip, and vary in thickness from a fraction of an inch to several feet. The country rock is granodioritemore » containing, in order of abundance, plagioclase (An/sub 30/ to An/sub 36/), quartz, orthoclase, biotite, and hornblende, with apatite, zircon, and sphene. Small bodies of aplite, pegmatite, and alaskite occur along some veins. The granodiorite adjacent to the veins is rather strongly altered. The alteration is similar throughout all of the deposits studied, in barren and orebearing portions alike. The essential minerals show a characteristic sequence of alteration, in the order hornblende, andesine, biotite, orthoclase, and quartz. Successive zones of alteration are characterized, from the vein outward, by maximum development of sericite (muscovite polytype 1M, in part), kaolinite, and montmorillonite. Other alteration products are quartz, pyrite, calcite, leucoxene, and chlorite. The alteration resulted in an increase in silica and ferric iron, a decrease in alumina, total iron, ferrous iron, lime, soda, and magnesia, and little change in potash, titania, phosphorus, carbon dioxide, and sulfur. Consideration of the stability fields of the sheet structure silicate minerals indicates little basis for interpretation of the temperatures prevailing during mineralization. (auth)« less

Leachability of uranium and other elements from freshly erupted volcanic ash

USGS Publications Warehouse

Smith, D.B.; Zielinski, R.A.; Rose, W.I.

1982-01-01

A study of leaching of freshly erupted basaltic and dacitic air-fall ash and bomb fragment samples, unaffected by rain, shows that glass dissolution is the dominant process by which uranium is initially mobilized from air-fall volcanic ash. Si, Li, and V are also preferentially mobilized by glass dissolution. Gaseous transfer followed by fixation of soluble uranium species on volcanic-ash particles is not an important process affecting uranium mobility. Gaseous transfer, however, may be important in forming water-soluble phases, adsorbed to ash surfaces, enriched in the economically and environmentally important elements Zn, Cu, Cd, Pb, B, F, and Ba. Quick removal of these adsorbed elements by the first exposure of freshly erupted ash to rain and surface water may pose short-term hazards to certain forms of aquatic and terrestrial life. Such rapid release of material may also represent the first step in transportation of economically important elements to environments favorable for precipitation into deposits of commercial interest. Ash samples collected from the active Guatemalan volcanoes Fuego and Pacaya (high-Al basalts) and Santiaguito (hornblende-hypersthene dacite); bomb fragments from Augustine volcano (andesite-dacite), Alaska, and Heimaey (basalt), Vestmann Islands, Iceland; and fragments of "rhyolitic" pumice from various historic eruptions were subjected to three successive leaches with a constant water-to-ash weight ratio of 4:1. The volcanic material was successively leached by: (1) distilled-deionized water (pH = 5.0-5.5) at room temperature for 24 h, which removes water-soluble gases and salts adsorbed on ash surfaces during eruption; (2) dilute HCl solution (pH = 3.5-4.0) at room temperature for 24 h, which continues the attack initiated by the water and also attacks acid-soluble sulfides and oxides; (3) a solution 0.05 M in both Na,CO, and NaHCO, (pH = 9.9) at 80°C for one week, which preferentially dissolves volcanic glass. The first two leaches mimic interaction of ash with rain produced in the vicinity of an active eruption. The third leach accelerates the effect of prolonged contact of volcanic ash with alkaline ground water present during ash diagenesis.

Bacterial community succession during in situ uranium bioremediation: spatial similarities along controlled flow paths.

PubMed

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J; Carley, Jack; Corbin, Gail A; Carroll, Sue L; Watson, David B; Jardine, Phil M; Zhou, Jizhong; Criddle, Craig S; Fields, Matthew W

2009-01-01

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5-year period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate and ethanol were strongly correlated with particular bacterial populations. As sulfate and U(VI) levels declined, sequences representative of sulfate reducers and metal reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared with the population variation through canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bioreduction; however, the two biostimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.

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.

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

Geochemistry of Peruvian near-surface sediments

NASA Astrophysics Data System (ADS)

Böning, Philipp; Brumsack, Hans-Jürgen; Böttcher, Michael E.; Schnetger, Bernhard; Kriete, Cornelia; Kallmeyer, Jens; Borchers, Sven Lars

2004-11-01

Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ 34S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ 34S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ 34S of dissolved sulfate showed only minor downcore increases. Strong 32S enrichments in sedimentary pyrite (to -48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.

Experimental formation of Pb, Sn, Ge and Sb sulfides, selenides and chlorides in the presence of sal ammoniac: A contribution to the understanding of the mineral formation processes in coal wastes self-burning

NASA Astrophysics Data System (ADS)

Laufek, František; Veselovsky, František; Drábek, Milan; Kříbek, Bohdan; Klementová, Mariana

2017-04-01

The formation of sulfides, selenides and chlorides was experimentally studied at 800 or 900°C in the presence of sal ammoniac in a sealed silica glass tube. Synthetic PbS, PbSe, SnS, GeS, SnGeS2, PbSnS3, SnS and Sb2S3 or natural uraninite were used as a starting charge. Depending on the chemical composition of the sulfide/selenide charge, galena, unnamed SnGeS3 phase, herzenbergite, berndite, ottenmannite, stibnite and unnamed SnSb2S4 and Sn2Sb3S6 phases were identified in sublimates, together with cotunnite and an unnamed (NH4)2SnCl6 phase. When natural uraninite in a mixture with sal ammoniac was used as a charge, the reaction product comprised abundant cotunnite and minor challacolloite due to volatilization of radiogenic lead. When sulfur was introduced to the charge with uraninite and sal ammoniac, galena was found in reaction products. The results of our experiments revealed that if sulfide or selenide phases and NH4Cl are placed in a thermal gradient, it is possible to accelerate their mobility through a process of hydrogen chloride vapor transport. Within the transport process, new solid products are either isochemical or non-isochemical. The isochemical composition of resulting phases with charge probably represents simple sublimation of the original solid phase in form of self-vapor. The non-isochemical phases are probably formed due to combination of sublimation and condensation of various gas components including gaseous HCl. The valency change of metals (e.g. Sn2+ to Sn3+) in several reaction products indicates redox reactions in the gas mixture or during the solidification of resulting products. The role of ammoniac is not clear; however, formation of unnamed (NH4)2SnCl6 compound identified in one of our experiment, indicate possible formation of ammonium complexes. In contrast to experiments where sulfides or selenides were used as a part of charge, mobility of uraninite was not proved under experimental conditions employed. It is consistent with an absence of uranium minerals in products of self-burning. The product of uraninite thermal decomposition was predominantly lead chloride (cotunnite) resulting from the release of radiogenic lead from uraninite structure. However, when sulfur was added to the charge, skeletal crystals of galena were found in the reaction products. Acknowledgments: This study was carried out within the Czech Science Foundation grant project "A model of mobilization and geochemical cycles of potentially hazardous elements and organic compounds in burnt coal heaps" (GACR 15-11674S panel P210).

Geology of the Copper King Mine area, Prairie Divide, Larimer County, Colorado (Part 1)

USGS Publications Warehouse

Sims, Paul Kibler; Phair, George

1952-01-01

The Copper King mine, in Larimer County, Colo., in the northern part of the Front Range of Colorado, was operated for a short time prior to World War II for copper and zino, but since 1949, when pitchblende was discovered on the mine dump, it has been worked for uranium. The bedrock in the mine area consists predominantly of pre-Cambrian (Silver Plums) granite with minor migmatite and metasediments--biotite-quartz-plagioclase gneiss, biotite schist, quartzite, amphibolite, amphibole skarn, and biotite skols. The metasediments occur as inclusions that trend northeast in the granite. This trend is essentially parallel to the prevailing foliation in the granite. At places the metasediments are crosscut sharply by the granite to form angular, partly discordant, steep-walled bodies in the granite. Faults, confined to a narrow zone that extends through the mine, cut both the pre-Cambrian rocks and the contained sulfide deposits. The Copper King fault, a breccia zone, contains a deposit of pitchblende; the other faults are believed to be later than the ore. The two types of mineral deposits--massive sulfide and pitchblende deposits--in the mine area, are of widely different mineralogy, age, and origin. The massive sulfide deposits are small and consist of pyrite, sphalerite, chalcopyrite, pyrrhotite, and in places magnetite in amphibole skarn, mice skols, and quartzite. The deposit at the Copper King mine has yielded small quantities of high-grade sphalerite ore. The massive sulfides are pyrometasomatic deposits of pre-Cambrian age. The pitchblende at the Copper King mine is principally in the Copper King vein, a tight, hard breccia zone that cuts through both granite and the massive sulfide deposit. A small part of the pitchblende is in small fractures near the vein and in boxwork pyrite adjacent to the vein; the post-ore faults, close to their intersection with the Copper King vein, contain some radioactive material, but elsewhere, so far as is known, they are barren. The pitchblende in the deposit forms a steeply plunging ore shoot that has a horizontal length of more than 50 feet and a vertical height of about 85 feet. The thickness of the ore shoot averages about 2 feet, but it ranges from a feather edge to about 4 feet. The hard pitch-blende is intimately intergrown with siderite; other gangue minerals include pyrite, quartz, and finely comminuted fragments of the wall rocks. The vein was repeatedly reopened during mineral deposition as shown by several stages of brecciation and recommended by the vein matter. The pitchblende deposit probably formed at intermediate temperatures and depths and, according to the Pb/U ratio, is about 60 million years old--an early Tertiary age.

Quartz-pebble-conglomerate gold deposits: Chapter P in Mineral deposit models for resource assessment

USGS Publications Warehouse

Taylor, Ryan D.; Anderson, Eric D.

2018-05-17

Quartz-pebble-conglomerate gold deposits represent the largest repository of gold on Earth, largely due to the deposits of the Witwatersrand Basin, which account for nearly 40 percent of the total gold produced throughout Earth’s history. This deposit type has had a controversial history in regards to genetic models. However, most researchers conclude that they are paleoplacer deposits that have been modified by metamorphism and hydrothermal fluid flow subsequent to initial sedimentation.The deposits are found exclusively within fault-bounded depositional basins. The periphery of these basins commonly consists of granite-greenstone terranes, classic hosts for lode gold that source the detrital material infilling the basin. The gold reefs are typically located along unconformities or, less commonly, at the top of sedimentary beds. Large quartz pebbles and heavy-mineral concentrates are found associated with the gold. Deposits that formed prior to the Great Oxidation Event (circa 2.4 giga-annum [Ga]) contain pyrite, whereas younger deposits contain iron oxides. Uranium minerals and hydrocarbons are also notable features of some deposits.Much of the gold in these types of deposits forms crystalline features that are the product of local remobilization. However, some gold grains preserve textures that are undoubtedly of detrital origin. Other heavy minerals, such as pyrite, contain growth banding that is truncated along broken margins, which indicates that they were transported into place as opposed to forming by in situ growth in a hydrothermal setting.The ore tailings associated with these deposits commonly contain uranium-rich minerals and sulfides. Oxidation of the sulfides releases sulfuric acid and mobilizes various metals into the environment. The neutralizing potential of the tailings is minimal, since carbonate minerals are rare. The continuity of the tabular ore bodies, such as those of the Witwatersrand Basin, has allowed these mines to be the deepest in the world. The extreme depths create engineering complications and safety issues for the miners, such as rock bursts as a result of pressure release.The richness of these deposits makes them a desirable exploration target. However, the likelihood of future discoveries is minimal. Small deposits found in the United States include those found at Nemo in the Black Hills of South Dakota and Deep Lake in the Sierra Madre of Wyoming.

A study of contaminated soils near Crucea-Botus, ana uranium mine (East Carpathians, Romania): metal distribution and partitioning of natural actinides with implications for vegetation uptake

NASA Astrophysics Data System (ADS)

Petrescu, L.; Bilal, E.

2012-04-01

Between 1962 and 2009, National Company of Uranium - CNU, the former Romanian Rare Metals Mining Company, mined over 1,200,000 tones of pitchblende ore in the East Carpathians (Crucea-Botušana area, Bistrita Mountains). The exploration and mining facilities include 32 adits, situated between 780 and 1040 m above sea level. Radioactive waste resulted from mining are disposed next to the mining facilities. Mine dumps (32) cover an area of 364,000 square meters and consist of waste rock (rocks with sub-economic mineralization) and gangue minerals. Older dumps (18) have been already naturally reclaimed by forest vegetation, which played an important role in stabilizing the waste dump cover and in slowing down the uranium migration processes. The soils samples have been collected from different mine dumps in the Crucea-Botušana uranium deposit, mainly from 1, 4, 5, 6, 8, 9, 1/30 and 950 mine waste galleries. Soil samples were collected from the upper part and slope at each mine dump, from the vegetation root zones. Total uranium concentration in soils collected from Crucea-Botušana site ranged from 6.10 to 680.70 ppm, with a mean of 52.48 ppm (dry wt.). Total thorium varies between 7.70 and 115.30 ppm (dry wt.). This indicates that the adsorption of the radioactive elements by the soils is high and variable, influenced by the ore dump - sample relationship. The sequential extraction has emphasized the fact that the uranium is associated with all the mineral fractions present in the soil samples. A great percentage of U can be found in the carbonate (21.77%), organic (15.04%) and oxides fractions (15.88%) - in accordance with the high absorbed/adsorbed properties of this element. The percentage of uranium detected in the exchangeable fraction is rather small - 2.16%. It is also to be expected that the uranium should be irreversible adsorbed by the organic matter and by the clay minerals due to its ionic radius and to its positive charge. The fact that 21.77% of the total uranium can be found in the specifically absorbed and carbonate bound fraction, indicated the important role played by the carbonates in the retention of U; one the other hand this fraction is liable to release the uranium if the pH should happen to change. Thorium appear in high-enough concentration in the soil is scarcely available because 70.29% is present in residual fraction, and about 21.78% in the crystalline iron oxides occluded fraction and organically and secondary sulfide bound fraction. This is certainly due to the fact that this naturally occurring radionuclide can be associated with relatively insoluble mineral phases like alumino-silicates and refractory oxides. Its association with the organic matter (10.93%) suggests that it can form soluble organic complexes that can facilitate its removal by the stream waters. Grounded on these results, we were able to prove that the examined mine dumps can represent an impact on the environment, which constitute an argument in favor of the initiation of a program of remedying the quality of the environment from this mining zone. Although from our research it resulted that the natural actinides does not concentrate in the exchangeable fraction (Th) or it concentrates very little in it (U), the isolation of the mineral fraction of soil rich in U and Th helps us in the future identification of the links between the bioavailability and the pedogenesis, connections which control the cycle of the radioactive metals.

Uranium isotopes distinguish two geochemically distinct stages during the later Cambrian SPICE event

PubMed Central

Dahl, Tais W.; Boyle, Richard A.; Canfield, Donald E.; Connelly, James N.; Gill, Benjamin C.; Lenton, Timothy M.; Bizzarro, Martin

2015-01-01

Anoxic marine zones were common in early Paleozoic oceans (542–400 Ma), and present a potential link to atmospheric pO2 via feedbacks linking global marine phosphorous recycling, primary production and organic carbon burial. Uranium (U) isotopes in carbonate rocks track the extent of ocean anoxia, whereas carbon (C) and sulfur (S) isotopes track the burial of organic carbon and pyrite sulfur (primary long-term sources of atmospheric oxygen). In combination, these proxies therefore reveal the comparative dynamics of ocean anoxia and oxygen liberation to the atmosphere over million-year time scales. Here we report high-precision uranium isotopic data in marine carbonates deposited during the Late Cambrian ‘SPICE’ event, at ca. 499 Ma, documenting a well-defined −0.18‰ negative δ238U excursion that occurs at the onset of the SPICE event’s positive δ13C and δ34S excursions, but peaks (and tails off) before them. Dynamic modelling shows that the different response of the U reservoir cannot be attributed solely to differences in residence times or reservoir sizes - suggesting that two chemically distinct ocean states occurred within the SPICE event. The first ocean stage involved a global expansion of euxinic waters, triggering the spike in U burial, and peaking in conjunction with a well-known trilobite extinction event. During the second stage widespread euxinia waned, causing U removal to tail off, but enhanced organic carbon and pyrite burial continued, coinciding with evidence for severe sulfate depletion in the oceans (Gill et al., 2011). We discuss scenarios for how an interval of elevated pyrite and organic carbon burial could have been sustained without widespread euxinia in the water column (both non-sulfidic anoxia and/or a more oxygenated ocean state are possibilities). Either way, the SPICE event encompasses two different stages of elevated organic carbon and pyrite burial maintained by high nutrient fluxes to the ocean, and potentially sustained by internal marine geochemical feedbacks. PMID:25684783

Bacterial Community Succession During in situ Uranium Bioremediation: Spatial Similarities Along Controlled Flow Paths

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

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J.

2009-05-22

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction, and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5 y period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate, and ethanol strongly correlated with particular bacterialmore » populations. As sulfate and U(VI) levels declined, sequences representative of sulfate-reducers and metal-reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared to the population variation via canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bio-reduction; however, the two bio-stimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.« less

Hiereachical Bayesian Model for Combining Geochemical and Geophysical Data for Environmental Applications Software

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

Chen, Jinsong

2013-05-01

Development of a hierarchical Bayesian model to estimate the spatiotemporal distribution of aqueous geochemical parameters associated with in-situ bioremediation using surface spectral induced polarization (SIP) data and borehole geochemical measurements collected during a bioremediation experiment at a uranium-contaminated site near Rifle, Colorado. The SIP data are first inverted for Cole-Cole parameters including chargeability, time constant, resistivity at the DC frequency and dependence factor, at each pixel of two-dimensional grids using a previously developed stochastic method. Correlations between the inverted Cole-Cole parameters and the wellbore-based groundwater chemistry measurements indicative of key metabolic processes within the aquifer (e.g. ferrous iron, sulfate, uranium)more » were established and used as a basis for petrophysical model development. The developed Bayesian model consists of three levels of statistical sub-models: 1) data model, providing links between geochemical and geophysical attributes, 2) process model, describing the spatial and temporal variability of geochemical properties in the subsurface system, and 3) parameter model, describing prior distributions of various parameters and initial conditions. The unknown parameters are estimated using Markov chain Monte Carlo methods. By combining the temporally distributed geochemical data with the spatially distributed geophysical data, we obtain the spatio-temporal distribution of ferrous iron, sulfate and sulfide, and their associated uncertainity information. The obtained results can be used to assess the efficacy of the bioremediation treatment over space and time and to constrain reactive transport models.« less

Comparison of the mineralogy of the Boss-Bixby, Missouri copper-iron deposit, and the Olympic Dam copper-uranium-gold deposit, South Australia

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

Brandom, R.T.; Hagni, R.D.; Allen, C.R.

1985-01-01

An ore microscopic examination of 80 polished sections prepared from selected drill core specimens from the Boss-Bixby, Missouri copper-iron deposit has shown that its mineral assemblage is similar to that of the Olympic Dam (Roxby Downs) copper-uranium-gold deposit in South Australia. A comparison with the mineralogy reported for Olympic Dam shows that both deposits contain: 1) the principal minerals, magnetite, hematite, chalcopyrite, and bornite, 2) the cobalt-bearing phases, carrollite and cobaltian pyrite, 3) the titanium oxides, rutile and anatase, 4) smaller amounts of martite, covellite, and electrum, 5) fluorite and carbonates, and 6) some alteration minerals. The deposits also aremore » similar with regard to the sequence of mineral deposition: 1) early oxides, 2) then sulfide minerals, and 3) a final oxide generation. The deposits, however, are dissimilar with regard to their host rock lithologies and structural settings. The Boss-Bixby ores occupy breccia zones within a hydrothermally altered basic intrusive and intruded silicic volcanics, whereas the Olympic Dam ores are contained in sedimentary breccias in a graben or trough. Also, some minerals have been found thus far to occur at only one of the deposits. The similarity of mineralogy in these deposits suggests that they were formed from ore fluids that had some similarities in character and that the St. Francois terrane of Missouri is an important region for further exploration for deposits with this mineral assemblage.« less

A preliminary evaluation of the nonfuel mineral potential of Somalia

USGS Publications Warehouse

Greenwood, W.R.

1982-01-01

Additional exploration in Somalia is warranted for a wide variety of metallic and nonmetallic deposits. In Precambrian rocks, deposit types favorable for exploration include: a banded iron formation; platinum-bearing mafic-ultramafic complexes; tin-bearing quartz veins; phosphorite; stratabound base-metal deposits; uranium associated with Precambrian(?) syenite; apatite, molybdenum, and alumina in alkalic rocks; Jurassic and Cretaceous black shales; possible bedded-barite and massive base- and precious-metal sulfide deposits; vein barite in Tertiary rocks in fault zones; sepiolite and bentonite for drilling muds and other industrial uses; celestite; possible Tertiary zeolite; and uranium deposits. Several of these deposit types could be Jointly developed and integrated into domestic industries; for example, phosphate and gypsum, or bentonite for pelletized iron from the banded iron deposits. Other deposits such as barite and sepiolite are of value because of their proximity to major drilling operations in the Arabian Gulf. Still other deposits, such as alumina and banded iron, might be marketable because of proximity to aluminum and iron-refining industries now being constructed in Saudi Arabia. Some deposits, such as celestite, can be developed with little capital investment; others, such as the iron deposits, would require large capital commitments. Exploration and evaluation for many of these deposits can be accomplished by Somali geologists with a few advisors. Most of the deposits require feasibility studies conducted by teams of economic geologists, extractive metallurgists, and economists. Some marginal deposits could be exploited if cooperative development schemes could be negotiated with governments in nearby countries.

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

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

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA

2008-05-12

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of themore » most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The primary objective of this project was to understand the complex interactions among the contaminants (i.e., Cr, Tc, and U), H{sub 2}S, and various soil constituents. The reaction with iron sulfide is also the focus of the research, which could be formed from iron oxide reduction by hydrogen sulfide. Factors controlling the reductive immobilization of these contaminants were identified and quantified. The results and fundamental knowledge obtained from this project shall help better evaluate the potential of in situ gaseous treatment to immobilize toxic and radioactive metals examined.« less

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

PubMed

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

2002-05-01

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

Metathesis of a UV imido complex: a route to a terminal UV sulfide† †Electronic supplementary information (ESI) available: Full computational and experimental details, NMR spectra, and detailed X-ray crystallographic data in CIF format. CCDC 1535285–1535289. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01111c Click here for additional data file. Click here for additional data file.

PubMed Central

Kelly, Rory P.; Falcone, Marta; Lamsfus, Carlos Alvarez; Scopelliti, Rosario; Maron, Laurent; Meyer, Karsten

2017-01-01

Herein, we report the synthesis and characterisation of the first terminal uranium(v) sulfide and a related UV trithiocarbonate complex supported by sterically demanding tris(tert-butoxy)siloxide ligands. The reaction of the potassium-bound UV imido complex, [U(NAd){OSi(OtBu)3}4K] (4), with CS2 led to the isolation of perthiodicarbonate [K(18c6)]2[C2S6] (6), with concomitant formation of the UIV complex, [U{OSi(OtBu)3}4], and S 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CNAd. In contrast, the reaction of the UV imido complex, [K(2.2.2-cryptand)][U(NAd){OSi(OtBu)3}4] (5), with one or two equivalents of CS2 afforded the trithiocarbonate complex, [K(2.2.2-cryptand)][U(CS3){OSi(OtBu)3}4] (7), which was isolated in 57% yield, with concomitant elimination of the admantyl thiocyanate product, SCNAd. Complex 7 is likely formed by fast nucleophilic addition of a UV terminal sulfide intermediate, resulting from the slow metathesis reaction of the imido complex with CS2, to a second CS2 molecule. The addition of a solution of H2S in thf (1.3 eq.) to 4 afforded the first isolable UV terminal sulfide complex, [K(2.2.2-cryptand)][US{OSi(OtBu)3}4] (8), in 41% yield. Based on DFT calculations, triple-bond character with a strong covalent interaction is suggested for the U–S bond in complex 7. PMID:28970911

Preliminary magnetotelluric results across Dalma Volcanics, Eastern India: Inferences on metallogeny

NASA Astrophysics Data System (ADS)

Maurya, Ved P.; Shalivahan; Bhattacharya, B. B.; Adhikari, P. K.; Das, L. K.

2015-04-01

The regional magnetotelluric (MT) survey across Dalma Volcanics (DVs) in North Singhbhum Mobile Belt (NSMB) was carried out to obtain the conductivity model and to understand the metallogeny. The structure in general is 2-D and the average strike is N60°W. 2-D inversions using TE + TM and TE + TM + Tzy were carried out. Both inversions derived models with similar features but with modified shape. The TE + TM + Tzy inversion brings up two conducting zones enveloping three anomalous conducting bodies. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis of the samples collected from 8 to 10 m pit from different stratigraphic units of Dalma volcano-sedimentary belt indicates the presence of gold, silver, uranium and copper. The study area is a felsic dominated rifted margin and shows high conductivity contrast along with high gravity, magnetic and significant radiometric anomaly. Thus, the conducting zones indicate the presence of volcanogenic massive sulfide (VMS) or volcano hosted gold deposit (Au-VMS) in NSMB.

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a dendritic quench texture and is usually surrounded by the sulfide matrix. These data indicate that multiple phases, each with a different Pt:Pd ratio can form upon quench of a homogenous sulfide melt. Thus, the analysis of PGE-rich sulfide domains within LMI may be best considered as a single phase when conducting exploration efforts.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2006-05-02

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2003-01-01

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit, Bohemian Massif, Czech Republic: fluid inclusion and stable isotope constraints

NASA Astrophysics Data System (ADS)

Dolníček, Zdeněk; René, Miloš; Hermannová, Sylvie; Prochaska, Walter

2014-04-01

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (˜50-140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0-25 wt.% NaCl eq.), low fluid δ18O values (-10 to +2 ‰ V-SMOW), low fluid δ13C values (-9 to -15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO4/Cl, NO3/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na-Ca-Cl basinal brines or shield brines, (3) SO4-NO3-Cl-(H)CO3 playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.

A rapid method for the sequential separation of polonium, plutonium, americium and uranium in drinking water.

PubMed

Lemons, B; Khaing, H; Ward, A; Thakur, P

2018-06-01

A new sequential separation method for the determination of polonium and actinides (Pu, Am and U) in drinking water samples has been developed that can be used for emergency response or routine water analyses. For the first time, the application of TEVA chromatography column in the sequential separation of polonium and plutonium has been studied. This method utilizes a rapid Fe +3 co-precipitation step to remove matrix interferences, followed by plutonium oxidation state adjustment to Pu 4+ and an incubation period of ~ 1 h at 50-60 °C to allow Po 2+ to oxidize to Po 4+ . The polonium and plutonium were then separated on a TEVA column, while separation of americium from uranium was performed on a TRU column. After separation, polonium was micro-precipitated with copper sulfide (CuS), while actinides were micro co-precipitated using neodymium fluoride (NdF 3 ) for counting by the alpha spectrometry. The method is simple, robust and can be performed quickly with excellent removal of interferences, high chemical recovery and very good alpha peak resolution. The efficiency and reliability of the procedures were tested by using spiked samples. The effect of several transition metals (Cu 2+ , Pb 2+ , Fe 3+ , Fe 2+ , and Ni 2+ ) on the performance of this method were also assessed to evaluate the potential matrix effects. Studies indicate that presence of up to 25 mg of these cations in the samples had no adverse effect on the recovery or the resolution of polonium alpha peaks. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

Coupled Mo-U abundances and isotopes in a small marine euxinic basin: Constraints on processes in euxinic basins

NASA Astrophysics Data System (ADS)

Bura-Nakić, Elvira; Andersen, Morten B.; Archer, Corey; de Souza, Gregory F.; Marguš, Marija; Vance, Derek

2018-02-01

Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (∼0.3‰ on 98Mo/95Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238U/235U fractionation of +0.6‰, in line with other studied euxinic basins. Combining the Mo and U systematics in Lake Rogoznica and other euxinic basins, it is apparent that the two different uptake mechanisms of U and Mo can lead to spatially and temporally variable Mo/U and Mo-U isotope systematics that depend on the rate of water renewal versus removal to sediment, the sulfide concentration, and the geometry of the basin. This study further emphasises the potential of combining multiple observations, from Mo-U enrichment and isotope systematics, for disentangling the various processes via which redox conditions control the chemistry of modern and ancient sediments.

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

PubMed Central

Hasler-Sheetal, Harald; Holmer, Marianne

2015-01-01

Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

PubMed

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Catalyzed Preparation of Amorphous Chalcogenides

DTIC Science & Technology

1998-01-30

hydrogen sulfide through lanthanum isopropoxide in dry benzene, as the solvent. The powder obtained was heat-treated in hydrogen sulfide finally 15...producing single-phase crystalline lanthanum sulfide (La2S3) . Amorphous particles were also prepared by reacting titanium tetrapropoxide [Ti...OC3H7)4] and hydrogen sulfide. Resulting powder was heat-treated in flowing hydrogen sulfide to produce crystalline titanium sulfide (TiS2) . 20

As, Bi, Hg, S, Sb, Sn and Te geochemistry of the J-M Reef, Stillwater Complex, Montana: constraints on the origin of PGE-enriched sulfides in layered intrusions

USGS Publications Warehouse

Zientek, M.L.; Fries, T.L.; Vian, R.W.

1990-01-01

The J-M Reef is an interval of disseminated sulfides in the Lower Banded series of the Stillwater Complex that is enriched in the platinum group elements (PGE). Palladium and Pt occur in solid solution in base-metal sulfides and as discrete PGE minerals. PGE minerals include sulfides, tellurides, arsenides, antimonides, bismuthides, and alloys with Fe, Sn, Hg, and Au. Several subpopulations can be delineated based on whole-rock chemical analyses for As, Bi, Cu, Hg, Pd, Pt, S, Sb and Te for samples collected from and adjacent to the J-M Reef. In general, samples from within the reef have higher Pt/Cu, Pd/Cu, Pd/Pt, Te/Bi and S/(Te+Bi) than those collected adjacent to the reef. Vertical compositional profiles through the reef suggest that Pd/Cu and Pt/Cu decrease systematically upsection from mineralized to barren rock. The majority of samples with elevated As, Sb and Hg occur adjacent to the reef, not within it, or in sulfide-poor rocks. Neither magma mixing nor fluid migration models readily explain why the minor quantities of sulfide minerals immediately adjacent to the sulfide-enriched layers that form the J-M Reef have different element ratios than the sulfide minerals that form the reef. If all the sulfides formed by exsolution during a magma mixing event and the modal proportion of sulfide now in the rocks are simply the result of mechanical processes that concentrated the sulfides into some layers and not others, then the composition of the sulfide would not be expected to be different. Models that rely upon ascending liquids or fluids are incompatible with the presence of sulfides that are not enriched in PGE immediately below or interlayered with the PGE-enriched sulfides layers. PGE-enriched postcumulus fluids should have reacted to the same extent with sulfides immediately outside the reef as within the reef. One explanation is that some of the sulfide minerals in the rocks outside the reef have a different origin than those that make up the reef. The sulfide minerals that form the reef may represent a cumulus sulfide phase that formed as the result of a magma-mixing event, achieved its high PGE contents at that time, and accumulated to form a layer. The rocks outside the reef may contain a large proportion of postcumulus sulfide minerals that formed as the last dregs of intercumulus liquids trapped in the interstitial spaces between the cumulus grains reached sulfur saturation and exsolved a sulfide liquid or precipitated a sulfide mineral. The PGE contents of these sulfides would be expected to be less than the cumulus sulfides that form the reef since they would have equilibrated with a much smaller volume of silicate liquid. Another explanation is that some of the sulfide droplets that formed as a result of the mixing event were trapped as inclusions in silicate minerals soon after they formed. This would reduce the amount of magma these sulfide droplets could equilibrate with and effectively reduce their PGE tenor. ?? 1990.

Permissive tracts for volcanogenic massive sulfide deposits in Mauritania (phase V, deliverable 76): Chapter L1 in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Horton, John D.

2012-01-01

This report contains the USGS results of the PRISM-II Mauritania Minerals Project and is presented in cooperation with the Ministry of Petroleum, Energy, and Mines of the Islamic Republic of Mauritania. The Report is composed of separate chapters consisting of multidisciplinary interpretive reports with accompanying plates on the geology, structure, geochronology, geophysics, hydrogeology, geochemistry, remote sensing (Landsat TM and ASTER), and SRTM and ASTER digital elevation models of Mauritania. The syntheses of these multidisciplinary data formed the basis for additional chapters containing interpretive reports on 12 different commodities and deposit types known to occur in Mauritania, accompanied by countrywide mineral resource potential maps of each commodity/deposit type. The commodities and deposit types represented include: (1) Ni, Cu, PGE, and Cr deposits hosted in ultramafic rocks; (2) orogenic, Carlin-like, and epithermal gold deposits; (3) polymetallic Pb-Zn-Cu vein deposits; (4) sediment-hosted Pb-Zn-Ag deposits of the SEDEX and Mississippi Valley-type; (5) sediment-hosted copper deposits; ( 6) volcanogenic massive sulfide deposits; (7) iron oxide copper-gold deposits; (8) uranium deposits; (9) Algoma-, Superior-, and oolitic-type iron deposits; (10) shoreline Ti-Zr placer deposits; (11) incompatible element deposits hosted in pegmatites, alkaline rocks, and carbonatites, and; (12) industrial mineral deposits. Additional chapters include the Mauritanian National Mineral Deposits Database are accompanied by an explanatory text and the Mauritania Minerals Project GIS that contains all of the interpretive layers created by USGS scientists. Raw data not in the public domain may be obtained from the Ministry of Petroleum, Energy, and Mines in Nouakchott, Mauritania.

investigating the use of geophysical techniques to detect hydrocarbon seeps

NASA Astrophysics Data System (ADS)

Somwe, Vincent Tambwe

In the Cement oil field, seeps occur in the Hydrocarbon Induced Diagenetic Aureole (HIDA).This 14 square km diagenetic alteration region is mainly characterized by the: (1) secondary carbonate minerals deposition that tends to form ridges throughout the oil field; (2) disseminated pyrite in the vicinity of the fault zones; (3) uranium occurrence and the change in color pattern from red to bleached red sandstone. Generally the HIDA of the Cement oil field is subdivided into four zones: (1) carbonate cemented sandstone zone (zone 1), (2) altered sandstone zone (zone 2), (3) sulfide zone (zone 3) and (4) unaltered sandstone zone (zone 4). This study investigated the use of geophysical techniques to detect alteration zones over the Cement oil field. Magnetic and electromagnetic data were acquired at 5 m interval using the geometric G858 magnetometer and the Geonics EM-31 respectively. Both total magnetic intensity and bulk conductivity were found to decrease across boundaries between unaltered and altered sandstones. Boundaries between sulfide and carbonate zones, which in most cases were located in fault zones, were found to be characterized by higher magnetic and bulk conductivity readings. The contrast between the background and the highest positive peak was found to be in the range of 0.5-10% for total magnetic intensity and 258-450% for bulk conductivity respectively; suggesting that the detection of hydrocarbon seeps would be more effective with EM techniques. The study suggests that geophysical techniques can be used to delineate contact between the different alteration zones especially where metallic minerals such as pyrite are precipitated. The occurrence of carbonate cemented sandstone in the Cement oil field can be used as a pathfinder for hydrocarbon reservoir. The change in color in the altered sandstone zone can still be useful in the hydrocarbon exploration.

Mineral Deposit Data for Epigenetic Base- and Precious-metal and Uranium-thorium Deposits in South-central and Southwestern Montana and Southern and Central Idaho

USGS Publications Warehouse

Klein, T.L.

2004-01-01

Metal deposits spatially associated with the Cretaceous Boulder and Idaho batholiths of southwestern Montana and southern and central Idaho have been exploited since the early 1860s. Au was first discovered in placer deposits; exploitation of vein deposits in bedrock soon followed. In 1865, high-grade Ag vein deposits were discovered and remained economically important until the 1890s. Early high-grade deposits of Au, Ag and Pb were found in the weathered portions of the veins systems. As mining progressed to deeper levels, Ag and Pb grades diminished. Exploration for and development of these vein deposits in this area have continued until the present. A majority of these base- and precious-metal vein deposits are classified as polymetallic veins (PMV) and polymetallic carbonate-replacement (PMR) deposits in this compilation. Porphyry Cu and Mo, epithermal (Au, Ag, Hg and Sb), base- and precious-metal and W skarn, W vein, and U and Th vein deposits are also common in this area. The world-class Butte Cu porphyry and the Butte high-sulfidation Cu vein deposits are in this study area. PMV and PMR deposits are the most numerous in the region and constitute about 85% of the deposit records compiled. Several types of syngenetic/diagenetic sulfide mineral deposits in rocks of the Belt Supergroup or their equivalents are common in the region and they have been the source of a substantial metal production over the last century. These syngenetic deposits and their metamorphosed/structurally remobilized equivalents were not included in this database; therefore, deposits in the Idaho portion of the Coeur d'Alene district and the Idaho Cobalt belt, for example, have not been included because many of them are believed to be of this type.

Volcanic sulfur degassing and the role of sulfides in controlling volcanic metal emissions

NASA Astrophysics Data System (ADS)

Edmonds, M.; Liu, E.

2017-12-01

Volcanoes emit prodigious quantities of sulfur and metals, their behaviour inextricably linked through pre-eruptive sulfide systematics and through degassing and speciation in the volcanic plume. Fundamental differences exist in the metal output of ocean island versus arc volcanoes, with volcanoes in Hawaii and Iceland outgassing large fluxes of gaseous and particulate chalcophiles; and arc volcanoes' plumes, in contrast, enriched in Zn, Cu, Tl and Pb. Metals and metalloids partition into a magmatic vapor phase from silicate melt at crustal pressures. Their abundance in magmatic vapor is influenced strongly by sulfide saturation and by the composition of the magmatic vapor phase, particularly with respect to chloride. These factors are highly dependent on tectonic setting. Metal outgassing is controlled by magma water content and redox: deep saturation in vapor and minimal sulfide in arc basalts yields metal-rich vapor; shallow degassing and resorption of sulfides feeds the metal content of volcanic gas in ocean islands. We present a detailed study of the sulfide systematics of the products of the 2014-2015 Holuhraun basaltic fissure eruption (Bárðarbunga volcanic system, Iceland) to illustrate the interplay between late water and sulfur outgassing; sulfide saturation and breakdown; and metal partitioning into a vapor phase. Sulfide globules, representing quenched droplets of an immiscible sulfide liquid, are preserved within erupted tephra. Sulfide globules in rapidly quenched tephra are preserved within both matrix glass and as inclusions in crystals. The stereologically-corrected 3D size distribution of sulfide globules ranges from <1 µm to 43 µm, with a modal diameter of 14-17 µm (by number). Sulfides are not uniformly distributed, and are commonly observed in association with either sub-millimetre-scale plagioclase-clinopyroxene-olivine glomerocrysts or with bubbles. Maximum dissolved sulfur concentrations of 1750 ppm in melt inclusions and matrix glass next to sulfides are consistent with empirical determinations of the sulfur content at sulfide saturation for MORB. The Holuhraun magma was sulfide-saturated on eruption and co-existed with an immiscible sulfide liquid throughout much of ol-cpx-plag crystallisation. Individual globules are associated with locally elevated dissolved sulfur concentrations, with concentration gradients away from sulfides preserved over distances of 10-40 µm from the melt-sulfide interfaces. We discuss the mechanisms of sulfide breakdown and its importance in supplying sulfur and metals to the atmosphere during eruption.

Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator.

PubMed

Wu, Dandan; Ma, Wenhui; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-05-18

In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The results of ICP analysis indicate that the dissolution of enhanced sulfurized malachite surface is significantly decreased. Zeta potential measurements indicate that a smaller isoelectric point value and a large number of copper-sulfide films formed on the malachite surface by enhancing sulfidation resulted in a large amount of sodium butyl xanthate absorbed onto the enhanced sulfurized malachite surface. EDS semi-quantitative analysis and XPS analysis show that malachite was easily sulfurized by sodium sulfide with ammonium ion. These results show that the addition of ammonium ion plays a significant role in the sulfidation of malachite and results in improved flotation performance.

Hydrogen sulfide production from cysteine and homocysteine by periodontal and oral bacteria.

PubMed

Yoshida, Akihiro; Yoshimura, Mamiko; Ohara, Naoya; Yoshimura, Shigeru; Nagashima, Shiori; Takehara, Tadamichi; Nakayama, Koji

2009-11-01

Hydrogen sulfide is one of the predominant volatile sulfur compounds (VSCs) produced by oral bacteria. This study developed and evaluated a system for detecting hydrogen sulfide production by oral bacteria. L-methionine-alpha-deamino-gamma-mercaptomethane-lyase (METase) and beta carbon-sulfur (beta C-S) lyase were used to degrade homocysteine and cysteine, respectively, to produce hydrogen sulfide. Enzymatic reactions resulting in hydrogen sulfide production were assayed by reaction with bismuth trichloride, which forms a black precipitate when mixed with hydrogen sulfide. The enzymatic activities of various oral bacteria that result in hydrogen sulfide production and the capacity of bacteria from periodontal sites to form hydrogen sulfide in reaction mixtures containing L-cysteine or DL-homocysteine were assayed. With L-cysteine as the substrate, Streptococcus anginosus FW73 produced the most hydrogen sulfide, whereas Porphyromonas gingivalis American Type Culture Collection (ATCC) 33277 and W83 and Fusobacterium nucleatum ATCC 10953 produced approximately 35% of the amount produced by the P. gingivalis strains. Finally, the hydrogen sulfide found in subgingival plaque was analyzed. Using bismuth trichloride, the hydrogen sulfide produced by oral bacteria was visually detectable as a black precipitate. Hydrogen sulfide production by oral bacteria was easily analyzed using bismuth trichloride. However, further innovation is required for practical use.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Experimental simulations of sulfide formation in the solar nebula.

PubMed

Lauretta, D S; Lodders, K; Fegley, B

1997-07-18

Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.

2004-01-01

Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

NASA Astrophysics Data System (ADS)

Holmer, Marianne; Pedersen, Ole; Krause-Jensen, Dorte; Olesen, Birgit; Hedegård Petersen, Malene; Schopmeyer, Stephanie; Koch, Marguerite; Lomstein, Bente Aa.; Jensen, Henning S.

2009-11-01

Sulfur and oxygen dynamics in the seagrasses Thalassia testudinum and Syringodium filiforme and their sediments were studied in the US Virgin Islands (USVI) in order to explore sulfide intrusion into tropical seagrasses. Four study sites were selected based on the iron concentration in sediments and on proximity to anthropogenic nutrient sources. Meadow characteristics (shoot density, above- and below-ground biomass, nutrient content) were sampled along with sediment biogeochemistry. Sulfide intrusion was high in T. testudinum, as up to 96% of total sulfur in the plant was derived from sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated with sulfide intrusion suggesting that active growth reduced sulfide intrusion. Sulfide intrusion was lower in S. filiforme (up to 44%) compared to T. testudinum consistent with a higher internal nighttime oxygen concentrations found for S. filiforme. When S. filiforme can take advantage of its ability to maintain high internal oxygen concentrations, as was the case on the USVI, it could increase its success in colonizing unvegetated disturbed sediments with potentially high sulfide concentrations.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

PubMed Central

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-01-01

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions. PMID:26512669

Nanostructured metal sulfides for energy storage

NASA Astrophysics Data System (ADS)

Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

2014-08-01

Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

Simultaneous sulfide removal, nitrification, and electricity generation in a microbial fuel cell equipped with an oxic cathode.

PubMed

Bao, Renbing; Zhang, Shaohui; Zhao, Li; Zhong, Liuxiang

2017-02-01

With sulfide as an anodic electron donor and ammonium as a cathodic substrate, the feasibility of simultaneous sulfide removal, nitrification, and electricity generation was investigated in a microbial fuel cell (MFC) equipped with an oxic cathode. Successful simultaneous sulfide removal, nitrification, and electricity generation in this MFC were achieved in 35 days, with the sulfide and ammonium removal percent of 92.7 ± 1.4 and 96.4 ± 0.3%, respectively. The maximum power density increased, but the internal resistance decreased with the increase of feeding sulfide concentration from 62.9 ± 0.3 to 238.5 ± 0.2 mg S/L. Stable ammonium removal with complete nitrification, preparing for future denitrification, was obtained throughout the current study. Sulfide removal loading significantly increased with the increase of feeding sulfide concentration at each external resistance, but no significant correlation between sulfide removal loading and external resistance was found at each feeding sulfide concentration. The charge recovery and anodic coulombic efficiency (CE) significantly decreased with the increase of external resistance. High feeding sulfide concentration led to low anodic CE. Granular sulfur deposition was found on the anode graphite fiber. The appropriate feeding sulfide concentration for sulfide removal and sulfur deposition was deemed to be 178.0 ± 1.7 mg S/L, achieving a sulfur deposition percent of 69.7 ± 0.6%.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu-Ni-PGE sulfides which require very high R factors, and settling of sulfide liquids.

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

Dam, William; Gil, Dr. April; Johnson, Raymond H.

The US Department of Energy Office of Legacy Management (LM) is responsible for maintaining protective public health and environmental conditions at former uranium mill tailings sites nationwide via long-term stewardship. One of these sites, a former uranium mill near Riverton, Wyoming, is within the boundary of the Wind River Indian Reservation and operated from 1958 to 1963. Tailings and contaminated material associated with mill operations were removed and transported to an offsite disposal cell in 1989. The remedial action was completed under Title I of the Uranium Mill Tailings Radiation Control Act of 1978. Milling operations, which included an unlinedmore » tailings impoundment and an unlined evaporation pond, contaminated the shallow groundwater, resulting in a downgradient groundwater plume that discharges to the Little Wind River. A natural flushing compliance strategy was implemented in 1998. This strategy allows contaminants of concern to naturally flush from the groundwater, provided that contaminants flush below US Environmental Protection Agency maximum concentration limits within 100 years. As part of the compliance strategy, LM has implemented a groundwater monitoring program along with institutional controls that include the installation of an alternate water supply, continued sampling of private wells, and restrictions on well drilling and gravel pit construction. LM works closely with local stakeholders and community members to ensure that these institutional controls are in place and maintained. The Riverton site provides an interesting case study where contaminant remobilization due to river flooding prompted a reevaluation of the conceptual site model to verify if the current compliance strategy would remain protective of human health and the environment. Concentrations of groundwater contaminants, which include sulfate, molybdenum, and uranium, were transiently elevated following flooding of the Little Wind River in 2010 and 2016. These flood events provided the impetus to investigate other aspects of the hydrologic system, including the unsaturated zone, naturally reduced (sulfidic) zones, and evaporite deposits. New site conceptual models, field and laboratory studies, and numerical models are being developed to explain how biogeochemical sediment–water interactions contribute to plume persistence and flood-related increases in groundwater concentrations. Updated human health and ecological risk assessments are progressing to evaluate the risk to human health and the environment based on current site conditions. Groundwater concentrations may remain above US Environmental Protection Agency maximum concentration limits beyond the 100-year natural flushing regulatory time frame. LM in its capacity as a long-term steward continues to monitor the site to ensure protectiveness is maintained and to determine the feasibility of alternative compliance and remediation strategies.« less

Sulfide and whole rock Re-Os systematics of eclogite and pyroxenite xenoliths from the Slave Craton, Canada

NASA Astrophysics Data System (ADS)

Aulbach, Sonja; Creaser, Robert A.; Pearson, Norm J.; Simonetti, Stefanie S.; Heaman, Larry M.; Griffin, William L.; Stachel, Thomas

2009-06-01

We characterized single sulfides in eclogite and pyroxenite xenoliths from the Diavik kimberlites (central Slave Craton, Canada) with regard to their petrography, major-element composition and Re-Os isotope systematics. Together with trace-element and Re-Os isotope compositions of whole rocks, these data allow identification of the major Re-Os host phases and provide constraints on the origin(s) of sulfides in these samples. The majority of sulfide minerals contain 8 to 28 at.% Ni, with intragranular sulfides having on average significantly lower contents (~ 6 at.%) than intergranular sulfides (~ 12 at.%). These high Ni-sulfides are not in equilibrium with an eclogitic assemblage and were likely introduced from a peridotitic source subsequent to eclogite formation. In contrast, their Re-Os abundances and Re/Os ratios (average ~ 825 ppb, 190 ppb and 10, respectively) overlap those of primary eclogitic sulfides. These conflicting compositional characteristics may document open-system disequilibrium processes accompanying the introduction of sulfides into eclogites. The general association of high 187Os/ 188Os with high 187Re/ 188Os of sulfides in three low-temperature eclogite xenoliths suggests that the addition is not young. In contrast, sulfides in a high-temperature eclogite plot on a ~ 90 Ma errorchron with radiogenic initial 187Os/ 188Os, perhaps indicative of young introduction of sulfides from a deep enriched source. Sulfides in a single pyroxenite xenolith have Ni, Re and Os contents intermediate between pristine eclogitic and peridotitic sulfides, and correlated Re-Os isotope systematics defining an age of 1.84 ± 0.14 Ga with a radiogenic 187Os/ 188Os i (0.16 ± 0.01). The age and 187Os/ 188Os i are identical to those obtained for eclogitic sulfide inclusions in diamonds from Diavik, thus supporting a link between eclogite and pyroxenite formation. Several eclogite and pyroxenite whole rocks show evidence for addition of secondary sulfides, but many plot on Paleoproterozoic Re-Os age arrays - particularly so at low Re/Os - coincident with previously determined ages using Lu-Hf and Pb-Pb techniques. They may represent sulfide-poor varieties that did not suffer secondary sulfide addition and that may be best suited to yielding meaningful Re-Os ages.

Temperature and cell-type dependency of sulfide effects on mitochondrial respiration.

PubMed

Groeger, Michael; Matallo, Jose; McCook, Oscar; Wagner, Florian; Wachter, Ulrich; Bastian, Olga; Gierer, Saskia; Reich, Vera; Stahl, Bettina; Huber-Lang, Markus; Szabó, Csaba; Georgieff, Michael; Radermacher, Peter; Calzia, Enrico; Wagner, Katja

2012-10-01

Previous studies suggest that sulfide-induced inhibition of cytochrome c oxidase (cCox) and, consequently, the metabolic and toxic effects of sulfide are less pronounced at low body temperature. Because the temperature-dependent effects of sulfide on the inflammatory response are still a matter of debate, we investigated the impact of varying temperature on the cCox excess capacity and the mitochondrial sulfide oxidation by the sulfide-ubiquinone oxidoreductase in macrophage-derived cell lines (AMJ2-C11 and RAW 264.7). Using an oxygraph chamber, the inhibition of mitochondrial respiration was measured by stepwise titrations with sulfide and the nonmetabolizable cCox inhibitor sodium azide at 25°C and 37°C. Using the latter of the two inhibitors, the excess capacity of the cCox was obtained. Furthermore, we quantified the capacity of these cells to withstand sulfide inhibition by measuring the amount required to inhibit respiration by 50% and 90% and the viability of the cells after 24-h exposure to 100 ppm of hydrogen sulfide. At low titration rates, the AMJ2-C11 cells, but not the RAW 264.7 cells, increased their capacity to withstand exogenously added sulfide. This effect was even greater at 25°C than at 37°C. Furthermore, only the AMJ2-C11 cells remained viable after sulfide exposure for 24 h. In contrast, only in the RAW 264.7 cells that an increase in cCox excess capacity was found at low temperatures. In macrophage-derived cell lines, both the excess capacity of cCox and the efficiency of sulfide elimination may increase at low temperatures. These properties may modify the effects of sulfide in immune cells and, potentially, the inflammatory response during sulfide exposure at different body temperatures.

The Evolution of Sulfide Tolerance in the Cyanobacteria

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

PubMed Central

Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

2015-01-01

Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

Sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1985-11-26

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Electrochemical hydrogen sulfide biosensors.

PubMed

Xu, Tailin; Scafa, Nikki; Xu, Li-Ping; Zhou, Shufeng; Abdullah Al-Ghanem, Khalid; Mahboob, Shahid; Fugetsu, Bunshi; Zhang, Xueji

2016-02-21

The measurement of sulfide, especially hydrogen sulfide, has held the attention of the analytical community due to its unique physiological and pathophysiological roles in biological systems. Electrochemical detection offers a rapid, highly sensitive, affordable, simple, and real-time technique to measure hydrogen sulfide concentration, which has been a well-documented and reliable method. This review details up-to-date research on the electrochemical detection of hydrogen sulfide (ion selective electrodes, polarographic hydrogen sulfide sensors, etc.) in biological samples for potential therapeutic use.

Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

USGS Publications Warehouse

Visscher, P.T.; Taylor, B.F.

1993-01-01

A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

Adaptation of cyanobacteria to the sulfide-rich microenvironment of black band disease of coral.

PubMed

Myers, Jamie L; Richardson, Laurie L

2009-02-01

Black band disease (BBD) is a cyanobacteria-dominated microbial mat that migrates across living coral colonies lysing coral tissue and leaving behind exposed coral skeleton. The mat is sulfide-rich due to the presence of sulfate-reducing bacteria, integral members of the BBD microbial community, and the sulfide they produce is lethal to corals. The effect of sulfide, normally toxic to cyanobacteria, on the photosynthetic capabilities of five BBD cyanobacterial isolates of the genera Geitlerinema (3), Leptolyngbya (1), and Oscillatoria (1) and six non-BBD cyanobacteria of the genera Leptolyngbya (3), Pseudanabaena (2), and Phormidium (1) was examined. Photosynthetic experiments were performed by measuring the photoincorporation of [(14)C] NaHCO(3) under the following conditions: (1) aerobic (no sulfide), (2) anaerobic with 0.5 mM sulfide, and (3) anaerobic with 0.5 mM sulfide and 10 microM 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). All five BBD cyanobacterial isolates tolerated sulfide by conducting sulfide-resistant oxygenic photosynthesis. Five of the non-BBD cyanobacterial isolates did not tolerate sulfide, although one Pseudanabaena isolate continued to photosynthesize in the presence of sulfide at a considerably reduced rate. None of the isolates conducted anoxygenic photosynthesis with sulfide as an electron donor. This is the first report on the physiology of a culture of Oscillatoria sp. found globally in BBD.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

NASA Astrophysics Data System (ADS)

Wu, Dandan; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-07-01

The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

Anti-inflammatory and cytoprotective properties of hydrogen sulfide.

PubMed

Gemici, Burcu; Wallace, John L

2015-01-01

Hydrogen sulfide is an endogenous gaseous mediator that plays important roles in many physiological processes in microbes, plants, and animals. This chapter focuses on the important roles of hydrogen sulfide in protecting tissues against injury, promoting the repair of damage, and downregulating the inflammatory responses. The chapter focuses largely, but not exclusively, on these roles of hydrogen sulfide in the gastrointestinal tract. Hydrogen sulfide is produced throughout the gastrointestinal tract, and it contributes to maintenance of mucosal integrity. Suppression of hydrogen sulfide synthesis renders the tissue more susceptible to injury and it impairs repair. In contrast, administration of hydrogen sulfide donors can increase resistance to injury and accelerate repair. Hydrogen sulfide synthesis is rapidly and dramatically enhanced in the gastrointestinal tract after injury is induced. These increases occur specifically at the site of tissue injury. Hydrogen sulfide also plays an important role in promoting resolution of inflammation, and restoration of normal tissue function. In recent years, these beneficial actions of hydrogen sulfide have provided the basis for development of novel hydrogen sulfide-releasing drugs. Nonsteroidal anti-inflammatory drugs that release small amounts of hydrogen sulfide are among the most advanced of the hydrogen sulfide-based drugs. Unlike the parent drugs, these modified drugs do not cause injury in the gastrointestinal tract, and do not interfere with healing of preexisting damage. Because of the increased safety profile of these drugs, they can be used in circumstances in which the toxicity of the parent drug would normally limit their use, such as in chemoprevention of cancer. © 2015 Elsevier Inc. All rights reserved.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1987-01-06

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

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

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on storage onboard ship even though they were filtered (0.2 μm) and handled to exclude oxygen contamination. Chemical additives such as formaldehyde, glutaraldehyde, hydroxylamine and ascorbic acid prevented or retarded the sulfide loss. Thiosulfate and azide did not inhibit sulfide loss. These studies suggest an anaerobic chemical oxidation of sulfide rather than a biological oxidation on stored and filtered samples.

Methods for producing hydrogen (BI) sulfide and/or removing metals

DOEpatents

Truex, Michael J [Richland, WA; Peyton, Brent M [Pullman, WA; Toth, James J [Kennewick, WA

2002-05-14

The present invention is a process wherein sulfide production by bacteria is efficiently turned on and off, using pH adjustment. The adjustment of pH impacts sulfide production by bacteria by altering the relative amounts of H.sub.2 S and HS-- in solution and thereby control the inhibition of the bacterial metabolism that produces sulfide. This process can be used to make a bioreactor produce sulfide "on-demand" so that the production of sulfide can be matched to its use as a metal precipitation reagent. The present invention is of significance because it enables the use of a biological reactor, a cost effective sulfide production system, by making the biological reactor produce hydrogen sulfide "on demand", and therefore responsive to production schedules, waste stream generation rate, and health and safety requirements/goals.

A preliminary cost analysis of the biotreatment of refinery spent-sulfidic caustic.

PubMed

Sublette, K L

1997-01-01

Caustics are used in petroleum refining to remove hydrogen sulfide from various hydrocarbon streams. Spent-sulfidic caustics from three refineries have been successfully biotreated on the bench and pilot scale, resulting in neutralization and removal of active Sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans strain F. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic. A commercial-scale treatment system has been designed that features a bioreactor with a suspended culture of flocculated T. denitrificans, a settler and acid and nutrient storage and delivery systems. A cost analysis has been performed for nine cases representing a range of spent caustic sulfide and hydroxide concentrations at a base treatment rate of 10 gpm. This analysis shows that refinery spent-sulfidic caustic can be biotreated for 4-8.3 cent/gal.

Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

PubMed

Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

1998-01-01

Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components.

Arsenic leaching and speciation in C&D debris landfills and the relationship with gypsum drywall content.

PubMed

Zhang, Jianye; Kim, Hwidong; Dubey, Brajesh; Townsend, Timothy

2017-01-01

The effects of sulfide levels on arsenic leaching and speciation were investigated using leachate generated from laboratory-scale construction and demolition (C&D) debris landfills, which were simulated lysimeters containing various percentages of gypsum drywall. The drywall percentages in lysimeters were 0, 1, 6, and 12.4wt% (weight percent) respectively. With the exception of a control lysimeter that contained 12.4wt% of drywall, each lysimeter contained chromated copper arsenate (CCA) treated wood, which accounts for 10wt% of the C&D waste. During the period of study, lysimeters were mostly under anaerobic conditions. Leachate analysis results showed that sulfide levels increased as the percentage of drywall increased in landfills, but arsenic concentrations in leachate were not linearly correlated with sulfide levels. Instead, the arsenic concentrations decreased as sulfide increased up to approximately 1000μg/L, but had an increase with further increase in sulfide levels, forming a V-shape on the arsenic vs. sulfide plot. The analysis of arsenic speciation in leachate showed different species distribution as sulfide levels changed; the fraction of arsenite (As(III)) increased as the sulfide level increased, and thioarsenate anions (As(V)) were detected when the sulfide level further increased (>10 4 μg/L). The formation of insoluble arsenic sulfide minerals at a lower range of sulfide and soluble thioarsenic anionic species at a higher range of sulfide likely contributed to the decreasing and increasing trend of arsenic leaching. Copyright © 2016. Published by Elsevier Ltd.

Sulfide-responsive transcriptional repressor SqrR functions as a master regulator of sulfide-dependent photosynthesis.

PubMed

Shimizu, Takayuki; Shen, Jiangchuan; Fang, Mingxu; Zhang, Yixiang; Hori, Koichi; Trinidad, Jonathan C; Bauer, Carl E; Giedroc, David P; Masuda, Shinji

2017-02-28

Sulfide was used as an electron donor early in the evolution of photosynthesis, with many extant photosynthetic bacteria still capable of using sulfur compounds such as hydrogen sulfide (H 2 S) as a photosynthetic electron donor. Although enzymes involved in H 2 S oxidation have been characterized, mechanisms of regulation of sulfide-dependent photosynthesis have not been elucidated. In this study, we have identified a sulfide-responsive transcriptional repressor, SqrR, that functions as a master regulator of sulfide-dependent gene expression in the purple photosynthetic bacterium Rhodobacter capsulatus SqrR has three cysteine residues, two of which, C41 and C107, are conserved in SqrR homologs from other bacteria. Analysis with liquid chromatography coupled with an electrospray-interface tandem-mass spectrometer reveals that SqrR forms an intramolecular tetrasulfide bond between C41 and C107 when incubated with the sulfur donor glutathione persulfide. SqrR is oxidized in sulfide-stressed cells, and tetrasulfide-cross-linked SqrR binds more weakly to a target promoter relative to unmodified SqrR. C41S and C107S R. capsulatus SqrRs lack the ability to respond to sulfide, and constitutively repress target gene expression in cells. These results establish that SqrR is a sensor of H 2 S-derived reactive sulfur species that maintain sulfide homeostasis in this photosynthetic bacterium and reveal the mechanism of sulfide-dependent transcriptional derepression of genes involved in sulfide metabolism.

Fractional crystallization-induced variations in sulfides from the Noril’sk-Talnakh mining district (polar Siberia, Russia)

USGS Publications Warehouse

Duran, C.J.; Barnes, S-J.; Pleše, P.; Prašek, M. Kudrna; Zientek, Michael L.; Pagé, P.

2017-01-01

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril’sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril’sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent DMSS/liq and DISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril’sk-Talnakh mining district.

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, Dean H.; Nelson, Art J.; Ahrenkiel, Richard K.

1996-01-01

A process for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness.

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, D.H.; Nelson, A.J.; Ahrenkiel, R.K.

1996-07-30

A process is described for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness. 12 figs.

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

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

Powell, M.A.; Somero, G.N.

1986-08-01

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide asmore » an inorganic energy source.« less

New cyclic sulfides, garlicnins I2, M, N, and O, from Allium sativum.

PubMed

Nohara, Toshihiro; Ono, Masateru; Nishioka, Naho; Masuda, Fuka; Fujiwara, Yukio; Ikeda, Tsuyoshi; Nakano, Daisuke; Kinjo, Junei

2018-01-01

One atypical thiolane-type sulfide, garlicnin I 2 (1), two 3,4-dimethylthiolane-type sulfides, garlicnins M (2) and N (3), and one thiabicyclic-type sulfide, garlicnin O (4), were isolated from the acetone extracts of Chinese garlic bulbs, Allium sativum and their structures were characterized. Hypothetical pathways for the production of the respective sulfides were discussed.

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Platinum-group mineralization at the margin of the Skaergaard intrusion, East Greenland

NASA Astrophysics Data System (ADS)

Andersen, Jens C. Ø.; Rollinson, Gavyn K.; McDonald, Iain; Tegner, Christian; Lesher, Charles E.

2017-08-01

Two occurrences of platinum-group elements (PGEs) along the northern margin of the Skaergaard intrusion include a sulfide-bearing gabbro with slightly less than 1 ppm PGE + Au and a clinopyroxene-actinolite-plagioclase-biotite-ilmenite schist with 16 vol% sulfide and 1.8 ppm PGE + Au. Both have assemblages of pyrrhotite, pentlandite, and chalcopyrite typical for orthomagmatic sulfides. Matching platinum-group mineral assemblages with sperrylite (PtAs2), kotulskite (Pd(Bi,Te)1-2), froodite (PdBi2), michenerite (PdBiTe), and electrum (Au,Ag) suggest a common origin. Petrological and geochemical similarities suggest that the occurrences are related to the Skaergaard intrusion. The Marginal Border Series locally displays Ni depletion consistent with sulfide fractionation, and the PGE fractionation trends of the occurrences are systematically enriched by 10-50 times over the chilled margin. The PGE can be explained by sulfide-silicate immiscibility in the Skaergaard magma with R factors of 110-220. Nickel depletion in olivine suggests that the process occurred within the host cumulate, and the low R factors require little sulfide mobility. The sulfide assemblages are different to the chalcopyrite-bornite-digenite assemblage found in the Skaergaard Layered Series and Platinova Reef. These differences can be explained by the early formation of sulfide melt, while magmatic differentiation or sulfur loss caused the unusual sulfide assemblage within the Layered Series. The PGEs indicate that the sulfides formed from the Skaergaard magma. The sulfides and PGEs could not have formed from the nearby Watkins Fjord wehrlite intrusion, which is nearly barren in sulfide. We suggest that silicate-sulfide immiscibility led to PGE concentration where the Skaergaard magma became contaminated with material from the Archean basement.

The Rediscovery of a Long Described Species Reveals Additional Complexity in Speciation Patterns of Poeciliid Fishes in Sulfide Springs

PubMed Central

Palacios, Maura; Arias-Rodriguez, Lenin; Plath, Martin; Eifert, Constanze; Lerp, Hannes; Lamboj, Anton; Voelker, Gary; Tobler, Michael

2013-01-01

The process of ecological speciation drives the evolution of locally adapted and reproductively isolated populations in response to divergent natural selection. In Southern Mexico, several lineages of the freshwater fish species of the genus Poecilia have independently colonized toxic, hydrogen sulfide-rich springs. Even though ecological speciation processes are increasingly well understood in this system, aligning the taxonomy of these fish with evolutionary processes has lagged behind. While some sulfide spring populations are classified as ecotypes of Poecilia mexicana, others, like P. sulphuraria, have been described as highly endemic species. Our study particularly focused on elucidating the taxonomy of the long described sulfide spring endemic, Poecilia thermalis Steindachner 1863, and investigates if similar evolutionary patterns of phenotypic trait divergence and reproductive isolation are present as observed in other sulfidic species of Poecilia. We applied a geometric morphometric approach to assess body shape similarity to other sulfidic and non-sulfidic fish of the genus Poecilia. We also conducted phylogenetic and population genetic analyses to establish the phylogenetic relationships of P. thermalis and used a population genetic approach to determine levels of gene flow among Poecilia from sulfidic and non-sulfidic sites. Our results indicate that P. thermalis' body shape has evolved in convergence with other sulfide spring populations in the genus. Phylogenetic analyses placed P. thermalis as most closely related to one population of P. sulphuraria, and population genetic analyses demonstrated that P. thermalis is genetically isolated from both P. mexicana ecotypes and P. sulphuraria. Based on these findings, we make taxonomic recommendations for P. thermalis. Overall, our study verifies the role of hydrogen sulfide as a main factor shaping convergent, phenotypic evolution and the emergence of reproductive isolation between Poecilia populations residing in adjacent sulfidic and non-sulfidic environments. PMID:23976979

Experimental Investigation on the Topotaxy of Sulfide and Silicate Melts in Peridotite: Implications for the Origin of PGE-depleted Cu-Ni Sulfide Deposit

NASA Astrophysics Data System (ADS)

Wang, Z.; Zhang, J.; Jin, Z.

2016-12-01

Cu-Ni sulfide deposit is generally considered partial melt originated from the mantle which is usually PGE-enriched. However, the largest Cu-Ni sulfide deposits of China (the Jinchuan Cu-Ni deposit) is PGE-depleted. Comparing to silicate melt, the nature and topotaxy of sulfide melt have remained poorly understood. Here we report experimental investigation on the topotaxy of sulfide and silicate melts in peridotite using a piston-cylinder press and a 5GPa Griggs-type deformation apparatus. The starting material consists of polycrystalline olivine or pyrolite and 1 wt% Fe-Ni-Cu sulfide. Hydrostatic and deformation experiments were conducted at a pressure of 1.5 GPa and a temperature of 1250°. Under hydrostatic conditions, our results reveal that the apparent dihedral angle of sulfide melt in an olivine matrix( 96°) is much larger than that of silicate + sulfide melt in pyrolite(<60°) under hydrostatic conditions. The sulfide melt pockets appear mostly as blobs in triple junctions with an immiscible Ni-poor center surrounded by a Ni-rich layer. Under deformation conditions, olivine develops pronounced fabrics with the pole of the (010) forming high concentrations approximately normal to the foliation plane and the [100] axes forming a girdle in the foliation plane. EBSD phase mapping analyses reveal strong shape preferred orientations (SPO) of sulfide +silicate melt in the 45, 90, 135 degree directions for deformation experiments indicating complete wetting of grain boundaries and forming a favorable source for ore deposits. Deformation also causes mixing of the Ni-rich and the Ni-poor sulfide melts. As the platinum-group elements(PGE) prefer to concentrate in the Ni-rich sulfide melt at high temperatures, our results suggest that the metallogenetic source of the PGE-depleted Cu-Ni deposits may have formed under relatively intense deformation and low temperatures with a small fraction of mixed sulfide and silicate melts.

Permissive tracts for uranium deposits in Mauritania (phase V, deliverable 80): Chapter N1 in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Fernette, Gregory; Horton, John D.

2012-01-01

This report contains the USGS results of the PRISM-II Mauritania Minerals Project and is presented in cooperation with the Ministry of Petroleum, Energy, and Mines of the Islamic Republic of Mauritania. The Report is composed of separate chapters consisting of multidisciplinary interpretive reports with accompanying plates on the geology, structure, geochronology, geophysics, hydrogeology, geochemistry, remote sensing (Landsat TM and ASTER), and SRTM and ASTER digital elevation models of Mauritania. The syntheses of these multidisciplinary data formed the basis for additional chapters containing interpretive reports on 12 different commodities and deposit types known to occur in Mauritania, accompanied by countrywide mineral resource potential maps of each commodity/deposit type. The commodities and deposit types represented include: (1) Ni, Cu, PGE, and Cr deposits hosted in ultramafic rocks; (2) orogenic, Carlin-like, and epithermal gold deposits; (3) polymetallic Pb-Zn-Cu vein deposits; (4) sediment-hosted Pb-Zn-Ag deposits of the SEDEX and Mississippi Valley-type; (5) sediment-hosted copper deposits; ( 6) volcanogenic massive sulfide deposits; (7) iron oxide copper-gold deposits; (8) uranium deposits; (9) Algoma-, Superior-, and oolitic-type iron deposits; (10) shoreline Ti-Zr placer deposits; (11) incompatible element deposits hosted in pegmatites, alkaline rocks, and carbonatites, and; (12) industrial mineral deposits. Additional chapters include the Mauritanian National Mineral Deposits Database are accompanied by an explanatory text and the Mauritania Minerals Project GIS that contains all of the interpretive layers created by USGS scientists. Raw data not in the public domain may be obtained from the Ministry of Petroleum, Energy, and Mines in Nouakchott, Mauritania.

Enzymatic iron and uranium reduction by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Roden, E.E.; Phillips, E.J.P.; Woodward, J.C.

1993-01-01

The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei, and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans. This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the So-reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments. ?? 1993.

ATMOSPHERIC CHEMISTRY OF SELECTED SULFUR-CONTAINING COMPOUNDS OUTDOOR SMOG CHAMBER STUDY - PHASE 1

EPA Science Inventory

The chemical behavior of hydrogen sulfide, carbonyl sulfide, carbon sulfide, methanethiol, ethanethiol, methyl sulfide, ethylsulfide, methyl-disulfide, ethyldisulfide, methylethylsulfide, thiophene, 2-methylthiophene, 3-methylthiophene, 2,5-dimethyl-thiophene and propene (used as...

Measurement of H2S in vivo and in vitro by the monobromobimane method

PubMed Central

Shen, Xinggui; Kolluru, Gopi K.; Yuan, Shuai; Kevil, Christopher

2015-01-01

The gasotransmitter hydrogen sulfide (H2S) is known as an important regulator in several physiological and pathological responses. Among the challenges facing the field is the accurate and reliable measurement of hydrogen sulfide bioavailability. We have reported an approach to discretely measure sulfide and sulfide pools using the monobromobimane (MBB) method coupled with RP-HPLC. The method involves the derivatization of sulfide with excess MBB under precise reaction conditions at room temperature to form sulfide-dibimane. The resultant fluorescent sulfide-dibimane (SDB) is analyzed by RP-HPLC using fluorescence detection with the limit of detection for SDB (2 nM). Care must be taken to avoid conditions that may confound H2S measurement with this method. Overall, RP-HPLC with fluorescence detection of SDB is a useful and powerful tool to measure biological sulfide levels. PMID:25725514

Simulation of sulfide buildup in wastewater and atmosphere of sewer networks.

PubMed

Nielsen, A H; Yongsiri, C; Hvitved-Jacobsen, T; Vollertsen, J

2005-01-01

A model concept for prediction of sulfide buildup in sewer networks is presented. The model concept is an extension to--and a further development of--the WATS model (Wastewater Aerobic-anaerobic Transformations in Sewers), which has been developed by Hvitved-Jacobsen and co-workers at Aalborg University. In addition to the sulfur cycle, the WATS model simulates changes in dissolved oxygen and carbon fractions of different biodegradability. The sulfur cycle was introduced via six processes: 1. sulfide production taking place in the biofilm covering the permanently wetted sewer walls; 2. biological sulfide oxidation in the permanently wetted biofilm; 3. chemical and biological sulfide oxidation in the water phase; 4. sulfide precipitation with metals present in the wastewater; 5. emission of hydrogen sulfide to the sewer atmosphere and 6. adsorption and oxidation of hydrogen sulfide on the moist sewer walls where concrete corrosion may take place.

Biological treatment of toxic petroleum spent caustic in fluidized bed bioreactor using immobilized cells of Thiobacillus RAI01.

PubMed

Potumarthi, Ravichandra; Mugeraya, Gopal; Jetty, Annapurna

2008-12-01

In the present studies, newly isolated Thiobacillus sp was used for the treatment of synthetic spent sulfide caustic in a laboratory-scale fluidized bed bioreactor. The sulfide oxidation was tested using Ca-alginate immobilized Thiobacillus sp. Initially, response surface methodology was applied for the optimization of four parameters to check the sulfide oxidation efficiency in batch mode. Further, reactor was operated in continuous mode for 51 days at different sulfide loading rates and retention times to test the sulfide oxidation and sulfate and thiosulfate formation. Sulfide conversions in the range of 90-98% were obtained at almost all sulfide loading rates and hydraulic retention times. However, increased loading rates resulted in lower sulfide oxidation capacity. All the experiments were conducted at constant pH of around 6 and temperature of 30 +/- 5 degrees C.

Sulfidation of Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts studied by Moessbauer emission spectroscopy

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

Craje, M.W.J.; Kraan, A.M. van der; Beer, V.H.J. de

1993-10-01

The structure of hydrodesulfurization catalysts is relevant to many industries. The sulfidation of uncalcined and calcined alumina-supported cobalt and cobalt-molybdenum catalysts was systematically studied by means of in situ Moessbauer emission spectroscopy (MES) at room temperature. The spectra obtained during the stepwise sulfidation of the uncalcined catalysts clearly resemble those observed for carbon-supported ones. Hence, the interpretation of the spectra of the alumina-supported catalysts is based on the conclusions drawn from the MES studies of the carbon-supported catalysts, which are less complex because Co ions do not diffuse into the support. It is demonstrated that not only in sulfided CoMo/Al[submore » 2]O[sub 3], but also in sulfided Co/Al[sub 2]O[sub 3], catalysts Co-sulfide species with a [open quotes]Co-Mo-S[close quotes]-type quadrupole splitting can be formed. It is concluded that the Co-sulfide species formed in sulfided Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts are essentially the same, only the particle size and ordering of the Co-sulfide species may differ, as in the case of Co/C and CoMo/C catalysts. The function of the Mo, which is present as MoS[sub 2], is merely to stabilize very small Co-sulfide particles, which in the limit contain only one single Co atom. Furthermore, it turns out that the value of the electric quadrupole splitting (Q.S. value) of the Co-sulfide phase in the sulfided catalysts depends on the sulfiding temperature and Co content. This observation leads to the conclusion that large Q.S. values point to the presence of very small Co-sulfide entities or particles (the lower limit being [open quotes]particles[close quotes] containing only one Co atom, such as proposed in the [open quotes]Co-Mo-S[close quotes] model), whereas small Q.S. values point to the presence of large Co-sulfide particles (the upper limit being crystalline Co[sub 9]S[sub 8]). 28 refs., 7 figs., 6 tabs.« less

A synthesis of magmatic Ni-Cu-(PGE) sulfide deposits in the ∼260 Ma Emeishan large igneous province, SW China and northern Vietnam

NASA Astrophysics Data System (ADS)

Wang, Christina Yan; Wei, Bo; Zhou, Mei-Fu; Minh, Dinh Huu; Qi, Liang

2018-04-01

Magmatic Ni-Cu-(PGE) sulfide deposits in the ca. 260-Ma Emeishan large igneous province (LIP) are all hosted in relatively small, mafic-ultramafic intrusions with surface areas usually less than 1 km2. These deposits are mainly distributed in the Danba, Panzhihua-Xichang (Panxi), Huili, Yuanmou, Midu, Funing and Jinping regions in SW China and the Ta Khoa region in northern Vietnam. They include Ni-Cu-(PGE) sulfide-dominated, Ni-Cu sulfide-dominated, and PGE-dominated types. Sulfide ores of the Ni-Cu-(PGE) and Ni-Cu sulfide-dominated deposits contain more than 10 vol% sulfides and have low PGE concentrations relative to the ores that contain <3 vol% sulfides in the PGE-dominated deposits. The parental magmas of the host mafic-ultramafic intrusions may have been derived primarily from low-Ti picritic magmas that were produced by high degrees of partial melting of a depleted mantle source. The primary low-Ti picrites of the Emeishan LIP have relatively restricted εNd(t) and γOs(t) isotopic compositions, however, some of the host intrusions exhibit a large range of both εNd(t) (-9.5 to +0.8) and γOs(t) (+5.4 to +77), indicating that they experienced variable degrees of crustal contamination during emplacement. In addition, sulfides from sulfide ores of the Ban Phuc intrusion in northern Vietnam and those from sulfide veins in country rocks have δ34S values ranging from -6.7 to -3.4‰, whereas sulfides from sulfide ores of the Baimazhai No.3, Yingpanjie, Jinbaoshan and Nantianwan intrusions in SW China have highly variable δ34S ranging from -0.2 to +21.4‰, indicating the addition of crustal sulfur into the mantle-derived mafic magmas. Platinum-group minerals (PGM) are abundant in the Ni-Cu-(PGE) sulfide-bearing intrusions, and they span a wide range of composition. More than 130 PGM grains have been identified in the Pt-Pd-rich Jinbaoshan intrusion, whereas only one small froodite (PdBi2) grain was observed in the Ni-Cu sulfide-dominated Baimazhai No. 3 intrusion. Overall, the three types of Ni-Cu-(PGE) sulfide deposits in the Emeishan LIP can be taken as a spectrum of Ni-Cu-(PGE) sulfide mineralization, the formation of which involved similar magmatic processes in open systems of magma conduits. The magma conduits developed along the cross-linking structures created by numerous strike-slip faults and each intrusion appears to be part of a connecting trellis of conduits that formed complex pathways from the mantle to the surface. The Ni-Cu sulfide-dominated deposits are attributed to a single sulfide segregation event in staging magma chambers, whereas the PGE-dominated deposits were likely formed by a multistage-dissolution, upgrading process in the staging chambers. The Ni-Cu-(PGE) sulfide-dominated deposits may have experienced interaction between successive pulses of S-undersaturated mafic magma and early segregated sulfide melts in the staging chambers. This study is intended to provide a better understanding of the magmatic processes related to the formation of conduit-type Ni-Cu-(PGE) sulfide deposits associated with continental flood basalt magmatism.

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

PubMed Central

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

PubMed

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

A method for measuring sulfide toxicity in the nematode Caenorhabditis elegans.

PubMed

Livshits, Leonid; Gross, Einav

2017-01-01

Cysteine catabolism by gut microbiota produces high levels of sulfide. Excessive sulfide can interfere with colon function, and therefore may be involved in the etiology and risk of relapse of ulcerative colitis, an inflammatory bowel disease affecting millions of people worldwide. Therefore, it is crucial to understand how cells/animals regulate the detoxification of sulfide generated by bacterial cysteine catabolism in the gut. Here we describe a simple and cost-effective way to explore the mechanism of sulfide toxicity in the nematode Caenorhabditis elegans ( C. elegans ). •A rapid cost-effective method to quantify and study sulfide tolerance in C. elegans and other free-living nematodes.•A cost effective method to measure the concentration of sulfide in the inverted plate assay.

Reduction of produced elementary sulfur in denitrifying sulfide removal process.

PubMed

Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

2011-05-01

Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

Survival of hydrogen sulfide oxidizing bacteria on corroded concrete surfaces of sewer systems.

PubMed

Jensen, H S; Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

2008-01-01

The activity of hydrogen sulfide oxidizing bacteria within corroded concrete from a sewer manhole was investigated. The bacteria were exposed to hydrogen sulfide starvation for up till 18 months, upon which their hydrogen sulfide oxidizing activity was measured. It was tested whether the observed reduction in biological activity was caused by a biological lag phase or by decay of the bacteria. The results showed that the bacterial activity declined with approximately 40% pr. month during the first two months of hydrogen sulfide starvation. After 2-3 months of starvation, the activity stabilized. Even after 6 months of starvation, exposure to hydrogen sulfide for 6 hours a day on three successive days could restore the bacteriological activity to about 80% of the initial activity. After 12 months of starvation, the activity could, however, not be restored, and after 18 months the biological activity approached zero. The long-term survival aspect of concrete corroding bacteria has implications for predicting hydrogen sulfide corrosion in sewer systems subject to irregular hydrogen sulfide loadings, e.g. as they occur in temperate climates where hydrogen sulfide often is a summer-problem only.

Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

PubMed

Cardoso, Ricardo Beristain; Sierra-Alvarez, Reyes; Rowlette, Pieter; Flores, Elias Razo; Gómez, Jorge; Field, Jim A

2006-12-20

Chemolithoautotrophic denitrifying microorganisms oxidize reduced inorganic sulfur compounds coupled to the reduction of nitrate as an electron acceptor. These denitrifiers can be applied to the removal of nitrogen and/or sulfur contamination from wastewater, groundwater, and gaseous streams. This study investigated the physiology and kinetics of chemolithotrophic denitrification by an enrichment culture utilizing hydrogen sulfide, elemental sulfur, or thiosulfate as electron donor. Complete oxidation of sulfide to sulfate was observed when nitrate was supplemented at concentrations equal or exceeding the stoichiometric requirement. In contrast, sulfide was only partially oxidized to elemental sulfur when nitrate concentrations were limiting. Sulfide was found to inhibit chemolithotrophic sulfoxidation, decreasing rates by approximately 21-fold when the sulfide concentration increased from 2.5 to 10.0 mM, respectively. Addition of low levels of acetate (0.5 mM) enhanced denitrification and sulfate formation, suggesting that acetate was utilized as a carbon source by chemolithotrophic denitrifiers. The results of this study indicate the potential of chemolithotrophic denitrification for the removal of hydrogen sulfide. The sulfide/nitrate ratio can be used to control the fate of sulfide oxidation to either elemental sulfur or sulfate. Copyright 2006 Wiley Periodicals, Inc.

VASQUEZ PEAK WILDERNESS STUDY AREA, AND ST. LOUIS PEAK, AND WILLIAMS FORK ROADLESS AREAS, COLORADO.

USGS Publications Warehouse

Theobald, P.K.; Bielski, A.M.

1984-01-01

A mineral-resource survey was conducted during the years 1979-82 in the Vasquez Peak Wilderness Study Area and in the St. Louis Peak and Williams Fork Roadless Areas, central Front Range, Colorado. Probable resource potential for the occurrence of copper, lead, zinc, and silver in massive sulfide deposits has been identified in calcareous metamorphic rocks in the northern part of the St. Louis Peak Roadless Area and in the southern part of the Williams Fork Roadless Area. A probable resource potential for vein-type uranium deposits is identified along the Berthoud Pass fault zone in the eastern part of the Vasquez Peak Wilderness Study Area. A large area encompassing the eastern and southeastern part of each of the three areas has probable and substantiated potential for either high-grade lead-zinc-silver vein deposits, or larger, lower-grade clustered vein deposits. A probable resource potential for stockwork molybdenum deposits related to porphyry molybdenum type mineralization exists beneath the lead-zinc-silver-rich veins. The nature of the geologic terrane indicates little likelihood for the occurrence of organic fuels.

SULFIDE MINERALS IN SEDIMENTS

EPA Science Inventory

The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

Method for inhibiting oxidation of metal sulfide-containing material

DOEpatents

Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

2006-12-26

The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

PubMed

Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

2014-03-01

Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). Copyright © 2013 Elsevier Ltd. All rights reserved.

Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing.

PubMed

Ganigué, Ramon; Jiang, Guangming; Liu, Yiqi; Sharma, Keshab; Wang, Yue-Cong; Gonzalez, José; Nguyen, Tung; Yuan, Zhiguo

2018-05-15

Water utilities worldwide spend annually billions of dollars to control sulfide-induced corrosion in sewers. Iron salts chemically oxidize and/or precipitate dissolved sulfide in sewage and are especially used in medium- and large-size sewers. Iron salt dosing rates are defined ad hoc, ignoring variation in sewage flows and sulfide levels. This often results in iron overdosing or poor sulfide control. Online dosing control can adjust the chemical dosing rates to current (and future) state of the sewer system, allowing high-precision, stable and cost-effective sulfide control. In this paper, we report a novel and robust online control strategy for the dosing of ferrous salt in sewers. The control considers the fluctuation of sewage flow, pH, sulfide levels and also the perturbation from rainfall. Sulfide production in the pipe is predicted using auto-regressive models (AR) based on current flow measurements, which in turn can be used to determine the dose of ferrous salt required for cost-effective sulfide control. Following comprehensive model-based assesment, the control was successfully validated and its effectiveness demonstrated in a 3-week field trial. The online control algorithm controlled sulfide below the target level (0.5 mg S/L) while reducing chemical dosing up to 30%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Cupriavidus necator H16 Uses Flavocytochrome c Sulfide Dehydrogenase To Oxidize Self-Produced and Added Sulfide

PubMed Central

Lü, Chuanjuan; Xia, Yongzhen; Liu, Daixi; Zhao, Rui; Gao, Rui

2017-01-01

ABSTRACT Production of sulfide (H2S, HS−, and S2−) by heterotrophic bacteria during aerobic growth is a common phenomenon. Some bacteria with sulfide:quinone oxidoreductase (SQR) and persulfide dioxygenase (PDO) can oxidize self-produced sulfide to sulfite and thiosulfate, but other bacteria without these enzymes release sulfide into the medium, from which H2S can volatilize into the gas phase. Here, we report that Cupriavidus necator H16, with the fccA and fccB genes encoding flavocytochrome c sulfide dehydrogenases (FCSDs), also oxidized self-produced H2S. A mutant in which fccA and fccB were deleted accumulated and released H2S. When fccA and fccB were expressed in Pseudomonas aeruginosa strain Pa3K with deletions of its sqr and pdo genes, the recombinant rapidly oxidized sulfide to sulfane sulfur. When PDO was also cloned into the recombinant, the recombinant with both FCSD and PDO oxidized sulfide to sulfite and thiosulfate. Thus, the proposed pathway is similar to the pathway catalyzed by SQR and PDO, in which FCSD oxidizes sulfide to polysulfide, polysulfide spontaneously reacts with reduced glutathione (GSH) to produce glutathione persulfide (GSSH), and PDO oxidizes GSSH to sulfite, which chemically reacts with polysulfide to produce thiosulfate. About 20.6% of sequenced bacterial genomes contain SQR, and only 3.9% contain FCSD. This is not a surprise, since SQR is more efficient in conserving energy because it passes electrons from sulfide oxidation into the electron transport chain at the quinone level, while FCSD passes electrons to cytochrome c. The transport of electrons from the latter to O2 conserves less energy. FCSDs are grouped into three subgroups, well conserved at the taxonomic level. Thus, our data show the diversity in sulfide oxidation by heterotrophic bacteria. IMPORTANCE Heterotrophic bacteria with SQR and PDO can oxidize self-produced sulfide and do not release H2S into the gas phase. C. necator H16 has FCSD but not SQR, and it does not release H2S. We confirmed that the bacterium used FCSD for the oxidation of self-produced sulfide. The bacterium also oxidized added sulfide. The common presence of SQRs, FCSDs, and PDOs in heterotrophic bacteria suggests the significant role of heterotrophic bacteria in sulfide oxidation, participating in sulfur biogeochemical cycling. Further, FCSDs have been identified in anaerobic photosynthetic bacteria and chemolithotrophic bacteria, but their physiological roles are unknown. We showed that heterotrophic bacteria use FCSDs to oxidize self-produced sulfide and extraneous sulfide, and they may be used for H2S bioremediation. PMID:28864655

The removal of heavy metals from contaminated soil by a combination of sulfidisation and flotation.

PubMed

Vanthuyne, Mathias; Maes, André

2002-05-06

The possibility of removing cadmium, copper, lead and zinc from Belgian loamy soil by a combination of sulfidisation pre-treatment and Denver flotation was investigated. The potentially available--sulfide convertible--metal content of the metal polluted soil was estimated by EDTA (0.1 M, pH 4.65) extraction and BCR sequential extraction. EDTA extraction is better at approximating the metal percentage that is expected to be convertible into a metal sulfide phase, in contrast to the sequential extraction procedure of 'Int. J. Environ. Anal. Chem. 51 (1993) pp. 135-151' in which transition metals present as iron oxide co-precipitates are dissolved by hydroxylammoniumchloride in the second extraction step. To compare the surface characteristics of metal sulfides formed by sulfidisation with those of crystalline metal sulfides, two types of synthetic sediments were prepared and extracted with 0.1 M EDTA (pH 4.65) in anoxic conditions. Separate metal sulfides or co-precipitates with iron sulfide were formed by sulfide conditioning. The Denver flotation of both types of synthetic sediments (kerosene as collector at high background electrolyte concentrations) resulted in similar concentrating factors for freshly formed metal sulfides as for fine-grained crystalline metal sulfides. The selective flotation of metal sulfides after sulfide conditioning of a polluted soil, using kerosene or potassium ethyl xanthate as collectors and MIBC as frother, was studied at high background electrolyte concentrations. The sulfidisations were made in ambient air and inside an anoxic glove box. The concentrating factors corrected by the potentially available metal percentage, determined by 0.1 M EDTA extraction, lie between 2 and 3. The selective flotation of these finely dispersed, amorphous, metal sulfides can possibly be improved by optimising the bubble-particle interaction.

Rocks Whose Compositions are Determined by Flow Differentiation of Olivine- and Sulfide Droplet-Laden Magma: the Jinchuan Story

NASA Astrophysics Data System (ADS)

Li, C.; Ripley, E. M.; de Waal, S. A.; Xu, Z.

2002-12-01

The Jinchuan intrusion in western China is an elongated, deeply-dipping dyke-like body of dominantly olivine-rich ultramafic rocks of high magnesium basaltic magma. It hosts the second largest Ni-Cu sulfide deposit in the world. More than 500 million tones of sulfide ore grading 1.2 percent Ni and 0.7 percent Cu occur mostly as next-textured and disseminated sulfide (pyrrhotite, pentlendite and chalcopyrite) with cumulus olivine in about half of the rocks of the intrusion. Based on different petrological zonations, the Jinchuan intrusion is further divided into three segments: eastern, central and western segments. The central segment is characterized by concentric enrichments of cumulus olivine and sulfide, whereas the eastern and western segments are characterized by the increase of both cumulus olivine and sulfide toward the footwall. The forsterite contents of fresh olivine from different segments are similar and vary between 82 and 86 mole percent. The small range of olivine compositional variation corresponds to less than 6 percent of fractional crystallization. Mass balance calculations based on sulfide solubility in basaltic magma indicate that the volume of the parental magma of the sulfide is many times larger than that which is currently represented in the intrusion. Large amounts of cumulus olivine (more than 40 weight percent) in the marginal samples and high concentrations of sulfide in the intrusion are consistent with an interpretation that the Jinchuan intrusion was formed by olivine- and sulfide droplet-laden magma ascending through a subvertical conduit to a higher level. Differentiation processes of the olivine- and sulfide droplet-laden magma varied in different parts of the conduit. Sub-vertical flow differentiation controlled the central segment of the conduit, resulting in further enrichment of olivine crystals and sulfide droplets in the conduit center. In contrast, sub-lateral flow and gravitational differentiation dominated in the eastern and western segments, resulting in further enrichments of olivine crystals and sulfide droplets toward the footwall contact.

Microbial control of hydrogen sulfide production

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

Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.

1995-12-31

A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of coresmore » and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.« less

Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

PubMed Central

Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

2016-01-01

Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic relationship. PMID:26872267

Technique for Simultaneous Determination of [35S]Sulfide and [14C]Carbon Dioxide in Anaerobic Aqueous Samples †

PubMed Central

Taylor, Craig D.; Ljungdahl, Per O.; Molongoski, John J.

1981-01-01

A technique for the simultaneous determination of [35S]sulfide and [14C]carbon dioxide produced in anaerobic aqueous samples dual-labeled with [35S]sulfate and a 14C-organic substrate is described. The method involves the passive distillation of sulfide and carbon dioxide from an acidified water sample and their subsequent separation by selective chemical absorption. The recovery of sulfide was 93% for amounts ranging from 0.35 to 50 μmol; recovery of carbon dioxide was 99% in amounts up to 20 μmol. Within these delineated ranges of total sulfide and carbon dioxide, 1 nmol of [35S]sulfide and 7.5 nmol of [14C]carbon dioxide were separated and quantified. Correction factors were formulated for low levels of radioisotopic cross-contamination by sulfide, carbon dioxide, and volatile organic acids. The overall standard error of the method was ±4% for sulfide and ±6% for carbon dioxide. PMID:16345742

Enhanced performance of denitrifying sulfide removal process at high carbon to nitrogen ratios under micro-aerobic condition.

PubMed

Chen, Chuan; Zhang, Ruo-Chen; Xu, Xi-Jun; Fang, Ning; Wang, Ai-Jie; Ren, Nan-Qi; Lee, Duu-Jong

2017-05-01

The success of denitrifying sulfide removal (DSR) processes, which simultaneously degrade sulfide, nitrate and organic carbon in the same reactor, counts on synergetic growths of autotrophic and heterotrophic denitrifiers. Feeding wastewaters at high C/N ratio would stimulate overgrowth of heterotrophic bacteria in the DSR reactor so deteriorating the growth of autotrophic denitrifiers. The DSR tests at C/N=1.26:1, 2:1 or 3:1 and S/N =5:6 or 5:8 under anaerobic (control) or micro-aerobic conditions were conducted. Anaerobic DSR process has <50% sulfide removal with no elemental sulfur transformation. Under micro-aerobic condition to remove <5% sulfide by chemical oxidation pathway, 100% sulfide removal is achieved by the DSR consortia. Continuous-flow tests under micro-aerobic condition have 70% sulfide removal and 55% elemental sulfur recovery. Trace oxygen enhances activity of sulfide-oxidizing, nitrate-reducing bacteria to accommodate properly the wastewater with high C/N ratios. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide and ammonium oxidation, acetate mineralization by denitrification in a multipurpose UASB reactor.

PubMed

Beristain-Cardoso, Ricardo; Gómez, Jorge; Méndez-Pampín, Ramón

2011-02-01

The physiological and kinetic behavior of a denitrifying granular sludge exposed to different sulfide loading rates (55-295 mg/L d) were evaluated in a UASB reactor fed with acetate, ammonium and nitrate. At any sulfide loading rates, the consumption efficiencies of sulfide, acetate and ammonium were above 95%, while nitrate consumption efficiencies were around 62-72%. At the highest sulfide loading rate the ammonium was used as electron donor for N(2) production. The increase of sulfide loading rate also affected the fate of sulfide oxidation, since elemental sulfur was the main end product instead of sulfate. However, the lithotrophic denitrifying kinetic was not affected. FISH oligonucleotide probes for Thiobacillus denitrificans, Thiomiscropira denitrificans, genus Paracoccus and Pseudomonas spp. were used to follow the microbial ecology. The results of this work have shown that four pollutants could simultaneously be removed, namely, sulfide, ammonium, acetate and nitrate under well defined denitrifying conditions. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

Sunken wood habitat for thiotrophic symbiosis in mangrove swamps.

PubMed

Laurent, Mélina C Z; Gros, Olivier; Brulport, Jean-Pierre; Gaill, Françoise; Bris, Nadine Le

2009-03-01

Large organic falls to the benthic environment, such as dead wood or whale bones, harbour organisms relying on sulfide-oxidizing symbionts. Nothing is known however, concerning sulfide enrichment at the wood surface and its relation to wood colonization by sulfide-oxidizing symbiotic organisms. In this study we combined in situ hydrogen sulfide and pH measurements on sunken wood, with associated fauna microscopy analyses in a tropical mangrove swamp. This shallow environment is known to harbour thiotrophic symbioses and is also abundantly supplied with sunken wood. A significant sulfide enrichment at the wood surface was revealed. A 72h sequence of measurements emphasized the wide fluctuation of sulfide levels (0.1->100muM) over time with both a tidal influence and rapid fluctuations. Protozoans observed on the wood surface were similar to Zoothamnium niveum and to vorticellids. Our SEM observations revealed their association with ectosymbiotic bacteria, which are likely to be sulfide-oxidizers. These results support the idea that sunken wood surfaces constitute an environment suitable for sulfide-oxidizing symbioses.

The effects of sulfide composition on the solubility of sulfur in coexisting silicate melts

NASA Astrophysics Data System (ADS)

Smythe, Duane; Wood, Bernard; Kiseeva, Ekaterina

2016-04-01

The extent to which sulfur dissolves in silicate melts saturated in an immiscible sulfide phase is a fundamental question in igneous petrology and plays a primary role in the generation of magmatic ore deposits, volcanic degassing and planetary differentiation. Terrestrial sulfide melts often contain over 20 weight percent Ni + Cu, however, most experimental studies investigating sulfur solubility in silicate melt have been primarily concerned with the effects of silicate melt composition, and pure FeS has been use as the immiscible sulfide melt (O'Neill and Mavrogenes, 2002; Li and Ripley, 2005). To investigation of the effects of sulfide composition, in addition to those of temperature, pressure and silicate melt composition, on sulfur solubility in silicate melts, we have carried out a series of experiments done at pressures between 1.5 and 3 GPa and temperatures from 1400 to 1800C over a range of compositions of both the silicate and sulfide melt. We find that the solubility of sulfur in silicate melts drops significantly with the substitution of Ni and Cu for Fe in the immiscible sulfide melt, decreasing by approximately 40% at mole fractions of NiS + Cu2S of 0.4. Combining our results with those from the previous studies investigating sulfur solubility in silicate melts we have also found that solubility increases with increasing temperature and decreases pressure. These results show that without considering the composition of the immiscible sulfide phase the sulfur content of silicate melts can be significantly overestimated. This may serve to explain the relatively low sulfur concentrations in MORB melts, which previous models predict to be undersaturated in a sulfide phase despite showing chemical and textural evidence for sulfide saturation. Li, C. & Ripley, E. M. (2005). Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita 40, 218-230. O'Neill, H. S. C. & Mavrogenes, J. A. (2002). The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400°C and 1 bar. Journal of Petrology 43, 1049-1087.

The cytochrome bd oxidase of Escherichia coli prevents respiratory inhibition by endogenous and exogenous hydrogen sulfide

PubMed Central

Korshunov, Sergey; Imlay, Karin R. C.; Imlay, James A.

2016-01-01

Summary When sulfur compounds are scarce or difficult to process, E. coli adapts by inducing the high-level expression of sulfur-compound importers. If cystine then becomes available, the cystine is rapidly overimported and reduced, leading to a burgeoning pool of intracellular cysteine. Most of the excess cysteine is exported, but some is adventitiously degraded, with the consequent release of sulfide. Sulfide is a potent ligand of copper and heme moieties, raising the prospect that it interferes with enzymes. We observed that when cystine was provided and sulfide levels rose, E. coli became strictly dependent upon cytochrome bd oxidase for continued respiration. Inspection revealed that low-micromolar levels of sulfide inhibited the proton-pumping cytochrome bo oxidase that is regarded as the primary respiratory oxidase. In the absence of the back-up cytochrome bd oxidase, growth failed. Exogenous sulfide elicited the same effect. The potency of sulfide was enhanced when oxygen concentrations were low. Natural oxic-anoxic interfaces are often sulfidic, including the intestinal environment where E. coli dwells. We propose that the sulfide resistance of the cytochrome bd oxidase is a key trait that permits respiration in such habitats. PMID:26991114

Mineralization, alteration, and hydrothermal metamorphism of the ophiolite-hosted Turner-Albright sulfide deposit, southwestern Oregon

USGS Publications Warehouse

Zierenberg, R.A.; Shanks, Wayne C.; Seyfried, W.E.; Koski, R.A.; Strickler, M.D.

1988-01-01

The Turner-Albright sulfide deposit, part of the Josephine ophiolite, formed on and below the seafloor during Late Jurassic volcanism at a back arc spreading center. Ore fluids were probably localized by faults which were active on the seafloor at the time of sulfide deposition. The uppermost massive sulfide formed on the seafloor at hydrothermal vents. The bulk of the sulfide mineralization formed below the seafloor within olivine basalt hyaloclastite erupted near the time of mineralization. Infiltration of hydrothermal fluid into the hyaloclastite altered the rock. The fluid responsible for the hydrothermal alteration was evolved seawater with low pH and Mg and high Fe. The average value of sulfide and the difference between sulfide and contemporaneous seawater sulfate values are similar to ophiolite-hosted sulfide deposits in Cyprus. Mudstone and clinopyroxene basalt above the sulfide horizons were not altered by the ore-transporting hydrothermal fluid, but these rocks were hydrothermally metamorphosed by altered seawater heated by deep circulation into hot oceanic crust. This subseafloor metamorphism produced a mineral assemblage typical of prehnite-pumpellyite facies metamorphism. Exchange with altered seawater increased the whole-rock ??18O of the basalts to values of 9.4-11.2%. -from Authors

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-02-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

PubMed Central

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-01-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

Publications - SR 68 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

Mining District; Base Metals; Bethel Mining District; Bismuth; Black Mining District; Bluff (Place ; Livengood Mining District; Lode; Marshall Mining District; Massive Sulfide Deposit; Massive Sulfide Occurrence; Massive Sulfide Prospect; Massive Sulfides; McGrath Mining District; Melozitna Mining District

Membrane for hydrogen recovery from streams containing hydrogen sulfide

DOEpatents

Agarwal, Pradeep K.

2007-01-16

A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

Mineralogical and geochemical characterization of waste rocks from a gold mine in northeastern Thailand: application for environmental impact protection.

PubMed

Assawincharoenkij, Thitiphan; Hauzenberger, Christoph; Ettinger, Karl; Sutthirat, Chakkaphan

2018-02-01

Waste rocks from gold mining in northeastern Thailand are classified as sandstone, siltstone, gossan, skarn, skarn-sulfide, massive sulfide, diorite, and limestone/marble. Among these rocks, skarn-sulfide and massive sulfide rocks have the potential to generate acid mine drainage (AMD) because they contain significant amounts of sulfide minerals, i.e., pyrrhotite, pyrite, arsenopyrite, and chalcopyrite. Moreover, both sulfide rocks present high contents of As and Cu, which are caused by the occurrence of arsenopyrite and chalcopyrite, respectively. Another main concern is gossan contents, which are composed of goethite, hydrous ferric oxide (HFO), quartz, gypsum, and oxidized pyroxene. X-ray maps using electron probe micro-analysis (EPMA) indicate distribution of some toxic elements in Fe-oxyhydroxide minerals in the gossan waste rock. Arsenic (up to 1.37 wt.%) and copper (up to 0.60 wt.%) are found in goethite, HFO, and along the oxidized rim of pyroxene. Therefore, the gossan rock appears to be a source of As, Cu, and Mn. As a result, massive sulfide, skarn-sulfide, and gossan have the potential to cause environmental impacts, particularly AMD and toxic element contamination. Consequently, the massive sulfide and skarn-sulfide waste rocks should be protected from oxygen and water to avoid an oxidizing environment, whereas the gossan waste rocks should be protected from the formation of AMD to prevent heavy metal contamination.

An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

NASA Astrophysics Data System (ADS)

Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (X_{{{Ni}}}^{{{sulfide}}} 0.4-0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6-0.7) at depths near 80-120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (X_{{{Ni}}}^{{{sulfide}}} 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

Nanoporous gold-based microbial biosensor for direct determination of sulfide.

PubMed

Liu, Zhuang; Ma, Hanyue; Sun, Huihui; Gao, Rui; Liu, Honglei; Wang, Xia; Xu, Ping; Xun, Luying

2017-12-15

Environmental pollution caused by sulfide compounds has become a major problem for public health. Hence, there is an urgent need to explore a sensitive, selective, and simple sulfide detection method for environmental monitoring and protection. Here, a novel microbial biosensor was developed using recombinant Escherichia coli BL21 (E. coli BL21) expressing sulfide:quinone oxidoreductase (SQR) for sulfide detection. As an important enzyme involved in the initial step of sulfide metabolism, SQR oxidizes sulfides to polysulfides and transfers electrons to the electron transport chain. Nanoporous gold (NPG) with its unique properties was selected for recombinant E. coli BL21 cells immobilization, and then glassy carbon electrode (GCE) was modified by the resulting E. coli/NPG biocomposites to construct an E. coli/NPG/GCE bioelectrode. Due to the catalytic oxidation properties of NPG for sulfide, the electrochemical reaction of the E. coli/NPG/GCE bioelectrode is attributed to the co-catalysis of SQR and NPG. For sulfide detection, the E. coli/NPG/GCE bioelectrode showed a good linear response ranging from 50μM to 5mM, with a high sensitivity of 18.35μAmM -1 cm -2 and a low detection limit of 2.55μM. The anti-interference ability of the E. coli/NPG/GCE bioelectrode is better than that of enzyme-based inhibitive biosensors. Further, the E. coli/NPG/GCE bioelectrode was successfully applied to the detection of sulfide in wastewater. These unique properties potentially make the E. coli/NPG/GCE bioelectrode an excellent choice for reliable sulfide detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

PubMed Central

Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

2011-01-01

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1992-07-07

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1991-10-22

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

Code of Federal Regulations, 2014 CFR

2014-07-01

... hydrogen sulfide, distn. residues. 721.10445 Section 721.10445 Protection of Environment ENVIRONMENTAL... hydrogen sulfide, distn. residues. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide, distn...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in...

40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

Code of Federal Regulations, 2013 CFR

2013-07-01

... hydrogen sulfide, distn. residues. 721.10445 Section 721.10445 Protection of Environment ENVIRONMENTAL... hydrogen sulfide, distn. residues. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide, distn...

MEASURING METAL SULFIDE COMPLEXES IN OXIC RIVER WATERS WITH SQUARE WAVE VOLTAMMETRY. (R825395)

EPA Science Inventory

A sulfide identification protocol was developed to quantify specific metal
sulfides that could exist in river water. Using a series of acid additions,
nitrogen purges, and voltammetric analyses, metal sulfides were identified and
semiquantified in three specific gr...

NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

EPA Science Inventory

An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

Method of generating chemiluminescent light

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1986-03-11

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Method of generating chemiluminescent light

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1986-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction.

Lanthanide complexes as luminogenic probes to measure sulfide levels in industrial samples.

PubMed

Thorson, Megan K; Ung, Phuc; Leaver, Franklin M; Corbin, Teresa S; Tuck, Kellie L; Graham, Bim; Barrios, Amy M

2015-10-08

A series of lanthanide-based, azide-appended complexes were investigated as hydrogen sulfide-sensitive probes. Europium complex 1 and Tb complex 3 both displayed a sulfide-dependent increase in luminescence, while Tb complex 2 displayed a decrease in luminescence upon exposure to NaHS. The utility of the complexes for monitoring sulfide levels in industrial oil and water samples was investigated. Complex 3 provided a sensitive measure of sulfide levels in petrochemical water samples (detection limit ∼ 250 nM), while complex 1 was capable of monitoring μM levels of sulfide in partially refined crude oil. Copyright © 2015 Elsevier B.V. All rights reserved.

Repulsive Interaction of Sulfide Layers on Compressor Impeller Blades Remanufactured Through Plasma Spray Welding

NASA Astrophysics Data System (ADS)

Chang, Y.; Zhou, D.; Wang, Y. L.; Huang, H. H.

2016-12-01

This study investigated the repulsive interaction of sulfide layers on compressor impeller blades remanufactured through plasma spray welding (PSW). Sulfide layers on the blades made of FV(520)B steel were prepared through multifarious corrosion experiments, and PSW was utilized to remanufacture blade specimens. The specimens were evaluated through optical microscopy, scanning electron microscopy, energy-dispersive spectroscopy, 3D surface topography, x-ray diffraction, ImageJ software analysis, Vicker's micro-hardness test and tensile tests. Results showed a large number of sulfide inclusions in the fusion zone generated by sulfide layers embodied into the molten pool during PSW. These sulfide inclusions seriously degraded the mechanical performance of the blades remanufactured through PSW.

Measurement of H2S in vivo and in vitro by the monobromobimane method.

PubMed

Shen, Xinggui; Kolluru, Gopi K; Yuan, Shuai; Kevil, Christopher G

2015-01-01

The gasotransmitter hydrogen sulfide (H2S) is known as an important regulator in several physiological and pathological responses. Among the challenges facing the field is the accurate and reliable measurement of hydrogen sulfide bioavailability. We have reported an approach to discretely measure sulfide and sulfide pools using the monobromobimane (MBB) method coupled with reversed phase high-performance liquid chromatography (RP-HPLC). The method involves the derivatization of sulfide with excess MBB under precise reaction conditions at room temperature to form sulfide dibimane (SDB). The resultant fluorescent SDB is analyzed by RP-HPLC using fluorescence detection with the limit of detection for SDB (2 nM). Care must be taken to avoid conditions that may confound H2S measurement with this method. Overall, RP-HPLC with fluorescence detection of SDB is a useful and powerful tool to measure biological sulfide levels. © 2015 Elsevier Inc. All rights reserved.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

2001-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

1999-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Sulfide scaling in low enthalpy geothermal environments; A survey

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

Criaud, A.; Fouillac, C.

1989-01-01

A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are farmore » less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.« less

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, B.S.; Gupta, R.P.

1999-06-22

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.504 Section 250.504...-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.604 Section 250.604...-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide...

Coupling between anammox and autotrophic denitrification for simultaneous removal of ammonium and sulfide by enriched marine sediments.

PubMed

Rios-Del Toro, E Emilia; Cervantes, Francisco J

2016-06-01

In the present study, the capacity of enrichments derived from marine sediments collected from different sites of the Mexican littoral to perform anaerobic ammonium oxidation (anammox) coupled to sulfide-dependent denitrification for simultaneous removal of ammonium and sulfide linked to nitrite reduction was evaluated. Sulfide-dependent denitrification out-competed anammox during the simultaneous oxidation of sulfide and ammonium. Significant accumulation of elemental sulfur (ca. 14-30 % of added sulfide) occurred during the coupling between the two respiratory processes, while ammonium was partly oxidized (31-47 %) due to nitrite limitation imposed in sediment incubations. Nevertheless, mass balances revealed up to 38 % more oxidation of the electron donors available (ammonium and sulfide) than that expected from stoichiometry. Recycling of nitrite, from nitrate produced through anammox, is proposed to contribute to extra oxidation of sulfide, while additional ammonium oxidation is suggested by sulfate-reducing anammox (SR-anammox). The complex interaction between nitrogenous and sulfurous compounds occurring through the concomitant presence of autotrophic denitrification, conventional anammox and SR-anammox may significantly drive the nitrogen and sulfur fluxes in marine environments.

Massive sulfide metallogenesis at a late Mesozoic sediment-covered spreading axis: Evidence from the Franciscan complex and contemporary analogues

USGS Publications Warehouse

Koski, Randolph A.; Lamons, Roberta C.; Dumoulin, Julie A.; Bouse, Robin M.

1993-01-01

The Island Mountain deposit, an anomalous massive sulfide in the Central belt of the Franciscan subduction complex, northern California Coast Ranges, formed during hydrothermal activity in a sediment-dominated paleo-sea-floor environment. Although the base of the massive sulfide is juxtaposed against a 500-m-wide melange band, its gradational upper contact within a coherent sequence of sandstone, siltstone, and mudstone indicates that hydrothermal activity was concurrent with turbidite deposition. Accumulations of sulfide breccia and clastic sulfide were produced by mass wasting of the sulfide mound prior to burial by turbidites. The bulk composition of sulfide samples (pyrrhotite rich; high Cu, As, and Au contents; radiogenic Pb isotope ratios) is consistent with a hydrothermal system dominated by fluid-sediment interaction. On the basis of a comparison with possible contemporary tectonic analogues at the southern Gorda Ridge and the Chile margin triple junction, we propose that massive sulfide mineralization in the Central belt of the Franciscan complex resulted from hydrothermal activity at a late Mesozoic sediment-covered ridge axis prior to collision with the North American plate.

Massive sulfide metallogenesis at a late Mesozoic sediment-covered spreading axis: Evidence from the Franciscan complex and contemporary analogues

NASA Astrophysics Data System (ADS)

Koski, Randolph A.; Lamons, Roberta C.; Dumoulin, Julie A.; Bouse, Robin M.

1993-02-01

The Island Mountain deposit, an anomalous massive sulfide in the Central belt of the Franciscan subduction complex, northern California Coast Ranges, formed during hydrothermal activity in a sediment-dominated paleo-sea-floor environment. Although the base of the massive sulfide is juxtaposed against a 500-m-wide melange band, its gradational upper contact within a coherent sequence of sandstone, siltstone, and mudstone indicates that hydrothermal activity was concurrent with turbidite deposition. Accumulations of sulfide breccia and clastic sulfide were produced by mass wasting of the sulfide mound prior to burial by turbidites. The bulk composition of sulfide samples (pyrrhotite rich; high Cu, As, and Au contents; radiogenic Pb isotope ratios) is consistent with a hydrothermal system dominated by fluid-sediment interaction. On the basis of a comparison with possible contemporary tectonic analogues at the southern Gorda Ridge and the Chile margin triple junction, we propose that massive sulfide mineralization in the Central belt of the Franciscan complex resulted from hydrothermal activity at a late Mesozoic sediment-covered ridge axis prior to collision with the North American plate.

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 Using FeS/H2S As a Reducing Agent

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.; McDonald, Gene; Bada, Jeffrey

1995-01-01

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purities, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role In the origin of metabolism or the origin of life.

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 using FeS/H2S as a Reducing Agent

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.; McDonald, Gene; Bada, Jeffrey

1995-01-01

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purines, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role in the origin of metabolism or the origin of life.

Surface modification of malachite with ethanediamine and its effect on sulfidization flotation

NASA Astrophysics Data System (ADS)

Feng, Qicheng; Zhao, Wenjuan; Wen, Shuming

2018-04-01

Ethanediamine was used to modify the mineral surface of malachite to improve its sulfidization and flotation behavior. The activation mechanism was investigated by adsorption experiments, X-ray photoelectron spectroscopy (XPS) analysis, and zeta potential measurements. Microflotation experiments showed that the flotation recovery of malachite was enhanced after the pretreatment of the mineral particles with ethanediamine prior to the addition of Na2S. Adsorption tests revealed that numerous sulfide ion species in the pulp solution were transferred onto the mineral surface through the formation of more copper sulfide species. This finding was confirmed by the results of the XPS measurements. Ethanediamine modification not only increased the contents of copper sulfide species on the malachite surface but also enhanced the reactivity of the sulfidization products. During sulfidization, Cu(II) species on the mineral surface were reduced into Cu(I) species, and the percentages of S22- and Sn2- relative to the total S increased after modification, resulting in increased surface hydrophobicity. The results of zeta potential measurements showed that the ethanediamine-modified mineral surface adsorbed with more sulfide ion species was advantageous to the attachment of xanthate species, thereby improving malachite floatability. The proposed ethanediamine modification followed by sulfidization xanthate flotation exhibits potential for industrial application.

Compositions and microstructures of CB sulfides: Implications for the thermal history of the CB chondrite parent body

NASA Astrophysics Data System (ADS)

Srinivasan, Poorna; Jones, Rhian H.; Brearley, Adrian J.

2017-10-01

We studied textures and compositions of sulfide inclusions in unzoned Fe,Ni metal particles within CBa Gujba, CBa Weatherford, CBb HH 237, and CBb QUE 94411 in order to constrain formation conditions and secondary thermal histories on the CB parent body. Unzoned metal particles in all four chondrites have very similar metal and sulfide compositions. Metal particles contain different types of sulfides, which we categorize as: homogeneous low-Cr sulfides composed of troilite, troilite-containing exsolved daubreelite lamellae, arcuate sulfides that occur along metal grain boundaries, and shock-melted sulfides composed of a mixture of troilite and Fe, Ni metal. Our model for formation proposes that the unzoned metal particles were initially metal droplets that formed from splashing by a partially molten impacting body. Sulfide inclusions later formed as a result of precipitation of excess S from solid metal at low temperatures, either during single stage cooling or during a reheating event by impacts. Sulfides containing exsolution lamellae record temperatures of ≪600 °C, and irregular Fe-FeS intergrowth textures suggest localized shock melting, both of which are indicative of heterogeneous heating by impact processes on the CB parent body. Our study shows that CBa and CBb chondrites formed in a similar environment, and also experienced similar secondary impact processing.

Compositions of Magmatic and Impact Melt Sulfides in Tissint And EETA79001: Precursors of Immiscible Sulfide Melt Blebs in Shergottite Impact Melts

NASA Technical Reports Server (NTRS)

Ross, D. K.; Rao, M. N.; Nyquist, L.; Agee, C.; Sutton, S.

2013-01-01

Immiscible sulfide melt spherules are locally very abundant in shergottite impact melts. These melts can also contain samples of Martian atmospheric gases [1], and cosmogenic nuclides [2] that are present in impact melt, but not in the host shergottite, indicating some components in the melt resided at the Martian surface. These observations show that some regolith components are, at least locally, present in the impact melts. This view also suggests that one source of the over-abundant sulfur in these impact melts could be sulfates that are major constituents of Martian regolith, and that the sulfates were reduced during shock heating to sulfide. An alternative view is that sulfide spherules in impact melts are produced solely by melting the crystalline sulfide minerals (dominantly pyrrhotite, Fe(1-x)S) that are present in shergottites [3]. In this abstract we report new analyses of the compositions of sulfide immiscible melt spherules and pyrrhotite in the shergottites Tissint, and EETA79001,507, and we use these data to investigate the possible origins of the immiscible sulfide melt spherules. In particular, we use the metal/S ratios determined in these blebs as potential diagnostic criteria for tracking the source material from which the numerous sulfide blebs were generated by shock in these melts.

Spectral induced polarization and electrodic potential monitoring of microbially mediated iron sulfide transformations

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

Hubbard, Susan; Personna, Y.R.; Ntarlagiannis, D.

2008-02-15

Stimulated sulfate-reduction is a bioremediation technique utilized for the sequestration of heavy metals in the subsurface.We performed laboratory column experiments to investigate the geoelectrical response of iron sulfide transformations by Desulfo vibriovulgaris. Two geoelectrical methods, (1) spectral induced polarization (SIP), and (2) electrodic potential measurements, were investigated. Aqueous geochemistry (sulfate, lactate, sulfide, and acetate), observations of precipitates (identified from electron microscopy as iron sulfide), and electrodic potentials on bisulfide ion (HS) sensitive silver-silver chloride (Ag-AgCl) electrodes (630 mV) were diagnostic of induced transitions between an aerobic iron sulfide forming conditions and aerobic conditions promoting iron sulfide dissolution. The SIP datamore » showed 10m rad anomalies during iron sulfide mineralization accompanying microbial activity under an anaerobic transition. These anomalies disappeared during iron sulfide dissolution under the subsequent aerobic transition. SIP model parameters based on a Cole-Cole relaxation model of the polarization at the mineral-fluid interface were converted to (1) estimated biomineral surface area to pore volume (Sp), and (2) an equivalent polarizable sphere diameter (d) controlling the relaxation time. The temporal variation in these model parameters is consistent with filling and emptying of pores by iron sulfide biofilms, as the system transitions between anaerobic (pore filling) and aerobic (pore emptying) conditions. The results suggest that combined SIP and electrodic potential measurements might be used to monitor spatiotemporal variability in microbial iron sulfide transformations in the field.« less

Nitrosopersulfide (SSNO(-)) accounts for sustained NO bioactivity of S-nitrosothiols following reaction with sulfide.

PubMed

Cortese-Krott, Miriam M; Fernandez, Bernadette O; Santos, José L T; Mergia, Evanthia; Grman, Marian; Nagy, Péter; Kelm, Malte; Butler, Anthony; Feelisch, Martin

2014-01-01

Sulfide salts are known to promote the release of nitric oxide (NO) from S-nitrosothiols and potentiate their vasorelaxant activity, but much of the cross-talk between hydrogen sulfide and NO is believed to occur via functional interactions of cell regulatory elements such as phosphodiesterases. Using RFL-6 cells as an NO reporter system we sought to investigate whether sulfide can also modulate nitrosothiol-mediated soluble guanylyl cyclase (sGC) activation following direct chemical interaction. We find a U-shaped dose response relationship where low sulfide concentrations attenuate sGC stimulation by S-nitrosopenicillamine (SNAP) and cyclic GMP levels are restored at equimolar ratios. Similar results are observed when intracellular sulfide levels are raised by pre-incubation with the sulfide donor, GYY4137. The outcome of direct sulfide/nitrosothiol interactions also critically depends on molar reactant ratios and is accompanied by oxygen consumption. With sulfide in excess, a 'yellow compound' accumulates that is indistinguishable from the product of solid-phase transnitrosation of either hydrosulfide or hydrodisulfide and assigned to be nitrosopersulfide (perthionitrite, SSNO(-); λ max 412 nm in aqueous buffers, pH 7.4; 448 nm in DMF). Time-resolved chemiluminescence and UV-visible spectroscopy analyses suggest that its generation is preceded by formation of the short-lived NO-donor, thionitrite (SNO(-)). In contrast to the latter, SSNO(-) is rather stable at physiological pH and generates both NO and polysulfides on decomposition, resulting in sustained potentiation of SNAP-induced sGC stimulation. Thus, sulfide reacts with nitrosothiols to form multiple bioactive products; SSNO(-) rather than SNO(-) may account for some of the longer-lived effects of nitrosothiols and contribute to sulfide and NO signaling.

Hydrogen sulfide production and volatilization in a polymictic eutrophic saline lake, Salton Sea, California.

PubMed

Reese, Brandi Kiel; Anderson, Michael A; Amrhein, Christopher

2008-11-15

The Salton Sea is a large shallow saline lake located in southern California that is noted for high sulfate concentrations, substantial algal productivity, and very warm water column temperatures. These conditions are well-suited for sulfide production, and sulfide has been implicated in summer fish kills, although no studies have been conducted to specifically understand hydrogen sulfide production and volatilization there. Despite polymictic mixing patterns and relatively short accumulation periods, the amount of sulfide produced is comparable to meromictic lakes. Sulfide levels in the Salton Sea reached concentrations of 1.2 mmol L(-1) of total free sulfide in the hypolimnion and 5.6 mmol L(-1) in the sediment pore water. Strong winds in late July mixed H2S into the surface water, where it depleted the entire water column of dissolved oxygen and reached a concentration of 0.1 mmol L(-1). Sulfide concentrations exceeded the toxicity threshold of tilapia (Oreochromis mossambicus) and combined with strong anoxia throughout the water column, resulted in a massive fish kill. The mixing of sulfide into the surface waters also increased atmospheric H2S concentrations, reaching 1.0 micromol m(-3). The flux of sulfide from the sediment into the water column was estimated to range from 2-3 mmol m(-2) day(-1) during the winter and up to 8 mmol m(-2) day(-1) during the summer. Application of the two-layer model for volatilization indicates that up to 19 mmol m(-2) day(-1) volatilized from the surface during the mixing event. We estimate that as much as 3400 Mg year(-1) or approximately 26% of sulfide that diffused into the water column from the deepest sediments may have been volatilized to the atmosphere.

Metagenomic and Biochemical Characterizations of Sulfur Oxidation Metabolism in Uncultured Large Sausage-Shaped Bacterium in Hot Spring Microbial Mats

PubMed Central

Tamaki, Hideyuki; Kamagata, Yoichi; Hanada, Satoshi

2012-01-01

So-called “sulfur-turf” microbial mats in sulfide containing hot springs (55–70°C, pH 7.3–8.3) in Japan were dominated by a large sausage-shaped bacterium (LSSB) that is closely related to the genus Sulfurihydrogenibium. Several previous reports proposed that the LSSB would be involved in sulfide oxidation in hot spring. However, the LSSB has not been isolated yet, thus there has been no clear evidence showing whether it possesses any genes and enzymes responsible for sulfide oxidation. To verify this, we investigated sulfide oxidation potential in the LSSB using a metagenomic approach and subsequent biochemical analysis. Genome fragments of the LSSB (a total of 3.7 Mb sequence including overlapping fragments) were obtained from the metagenomic fosmid library constructed from genomic DNA of the sulfur-turf mats. The sequence annotation clearly revealed that the LSSB possesses sulfur oxidation-related genes coding sulfide dehydrogenase (SD), sulfide-quinone reductase and sulfite dehydrogenase. The gene encoding SD, the key enzyme for sulfide oxidation, was successfully cloned and heterologously expressed in Escherichia coli. The purified recombinant enzyme clearly showed SD activity with optimum temperature and pH of 60°C and 8.0, respectively, which were consistent with the environmental conditions in the hot spring where the sulfur-turf thrives. Furthermore, the affinity of SD to sulfide was relatively high, which also reflected the environment where the sulfide could be continuously supplied. This is the first report showing that the LSSB harbors sulfide oxidizing metabolism adapted to the hot spring environment and can be involved in sulfide oxidation in the sulfur-turf microbial mats. PMID:23185438

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.

Multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates.

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

Chen, Ken Shuang

2004-11-01

This report documents the author's efforts in the deterministic modeling of copper-sulfidation corrosion on non-planar substrates such as diodes and electrical connectors. A new framework based on Goma was developed for multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates. In this framework, the moving sulfidation front is explicitly tracked by treating the finite-element mesh as a pseudo solid with an arbitrary Lagrangian-Eulerian formulation and repeatedly performing re-meshing using CUBIT and re-mapping using MAPVAR. Three one-dimensional studies were performed for verifying the framework in asymptotic regimes. Limited model validation was also carried out by comparing computed copper-sulfide thickness with experimentalmore » data. The framework was first demonstrated in modeling one-dimensional copper sulfidation with charge separation. It was found that both the thickness of the space-charge layers and the electrical potential at the sulfidation surface decrease rapidly as the Cu{sub 2}S layer thickens initially but eventually reach equilibrium values as Cu{sub 2}S layer becomes sufficiently thick; it was also found that electroneutrality is a reasonable approximation and that the electro-migration flux may be estimated by using the equilibrium potential difference between the sulfidation and annihilation surfaces when the Cu{sub 2}S layer is sufficiently thick. The framework was then employed to model copper sulfidation in the solid-state-diffusion controlled regime (i.e. stage II sulfidation) on a prototypical diode until a continuous Cu{sub 2}S film was formed on the diode surface. The framework was also applied to model copper sulfidation on an intermittent electrical contact between a gold-plated copper pin and gold-plated copper pad; the presence of Cu{sub 2}S was found to raise the effective electrical resistance drastically. Lastly, future research needs in modeling atmospheric copper sulfidation are discussed.« less

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

USGS Publications Warehouse

Ono, Shuhei; Shanks, Wayne C.; Rouxel, O.J.; Rumble, D.

2007-01-01

Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different ??33S (?????33S-0.515 ??34S) values of up to 0.04??? even if ??34S values are identical. Detection of such small ??33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006??? (2??). Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10??N, 13??N, and 21??S and Mid-Atlantic Ridge (MAR) 37??N yield ??33S values ranging from -0.002 to 0.033 and ??34S from -0.5??? to 5.3???. The combined ??34S and ??33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13??N and marcasite from MAR 37??N are in isotope disequilibrium not only in ??34S but also in ??33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low ??33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles. ?? 2006 Elsevier Inc. All rights reserved.

Correlating Cu-sulfide and Au mineralization in the Ertsberg-Grasberg District using LA-ICP-MS and HRXCT

NASA Astrophysics Data System (ADS)

Wright, K. A.; Miller, N. R.; Ketcham, R. A.; Kyle, R.

2016-12-01

The Ertsberg-Grasberg district in Papua, Indonesia, hosts to two of the largest intrusion-related Cu-Au deposits in the world: the Ertsberg East Skarn system and the Grasberg Intrusive Complex. Cu mineralization within the Grasberg porphyry and Ertsberg skarn systems primarily consists of bornite and chalcopyrite, with minor digenite and idiate. Native Au is commonly found in association with Cu mineralization where Au occurs as inclusions within or immediately proximal to primary Cu-sulfide minerals. At hydrothermal-ore forming temperatures, approximately 400° to 700° C, bornite and chalcopyrite can host up to 1800 ppm Au within the Cu-sulfide lattice. Upon retrograde cooling of the hydrothermal system, the ability of bornite and chalcopyrite to host Au decreases significantly to about 10 ppm, indicating that the Au could be expulsed from the sulfide lattice. Given the close association of native Au and Cu-sulfide concentrations, it is possible that native gold grains form as the Au emerges from the Cu-sulfides. Constraining the genetic and spatio-temporal relationship between Cu-sulfide and Au mineralization within these deposits is of significant interest with regard to the geometallurgical processing of the ore, and to future exploration. This study seeks to evaluate this relationship using High Resolution X-ray Computed Tomography (HRXCT) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Previous HRXCT studies on Ertsberg-Grasberg ore samples have identified numerous occurrences of native Au grains at the edges of Cu-sulfide masses. HRXCT data are used here to construct 3D Voronoi regions of potential Au "diffusional drainage" from within the Cu-sulfides, where the expectation is a positive correlation between Au grain size and modified Voronoi polyhedron volume, defined as the volume of sulfide closer to that grain than any other via a connected path through sulfide. LA-ICP-MS data are used to determine variations in Au contents of Cu-sulfide minerals using 2D transects away from Au inclusions in 3D contact with Cu-sulfide minerals.

Sulfide binding properties of truncated hemoglobins.

PubMed

Nicoletti, Francesco P; Comandini, Alessandra; Bonamore, Alessandra; Boechi, Leonardo; Boubeta, Fernando Martin; Feis, Alessandro; Smulevich, Giulietta; Boffi, Alberto

2010-03-16

The truncated hemoglobins from Bacillus subtilis (Bs-trHb) and Thermobifida fusca (Tf-trHb) have been shown to form high-affinity complexes with hydrogen sulfide in their ferric state. The recombinant proteins, as extracted from Escherichia coli cells after overexpression, are indeed partially saturated with sulfide, and even highly purified samples still contain a small but significant amount of iron-bound sulfide. Thus, a complete thermodynamic and kinetic study has been undertaken by means of equilibrium and kinetic displacement experiments to assess the relevant sulfide binding parameters. The body of experimental data indicates that both proteins possess a high affinity for hydrogen sulfide (K = 5.0 x 10(6) and 2.8 x 10(6) M(-1) for Bs-trHb and Tf-trHb, respectively, at pH 7.0), though lower with respect to that reported previously for the sulfide avid Lucina pectinata I hemoglobins (2.9 x 10(8) M(-1)). From the kinetic point of view, the overall high affinity resides in the slow rate of sulfide release, attributed to hydrogen bonding stabilization of the bound ligand by distal residue WG8. A set of point mutants in which these residues have been replaced with Phe indicates that the WG8 residue represents the major kinetic barrier to the escape of the bound sulfide species. Accordingly, classical molecular dynamics simulations of SH(-)-bound ferric Tf-trHb show that WG8 plays a key role in the stabilization of coordinated SH(-) whereas the YCD1 and YB10 contributions are negligible. Interestingly, the triple Tf-trHb mutant bearing only Phe residues in the relevant B10, G8, and CD1 positions is endowed with a higher overall affinity for sulfide characterized by a very fast second-order rate constant and 2 order of magnitude faster kinetics of sulfide release with respect to the wild-type protein. Resonance Raman spectroscopy data indicate that the sulfide adducts are typical of a ferric iron low-spin derivative. In analogy with other low-spin ferric sulfide adducts, the strong band at 375 cm(-1) is tentatively assigned to a Fe-S stretching band. The high affinity for hydrogen sulfide is thought to have a possible physiological significance as H(2)S is produced in bacteria at metabolic steps involved in cysteine biosynthesis and hence in thiol redox homeostasis.

Geochemical features of sulfides from the Deyin-1 hydrothermal field at the southern Mid-Atlantic Ridge near 15°S

NASA Astrophysics Data System (ADS)

Wang, Shujie; Li, Huaiming; Zhai, Shikui; Yu, Zenghui; Cai, Zongwei

2017-12-01

In this study, geochemical compositions of elements in sulfide samples collected from the Deyin-1 hydrothermal field near the 15°S southern Mid-Atlantic Ridge (SMAR) were analyzed by the X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) to examine the enrichment regulations of ore-forming elements and hydrothermal mineralization. These sulfide precipitates can be classified macroscopically into three types: Fe-rich sulfide, Fe-Cu-rich sulfide and Fe-Zn-rich sulfide, and are characterized by the enrichment of base metal elements along with a sequence of Fe>Zn>Cu. Compared with sulfides from other hydrothermal fields on MAR, Zn concentrations of sulfides in the research area are significantly high, while Cu concentrations are relatively low. For all major, trace or rare-earth elements (REE), their concentrations and related characteristic parameters exhibit significant variations (up to one or two orders of magnitude), which indicates the sulfides from different hydrothermal vents or even a same station were formed at different stages of hydrothermal mineralization, and suggests the variations of chemical compositions of the hydrothermal fluid with respect to time. The hydrothermal temperatures of sulfides precipitation decreased gradually from station TVG10 (st.TVG10) to st.TVG12, and to st.TVG11, indicating that the precipitation of hydrothermal sulfides is subjected to conditions changed from high temperature to low temperature, and that the hydrothermal activity of study area was at the late stage of a general trend of evolution from strong to weak. The abnormally low concentrations of REE in sulfides and their similar chondrite-normalized REE patterns show that REEs in all sulfides were derived from a same source, but underwent different processes of migration or enrichment, or sulfides were formed at different stages of hydrothermal mineralization. The sulfides collected from the active hydrothermal vent were mainly attributed to precipitating directly from the hydrothermal fluid, while those collected from the extinct hydrothermal chimney might have already been altered by the seawater. Generally, ore-forming elements in the sulfides can be divided into three groups: Fe-based element group, Cu-based element group and Zn-based element group. The first group includes Fe, Mn, Cr, Mo, Sn, Rb and bio-enriching elements, such as P and Si, reflecting the similar characteristics to Fe in the study area. And the second group contains Cu, W, Co, Se, Te and Bi, suggesting the similar behavior with Cu. Moreover, the third group includes Zn, Hf, Hg, Cd, Ta, Ga, Pb, As, Ag, Ni and Sb, which indicates the geochemical characteristics of most dispersed trace elements controlled by Zn-bearing minerals to some extent.

Sulfide minerals as new Sm-Nd geochronometers for ore genesis dating of mafic-ultramafic layered intrusions

NASA Astrophysics Data System (ADS)

Serov, Pavel; Ekimova, Nadezhda; Bayanova, Tamara

2014-05-01

The main method of dating the ore process was the Re-Os method of sulfides (Luck, Allegre, 1983; Walker et. al., 1991). However, studies of Re-Os systematics of sulfide minerals do not always give the correct ages and showing the disturbances of the Re-Os systematics. At the same time, Sm-Nd age of sulfides in good agreement with the U-Pb dating on zircon and baddeleyite and suggests that the Sm-Nd system of sulfides is more resistant to secondary alteration processes. Our studies have shown that along with rock-forming, ore minerals (sulfides) can be used to determine the ore genesis time of industrially important geological sites, since exactly with the sulfides the industry Pt-Pd mineralization is closely connected. The Sm-Nd investigations steadily employ new minerals-geochronometers. Of these, sulfides of PGE-bearing layered intrusions are quite important in terms of dating the process of ore origin. Studying the REE distribution in the sulfides of MOR hydrothermal sources has shown possible REE presence in the sulfide lattice (Rimskaya-Korsakova et. al., 2003). These are difficult to carry out because the concentrations of Sm and Nd isotopes in sulfides are much lower than chondrites (Rimskaya-Korsakova et. al., 2003). For the first time in Russia with sulfide and rock-forming minerals and WR in Sm-Nd method have been dated impregnated and brecciform ores of the following objects: Pilguyarvi Cu-Ni deposits, Pechenga (1965±87 Ma); impregnated (2433±83 Ma) and redeposited (1903±24 Ma) ores of Ahmavaara intrusion (Finland); ore gabbronorites of Penikat PGE-bearing layered intrusion (2426±38 Ma (Ekimova et.al., 2011); Pt-Pd gabbro-pegmatite ores (2476± 41 Ma, which agrees with the U-Pb zircon age - 2470±9 Ma (Bayanova, 2004) and gabbronorites (2483±86 Ma) of PGE Kievei deposit and Fedorova Tundra metagabbroids (2494±54 Ma); Monchetundra gabbronorites - 2489±49 Ma. In (Kong et. al., 2000) sulfides from two metamorphosed chondrites studied by instrumental neutron activation analysis (INAA) and ion probe. As shown, the level of REE in the sulfide phase determined by the ion probe is quite similar to that obtained by INAA. Although the concentrations of REE in the enstatite and the Fe, Si, Cr-rich inclusions are comparable to those in sulfide, estimates based on mass balance calculations show that the silicate inclusions would not noticeably contribute to the REE budget in sulfides (Kong et. al., 2000). These studies were supported by the RFBR 13-05-00493, OFI-M 13-05-12055, State Earth Division Program #4 and IGCP-599.

Siderophile and chalcophile metals as tracers of the evolution of the Siberian Trap in the Noril'sk region, Russia

NASA Astrophysics Data System (ADS)

Brügmann, G. E.; Naldrett, A. J.; Asif, M.; Lightfoot, P. C.; Gorbachev, N. S.; Fedorenko, V. A.

1993-05-01

In this study Cu, Ni, and platinum-group elements (PGE) were determined in a sequence of basaltic and picritic lavas from the Siberian Trap in the Noril'sk area of Russia to constrain genetic relationships between the basalts and the petrogenesis of Ni-Cu-PGE sulfide deposits associated with the Talnakh and Noril'sk intrusions. In the most primitive basalts (8-19 wt% MgO) of the Tuklonsky (Tk) suite, Pt and Pd concentrations range from 4-13 ppb, increasing with decreasing MgO content; whereas Ir contents decrease with MgO from 0.8-0.05 ppb. The contrasting behavior of these elements, which all have very high sulfide-silicate partition coefficients, as well as the primitive mantle-like ratios of Cu/Y and Pd/Y, suggests that these magmas were not sulfide-saturated. The high PGE abundances imply that their parental magmas were also not sulfide saturated during partial melting in the mantle. Due to sulfide segregation, the overlying basalts of the Nadezhdinsky (Nd) series are low in Cu and Ni (52 and 38 ppm, respectively); highly depleted in all PGE; and have very low Cu/Y, Pd/Y, and Pd/Cu ratios. However, in stratigraphically higher levels, Cu, Ni, and PGE concentrations increase systematically through the Morongovsky (Mr) suite to reach a concentration plateau in the uppermost Mokulaevsky (Mk) suite (Pt 8 ppb; Pd: 9 ppb; Ir: 0.12 ppb; Rh: 0.4 ppb). At the same time, ratios such as Cu/Y increase and approach primitive mantle values. However, ratios involving PGE, such as Pd/Y, remain low, suggesting the removal of small amounts of sulfide (0.01-0.03%). The compositional variations in the basalts and the sulfide liquids can be quantitatively described by fractional segregation of a sulfide liquid in an open- or closed-system magma chamber. The latter model suggests that the basalts represent the eruption products of a zoned magma chamber in which light magma, with crustal components contaminated, overlies less contaminated, denser magma. Crustal contamination caused sulfide saturation, and the resulting sulfide liquids settled through a magma column and accumulated at the bottom of the chamber. In this model, the sulfide liquid is not in equilibrium with the whole magma mass, and sulfide segregation is compared with the zone-refining process of metallurgy. The sulfides become more enriched as they move through the magma; and although the magma left behind is depleted in PGE, Cu, and Ni, their concentrations also increase with depth. Eventually, the magma chamber is emptied from the top to the bottom, producing the flood basalt sequence and the associated intrusions and ore deposits. In the open-system model, sulfide saturation was initially caused by assimilation of crustal material by the Tuklonsky magma. Continuous and simultaneous replenishment, assimilation, and crystallization processes formed the lower Nd lavas. The concurrent removal of 0.5-1% sulfide strongly depleted these magmas in chalcophile and siderophile metals. Due to the continuous replenishment of the magma chamber with uncontaminated PGE-rich magma, succeeding lavas (Mr, Mk) show diminishing signs of crustal contamination and become less sulfide-saturated, as indicated by the increasing Ni, Cu, and PGE abundances. During the evolution of the chamber, the magma remained sulfur-saturated, and sulfides accumulated at the base. The composition of the sulfide ores could be regarded as a mixture consisting of low Ni-, Cu-, and PGE-sulfides derived with a low silicate/sulfide ratio (100) from the Tk-Nd magma and high Ni-, Cu-, and PGE-sulfides formed with a high ratio (10,000) from the Mr-Mk magma.

40 CFR 60.648 - Optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure. 1

Code of Federal Regulations, 2011 CFR

2011-07-01

... hydrogen sulfide in acid gas-Tutwiler Procedure. 1 60.648 Section 60.648 Protection of Environment... procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure. 1 1 Gas Engineers Handbook, Fuel.... In principle, this method consists of titrating hydrogen sulfide in a gas sample directly with a...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

40 CFR 60.648 - Optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure. 1

Code of Federal Regulations, 2010 CFR

2010-07-01

... hydrogen sulfide in acid gas-Tutwiler Procedure. 1 60.648 Section 60.648 Protection of Environment... procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure. 1 1 Gas Engineers Handbook, Fuel.... In principle, this method consists of titrating hydrogen sulfide in a gas sample directly with a...

40 CFR 60.648 - Optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure. 1

Code of Federal Regulations, 2013 CFR

2013-07-01

... hydrogen sulfide in acid gas-Tutwiler Procedure. 1 60.648 Section 60.648 Protection of Environment..., 2011 § 60.648 Optional procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure. 1 1 Gas... dilute solutions are used. In principle, this method consists of titrating hydrogen sulfide in a gas...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

40 CFR 60.648 - Optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure. 1

Code of Federal Regulations, 2012 CFR

2012-07-01

... hydrogen sulfide in acid gas-Tutwiler Procedure. 1 60.648 Section 60.648 Protection of Environment... procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure. 1 1 Gas Engineers Handbook, Fuel.... In principle, this method consists of titrating hydrogen sulfide in a gas sample directly with a...

40 CFR 60.5408 - What is an optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure?

Code of Federal Regulations, 2013 CFR

2013-07-01

... measuring hydrogen sulfide in acid gas-Tutwiler Procedure? 60.5408 Section 60.5408 Protection of Environment... § 60.5408 What is an optional procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure... of titrating hydrogen sulfide in a gas sample directly with a standard solution of iodine. (b...

30 CFR 250.504 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

40 CFR 60.5408 - What is an optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure?

Code of Federal Regulations, 2014 CFR

2014-07-01

... measuring hydrogen sulfide in acid gas-Tutwiler Procedure? 60.5408 Section 60.5408 Protection of Environment... § 60.5408 What is an optional procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure... of titrating hydrogen sulfide in a gas sample directly with a standard solution of iodine. (b...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

30 CFR 250.604 - Hydrogen sulfide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of this...

40 CFR 60.648 - Optional procedure for measuring hydrogen sulfide in acid gas-Tutwiler Procedure. 1

Code of Federal Regulations, 2014 CFR

2014-07-01

... hydrogen sulfide in acid gas-Tutwiler Procedure. 1 60.648 Section 60.648 Protection of Environment..., 2011 § 60.648 Optional procedure for measuring hydrogen sulfide in acid gas—Tutwiler Procedure. 1 1 Gas... dilute solutions are used. In principle, this method consists of titrating hydrogen sulfide in a gas...

The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

NASA Technical Reports Server (NTRS)

Jacobson, N. S.; Worrell, W. L.

1985-01-01

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

Gallium-bearing sphalerite in a metal-sulfide nodule of the Qingzhen (EH3) chondrite

NASA Technical Reports Server (NTRS)

Rambaldi, E. R.; Rajan, R. S.; Housley, R. M.; Wang, D.

1986-01-01

The composition and possible history of the Qingshen (EH3) chondrite is presented. The chondrite contains a population of spheroidal metal-sulfide nodules, which display textural evidence of reheating and melting. Evidence of metal sulfuration is also present, suggesting replacement of metal by sulfide during melting. This process has led to the nucleation of perryite along metal-sulfide interfaces. The Ga-bearing sphalerite that was found may have formed by injection of molten sulfide droplets into the metal followed by subsolidus diffusion of Ga from the metal into the sulfide. The latter may occur because of Ga supersaturation in the metal during progressive sulfuration and its decreased affinity for the metal phase during cooling below the taenite-kamacite transition point.

Zelda and company - Petrogenesis of sulfide-rich Fremdlinge and constraints on solar nebula processes

NASA Technical Reports Server (NTRS)

Armstrong, John T.; Hutcheon, Ian D.; Wasserburg, G. J.

1987-01-01

A detailed petrographic and chemical study of Zelda (a gigantic sulfide-rich Fremdling from the Allende Ca-rich inclusion, CAI, Egg 6) and its contact with the host was conducted using analytical SEM and electron-microprobe techniques, and the results were compared with those obtained on other sulfide-rich and oxide-rich Fremdlinge. Strong evidence is presented that Zelda, a type-example of sulfide-rich Fremdlinge, has been formed from a preexisting Ur-Fremdling, similar by composition to Willy, by closed-system sulfidization of magnetite and metal. At least two different sulfidization mechanisms appear to have occurred in altering Fremdlinge: one producing compositionally homogeneous equigranular objects such as Zelda, the other producing compositionally and texturally heterogeneous objects.

The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

NASA Technical Reports Server (NTRS)

Jacobson, N. S.; Worrell, W. L.

1984-01-01

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

NASA Astrophysics Data System (ADS)

Aller, Robert C.; Rude, Peter D.

1988-03-01

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO 4- under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn +4 are apparently more effective than Mn +3 in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly aulolrophic CO 2 fixation. Lack of sensitivity to chlorate suggests that a No 3- reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O 2. Alkalinity is also simultaneously depeleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial Proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

Technological aspects of the microbial treatment of sulfide-rich wastewaters: a case study.

PubMed

Sublette, K L; Kolhatkar, R; Raterman, K

1998-01-01

Thiobacillus denitrificans has been shown to be an effective biocatalyst for the treatment of a variety of sulfide-laden waste streams including sour water, sour gases, and refinery spent-sulfidic caustics. The term 'sour' originated in the petroleum industry to describe a waste contaminated with hydrogen sulfide or salts of sulfide and bisulfide. The microbial treatment of sour waste streams resulting from the production or refining of natural gas and crude oil have been investigated in this laboratory for many years. The application of this technology to the treatment of sour wastes on a commercially useful scale has presented several technical barriers including substrate inhibition (sulfide), product inhibition (sulfate), the need for septic operation, biomass recycle and recovery, mixed waste issues, and the need for large-scale cultivation of the organism for process startup. The removal of these barriers through process improvements are discussed in terms of a case study of the full-scale treatment of sulfide-rich wastewater. The ability of T. denitrificans to deodorize and detoxify an oil-field produced water containing sulfides was evaluated under full-scale field conditions at Amoco Production Co. Salt Creek Field in Midwest, WY. More than 800 m3/d of produced water containing 100 mg/L sulfide and total dissolved solids of 4800 mg/L were successfully biotreated in an earthen pit (3000 m3) over a six-month period. Complete removal of sulfides and elimination of associated odors were observed. The system could be upset by severe hydraulic disturbances; however, the system recovered rapidly when normal influent flow rates were restored.

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

Vitvitsky, Victor; Yadav, Pramod K.; An, Sojin

Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against itmore » in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal.« less

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

1994-01-01

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

PubMed Central

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-01-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1–40 μM in sulfide detection with a high sensitivity of 1720 μA mM−1 cm−2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported. PMID:27515253

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

NASA Astrophysics Data System (ADS)

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-08-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1-40 μM in sulfide detection with a high sensitivity of 1720 μA mM-1 cm-2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported.

Effects of Wood Pollution on Pore-Water Sulfide Levels and Eelgrass Germination

NASA Astrophysics Data System (ADS)

Ekelem, C.

2016-02-01

Historically, sawmills released wood waste onto coastal shorelines throughout the Pacific Northwest of the USA, enriching marine sediments with organic material. The increase in organic carbon boosts the bacterial reduction of sulfate and results in the production of a toxic metabolite, hydrogen sulfide. Hydrogen sulfide is a phytotoxin and can decrease the growth and survival of eelgrass. This is a critical issue since eelgrass, Zostera marina, forms habitat for many species, stabilizes sediment, and plays a role in nutrient cycling and sediment chemistry. The objective of our study was to determine the effects of wood debris on sediment pore-water hydrogen sulfide concentrations and eelgrass germination. To test the impact of wood inputs on sulfide production and seed germination, we conducted a laboratory mesocosm experiment, adding sawdust to marine sediments and measuring the sulfide levels weekly. We subsequently planted seeds in the mesocosms and measured germination rates. Higher concentrations of sawdust led to higher levels of pore-water hydrogen sulfide and drastically slower eelgrass germination rates. Treatments with greater than 10% wood enrichment developed free sulfide concentrations of 0.815 (± 0.427) mM after 118 days, suggesting sediments with greater than 10% wood pollution may have threateningly high pore-water hydrogen sulfide levels. These results can be used to set thresholds for remediation efforts and guide seed distribution in wood polluted areas.

Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

PubMed

Tomei Torres, Francisco A

2017-06-21

Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

Oxygenic and anoxygenic photosynthesis in a microbial mat from an anoxic and sulfidic spring.

PubMed

de Beer, Dirk; Weber, Miriam; Chennu, Arjun; Hamilton, Trinity; Lott, Christian; Macalady, Jennifer; M Klatt, Judith

2017-03-01

Oxygenic and anoxygenic photosynthesis were studied with microsensors in microbial mats found at 9-10 m depth in anoxic and sulfidic water in Little Salt Spring (Florida, USA). The lake sediments were covered with a 1-2 mm thick red mat dominated by filamentous Cyanobacteria, below which Green Sulfur Bacteria (GSB, Chlorobiaceae) were highly abundant. Within 4 mm inside the mats, the incident radiation was attenuated to undetectable levels. In situ microsensor data showed both oxygenic photosynthesis in the red surface layer and light-induced sulfide dynamics up to 1 cm depth. Anoxygenic photosynthesis occurred during all daylight hours, with complete sulfide depletion around midday. Oxygenic photosynthesis was limited to 4 h per day, due to sulfide inhibition in the early morning and late afternoon. Laboratory measurements on retrieved samples showed that oxygenic photosynthesis was fully but reversibly inhibited by sulfide. In patches Fe(III) alleviated the inhibition of oxygenic photosynthesis by sulfide. GSB were resistant to oxygen and showed a low affinity to sulfide. Their light response showed saturation at very low intensities. © 2016 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Negative Regulation of Autophagy by Sulfide Is Independent of Reactive Oxygen Species1

PubMed Central

Laureano-Marín, Ana M.; Moreno, Inmaculada

2016-01-01

Accumulating experimental evidence in mammalian, and recently plant, systems has led to a change in our understanding of the role played by hydrogen sulfide in life processes. In plants, hydrogen sulfide mitigates stress and regulates important plant processes such as photosynthesis, stomatal movement, and autophagy, although the underlying mechanism is not well known. In this study, we provide new experimental evidence that, together with our previous findings, demonstrates the role of hydrogen sulfide in regulating autophagy. We used green fluorescent protein fluorescence associated with autophagic bodies and immunoblot analysis of the ATG8 protein to show that sulfide (and no other molecules such as sulfur-containing molecules or ammonium) was able to inhibit the autophagy induced in Arabidopsis (Arabidopsis thaliana) roots under nitrogen deprivation. Our results showed that sulfide was unable to scavenge reactive oxygen species generated by nitrogen limitation, in contrast to well-established reducers. In addition, reducers were unable to inhibit the accumulation of autophagic bodies and ATG8 protein forms to the same extent as sulfide. Therefore, we conclude that sulfide represses autophagy via a mechanism that is independent of redox conditions. PMID:27208225

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.

Negative Regulation of Autophagy by Sulfide Is Independent of Reactive Oxygen Species.

PubMed

Laureano-Marín, Ana M; Moreno, Inmaculada; Romero, Luis C; Gotor, Cecilia

2016-06-01

Accumulating experimental evidence in mammalian, and recently plant, systems has led to a change in our understanding of the role played by hydrogen sulfide in life processes. In plants, hydrogen sulfide mitigates stress and regulates important plant processes such as photosynthesis, stomatal movement, and autophagy, although the underlying mechanism is not well known. In this study, we provide new experimental evidence that, together with our previous findings, demonstrates the role of hydrogen sulfide in regulating autophagy. We used green fluorescent protein fluorescence associated with autophagic bodies and immunoblot analysis of the ATG8 protein to show that sulfide (and no other molecules such as sulfur-containing molecules or ammonium) was able to inhibit the autophagy induced in Arabidopsis (Arabidopsis thaliana) roots under nitrogen deprivation. Our results showed that sulfide was unable to scavenge reactive oxygen species generated by nitrogen limitation, in contrast to well-established reducers. In addition, reducers were unable to inhibit the accumulation of autophagic bodies and ATG8 protein forms to the same extent as sulfide. Therefore, we conclude that sulfide represses autophagy via a mechanism that is independent of redox conditions. © 2016 American Society of Plant Biologists. All Rights Reserved.

Extraction of lead from waste CRT funnel glass by generating lead sulfide - An approach for electronic waste management.

PubMed

Hu, Biao; Hui, Wenlong

2017-09-01

Waste cathode ray tube (CRT) funnel glass is the key and difficult points in waste electrical and electronic equipment (WEEE) disposal. In this paper, a novel and effective process for the detoxification and reutilization of waste CRT funnel glass was developed by generating lead sulfide precipitate via a high-temperature melting process. The central function in this process was the generation of lead sulfide, which gathered at the bottom of the crucible and was then separated from the slag. Sodium carbonate was used as a flux and reaction agent, and sodium sulfide was used as a precipitating agent. The experimental results revealed that the lead sulfide recovery rate initially increased with an increase in the amount of added sodium carbonate, the amount of sodium sulfide, the temperature, and the holding time and then reached an equilibrium value. The maximum lead sulfide recovery rate was approximately 93%, at the optimum sodium carbonate level, sodium sulfide level, temperature, and holding time of 25%, 8%, 1200°C, and 2h, respectively. The glass slag can be made into sodium and potassium silicate by hydrolysis in an environmental and economical process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Complementary effect of natural and sexual selection against immigrants maintains differentiation between locally adapted fish

NASA Astrophysics Data System (ADS)

Plath, Martin; Riesch, Rüdiger; Oranth, Alexandra; Dzienko, Justina; Karau, Nora; Schießl, Angela; Stadler, Stefan; Wigh, Adriana; Zimmer, Claudia; Arias-Rodriguez, Lenin; Schlupp, Ingo; Tobler, Michael

2010-08-01

Adaptation to ecologically heterogeneous environments can drive speciation. But what mechanisms maintain reproductive isolation among locally adapted populations? Using poeciliid fishes in a system with naturally occurring toxic hydrogen sulfide, we show that (a) fish from non-sulfidic sites ( Poecilia mexicana) show high mortality (95 %) after 24 h when exposed to the toxicant, while locally adapted fish from sulfidic sites ( Poecilia sulphuraria) experience low mortality (13 %) when transferred to non-sulfidic water. (b) Mate choice tests revealed that P. mexicana females exhibit a preference for conspecific males in non-sulfidic water, but not in sulfidic water, whereas P. sulphuraria females never showed a preference. Increased costs of mate choice in sulfidic, hypoxic water, and the lack of selection for reinforcement due to the low survival of P. mexicana may explain the absence of a preference in P. sulphuraria females. Taken together, our study may be the first to demonstrate independent—but complementary—effects of natural and sexual selection against immigrants maintaining differentiation between locally adapted fish populations.

Production of sulfur gases and carbon dioxide by synthetic weathering of crushed drill cores from the Santa Cruz porphyry copper deposit near Casa Grande, Pinal County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Ryder, J.L.; Sutley, S.J.; Botinelly, T.

1990-01-01

Samples of ground drill cores from the southern part of the Santa Cruz porphyry copper deposit, Casa Grande, Arizona, were oxidized in simulated weathering experiments. The samples were also separated into various mineral fractions and analyzed for contents of metals and sulfide minerals. The principal sulfide mineral present was pyrite. Gases produced in the weathering experiments were measured by gas chromatography. Carbon dioxide, oxygen, carbonyl sulfide, sulfur dioxide and carbon disulfide were found in the gases; no hydrogen sulfide, organic sulfides, or mercaptans were detected. Oxygen concentration was very important for production of the volatiles measured; in general, oxygen concentration was more important to gas production than were metallic element content, sulfide mineral content, or mineral fraction (oxide or sulfide) of the sample. The various volatile species also appeared to be interactive; some of the volatiles measured may have been formed through gas reactions. ?? 1990.

Alkaline sulfide pretreatment of an antimonial refractory Au-Ag ore for improved cyanidation

NASA Astrophysics Data System (ADS)

Alp, Ibrahim; Celep, Oktay; Deveci, Haci

2010-11-01

This paper presents the alkaline sulfide pretreatment of an antimonial refractory gold and silver ore. In the ore, gold occurs mainly as gold-silver alloys and as associated with quartz and framboidal pyrite grains, and, to a small extent, as the inclusions within antimonial sulfides. Silver is present extensively as antimonial sulfides such as andorite. Alkaline sulfide pretreatment was shown to allow the decomposition of the antimonial sulfide minerals (up to 98% Sb removal) and to remarkably improve the amenability of gold (e.g., from <49% up to 83%) and silver (e.g., from <18% up to 90%) to subsequent cyanide leaching. An increase in reagent concentration (1-4 mol/L Na2S or NaOH) and temperature (20-80°C), and a decrease in particle size seem to produce an enhancing effect on metal extraction. These findings suggest that alkaline sulfide leaching can be suitably used as a chemical pretreatment method prior to the conventional cyanidation for antimonial refractory gold and silver ores.

Complementary effect of natural and sexual selection against immigrants maintains differentiation between locally adapted fish.

PubMed

Plath, Martin; Riesch, Rüdiger; Oranth, Alexandra; Dzienko, Justina; Karau, Nora; Schiessl, Angela; Stadler, Stefan; Wigh, Adriana; Zimmer, Claudia; Arias-Rodriguez, Lenin; Schlupp, Ingo; Tobler, Michael

2010-08-01

Adaptation to ecologically heterogeneous environments can drive speciation. But what mechanisms maintain reproductive isolation among locally adapted populations? Using poeciliid fishes in a system with naturally occurring toxic hydrogen sulfide, we show that (a) fish from non-sulfidic sites (Poecilia mexicana) show high mortality (95 %) after 24 h when exposed to the toxicant, while locally adapted fish from sulfidic sites (Poecilia sulphuraria) experience low mortality (13 %) when transferred to non-sulfidic water. (b) Mate choice tests revealed that P. mexicana females exhibit a preference for conspecific males in non-sulfidic water, but not in sulfidic water, whereas P. sulphuraria females never showed a preference. Increased costs of mate choice in sulfidic, hypoxic water, and the lack of selection for reinforcement due to the low survival of P. mexicana may explain the absence of a preference in P. sulphuraria females. Taken together, our study may be the first to demonstrate independent-but complementary-effects of natural and sexual selection against immigrants maintaining differentiation between locally adapted fish populations.

Selenium Sulfide

MedlinePlus

... minutes.Do not leave selenium sulfide on your hair, scalp, or skin for long periods (e.g., ... jewelry; selenium sulfide may damage it. Wash your hair with ordinary shampoo and rinse it well. Shake ...

Atomic layer deposition of metal sulfide thin films using non-halogenated precursors

DOEpatents

Martinson, Alex B. F.; Elam, Jeffrey W.; Pellin, Michael J.

2015-05-26

A method for preparing a metal sulfide thin film using ALD and structures incorporating the metal sulfide thin film. The method includes providing an ALD reactor, a substrate, a first precursor comprising a metal and a second precursor comprising a sulfur compound. The first and the second precursors are reacted in the ALD precursor to form a metal sulfide thin film on the substrate. In a particular embodiment, the metal compound comprises Bis(N,N'-di-sec-butylacetamidinato)dicopper(I) and the sulfur compound comprises hydrogen sulfide (H.sub.2S) to prepare a Cu.sub.2S film. The resulting metal sulfide thin film may be used in among other devices, photovoltaic devices, including interdigitated photovoltaic devices that may use relatively abundant materials for electrical energy production.

Uncharged positive electrode composition

DOEpatents

Kaun, Thomas D.; Vissers, Donald R.; Shimotake, Hiroshi

1977-03-08

An uncharged positive-electrode composition contains particulate lithium sulfide, another alkali metal or alkaline earth metal compound other than sulfide, e.g., lithium carbide, and a transition metal powder. The composition along with a binder, such as electrolytic salt or a thermosetting resin is applied onto an electrically conductive substrate to form a plaque. The plaque is assembled as a positive electrode within an electrochemical cell opposite to a negative electrode containing a material such as aluminum or silicon for alloying with lithium. During charging, lithium alloy is formed within the negative electrode and transition metal sulfide such as iron sulfide is produced within the positive electrode. Excess negative electrode capacity over that from the transition metal sulfide is provided due to the electrochemical reaction of the other than sulfide alkali metal or alkaline earth metal compound.

Ore genesis dating: implication of Sm-Nd method using sulfide minerals for mafic-ultramafic layered intrusions of Fennoscandian Shield

NASA Astrophysics Data System (ADS)

Serov, Pavel; Bayanova, Tamara; Steshenko, Ekaterina; Ekimova, Nadezhda

2015-04-01

The main method of dating the ore process was the Re-Os method of sulfides (Luck, Allegre, 1983; Walker et. al., 1991). However, studies of Re-Os systematics of sulfide minerals do not always give the correct ages and showing the disturbances of the Re-Os systematics. At the same time, Sm-Nd age of sulfides in good agreement with the U-Pb dating on zircon and baddeleyite and suggests that the Sm-Nd system of sulfides is more resistant to secondary alteration processes. Our studies have shown that along with rock-forming, ore minerals (sulfides) can be used to determine the ore genesis time of industrially important geological sites, since exactly with the sulfides the industry Pt-Pd mineralization is closely connected. In to Sm-Nd measurements steadily introduce new minerals-geochronometers (i.e. titanite, burbancite, eudialite etc.). Of these, sulfides of PGE-bearing layered intrusions are quite important in terms of dating the process of ore origin. Studying the REE distribution in the sulfides of MOR hydrothermal sources has shown possible REE presence in the sulfide lattice (Rimskaya-Korsakova et. al., 2003). These are difficult to carry out because the concentrations of Sm and Nd isotopes in sulfides are much lower than those in chondrites (Rimskaya-Korsakova et. al., 2003). In (Kong et. al., 2000) sulfides from two metamorphosed chondrites were studied by instrumental neutron activation analysis (INAA) and ion probe. As shown, the level of REE in the sulfide phase determined by the ion probe is quite similar to that obtained by INAA. Although the concentrations of REE in the enstatite and the Fe, Si, Cr-rich inclusions are comparable to those in sulfide, estimates based on mass balance calculations show that the silicate inclusions would not noticeably contribute to the REE budget in sulfides (Kong et. al., 2000). For the first time in Russian geochemistry laboratories using sulfide and rock-forming minerals and WR in Sm-Nd method have been dated impregnated and brecciform ores of the following objects - Pilguyarvi Cu-Ni deposits, Pechenga (1965±87 Ma); impregnated (2433±83 Ma) and redeposited (1903±24 Ma) ores of Ahmavaara intrusion (Finland); Kolvitsa massif metagabbro (1990±92 Ma, which reflect the age of Sm-Nd system closure in sulfide minerals); olivine orthopyroxenites of Sopcha 'Ore bed' (2442±59 Ma); ore gabbronorites of Penikat PGE-bearing layered intrusion (2426±38 Ma (Ekimova et.al., 2011); Pt-Pd gabbro-pegmatite ores (2476± 41 Ma, which agrees well with the U-Pb zircon age - 2470±9 Ma (Bayanova, 2004) and gabbronorites (2483±86 Ma) of PGE Kievey deposit and Fedorova Tundra metagabbroids (2494±54 Ma); Monchetundra gabbronorites - 2489±49 Ma. All investigations are devoted to memory of academician RAS, professor F. Mitrofanov (Russia), he was a leader of scientific school for geology, geochemistry and metallogenesis of ore deposits. The studies were supported by the RFBR 13-05-00493, OFI-M 13-05-12055, Department of Earth Sciences RAS (programs 2 and 4), IGCP-599.

Removal of insoluble heavy metal sulfides from water.

PubMed

Banfalvi, Gaspar

2006-05-01

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, H.W. Jr.; Horton, J.A.; Elliott, G.R.B.

1995-06-06

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO{sub 3}), or any other substantially stable uranium oxide, to form the uranium dioxide (UO{sub 2}). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl{sub 4}), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation. 4 figs.

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, Jr., Howard W.; Horton, James A.; Elliott, Guy R. B.

1995-01-01

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO.sub.3), or any other substantially stable uranium oxide, to form the uranium dioxide (UO.sub.2). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl.sub.4), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation.

Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

NASA Technical Reports Server (NTRS)

Righter, Kevin

2009-01-01

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Metallic sulfide additives for positive electrode material within a secondary electrochemical cell

DOEpatents

Walsh, William J.; McPheeters, Charles C.; Yao, Neng-ping; Koura, Kobuyuki

1976-01-01

An improved active material for use within the positive electrode of a secondary electrochemical cell includes a mixture of iron disulfide and a sulfide of a polyvalent metal. Various metal sulfides, particularly sulfides of cobalt, nickel, copper, cerium and manganese, are added in minor weight proportion in respect to iron disulfide for improving the electrode performance and reducing current collector requirements.

Remediation of arsenic-contaminated groundwater by in-situ stimulating biogenic precipitation of iron sulfides.

PubMed

Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Liu, Yaqing; Su, Chunli; Zhu, Yapeng; Wang, Zhiqiang

2017-02-01

Severe health problems due to elevated arsenic (As) in groundwater have made it urgent to develop cost-effective technologies for As removal. This field experimental study tested the feasibility of in-situ As immobilization via As incorporation into newly formed biogenic Fe(II) sulfides in a typical As-affected strongly reducing aquifer at the central part of Datong Basin, China. After periodic supply of FeSO 4 into the aquifer for 25 d to stimulate microbial sulfate reduction, dissolved sulfide concentrations increased during the experiment, but the supplied Fe(II) reacted quickly with sulfide to form Fe(II)-sulfides existing majorly as mackinawite as well as a small amount of pyrite-like minerals in sediments, thereby restricting sulfide build-up in groundwater. After the completion of field experiment, groundwater As concentration decreased from an initial average value of 593 μg/L to 159 μg/L, with an overall As removal rate of 73%, and it further declined to 136 μg/L adding the removal rate up to 77% in 30 d after the experiment. The arsenite/As total ratio gradually increased over time, making arsenite to be the predominant species in groundwater residual As. The good correlations between dissolved Fe(II), sulfide and As concentrations, the increased abundance of As in newly-formed Fe sulfides as well as the reactive-transport modeling results all indicate that As could have been adsorbed onto and co-precipitated with Fe(II)-sulfide coatings once microbial sulfate reduction was stimulated after FeSO 4 supply. Under the strongly reducing conditions, sulfide may facilitate arsenate reduction into arsenite and promote As incorporation into pyrite or arsenopyrite. Therefore, the major mechanisms for the in-situ As-contaminated groundwater remediation can be As surface-adsorption on and co-precipitation with Fe(II) sulfides produced during the experimental period. Copyright © 2016. Published by Elsevier Ltd.

Toxicity of sulfide to early life stages of wild rice (Zizania palustris).

PubMed

Fort, Douglas J; Todhunter, Kevin; Fort, Troy D; Mathis, Michael B; Walker, Rachel; Hansel, Mike; Hall, Scott; Richards, Robin; Anderson, Kurt

2017-08-01

The sensitivity of wild rice (Zizania palustris) to sulfide is not well understood. Because sulfate in surface waters is reduced to sulfide by anaerobic bacteria in sediments and historical information indicated that 10 mg/L sulfate in Minnesota (USA) surface water reduced Z. palustris abundance, the Minnesota Pollution Control Agency established 10 mg/L sulfate as a water quality criterion in 1973. A 21-d daily-renewal hydroponic study was conducted to evaluate sulfide toxicity to wild rice and the potential mitigation of sulfide toxicity by iron (Fe). The hydroponic design used hypoxic test media for seed and root exposure and aerobic headspace for the vegetative portion of the plant. Test concentrations were 0.3, 1.6, 3.1, 7.8, and 12.5 mg/L sulfide in test media with 0.8, 2.8, and 10.8 mg/L total Fe used to evaluate the impact of iron on sulfide toxicity. Visual assessments (i.e., no plants harvested) of seed activation, mesocotyl emergence, seedling survival, and phytoxicity were conducted 10 d after dark-phase exposure. Each treatment was also evaluated for time to 30% emergence (ET30), total plant biomass, root and shoot lengths, and signs of phytotoxicity at study conclusion (21 d). The results indicate that exposure of developing wild rice to sulfide at ≥3.1 mg sulfide/L in the presence of 0.8 mg/L Fe reduced mesocotyl emergence. Sulfide toxicity was mitigated by the addition of Fe at 2.8 mg/L and 10.8 mg/L relative to the control value of 0.8 mg Fe/L, demonstrating the importance of iron in mitigating sulfide toxicity to wild rice. Ultimately, determination of site-specific sulfate criteria taking into account factors that alter toxicity, including sediment Fe and organic carbon, are necessary. Environ Toxicol Chem 2017;36:2217-2226. © 2017 SETAC. © 2017 SETAC.

Energy metabolism and metabolomics response of Pacific white shrimp Litopenaeus vannamei to sulfide toxicity.

PubMed

Li, Tongyu; Li, Erchao; Suo, Yantong; Xu, Zhixin; Jia, Yongyi; Qin, Jian G; Chen, Liqiao; Gu, Zhimin

2017-02-01

The toxicity and poisoning mechanisms of sulfide were studied in Litopenaeus vannamei from the perspective of energy metabolism and metabolomics. The lethal concentrations of sulfide in L. vannamei (LC50) at 24h, 48h, 72h, and 96h were determined. Sulfide at a concentration of 0, 1/10 (425.5μg/L), and 1/5 (851μg/L) of the LC 50 at 96h was used to test the metabolic responses of L. vannamei for 21days. The chronic exposure of shrimp to a higher sulfide concentration of 851μg/L decreased shrimp survival but did not affect weight gain or the hepatopancreas index. The glycogen content in the hepatopancreas and muscle and the activity of hepatopancreas cytochrome C oxidase of the shrimp exposed to all sulfide concentrations were significantly lower, and the serum glucose and lactic acid levels and lactic acid dehydrogenase activity were significantly lower than those in the control. Metabolomics assays showed that shrimp exposed to sulfide had lower amounts of serum pyruvic acid, succinic acid, glycine, alanine, and proline in the 425.5μg/L group and phosphate, succinic acid, beta-alanine, serine, and l-histidine in the 851μg/L group than in the control. Chronic sulfide exposure could disturb protein synthesis in shrimp but enhance gluconeogenesis and substrate absorption for ATP synthesis and tricarboxylic acid cycles to provide extra energy to cope with sulfide stress. Chronic sulfide exposure could adversely affect the health status of L. vannamei, as indicated by the high amounts of serum n-ethylmaleamic acid, pyroglutamic acid, aspartic acid and phenylalanine relative to the control. This study indicates that chronic exposure of shrimp to sulfide can decrease health and lower survival through functional changes in gluconeogenesis, protein synthesis and energy metabolism. Copyright © 2016 Elsevier B.V. All rights reserved.

Transition of Blast Furnace Slag from Silicate Based to Aluminate Based: Sulfide Capacity

NASA Astrophysics Data System (ADS)

Yan, Zhiming; Lv, Xuewei; Pang, Zhengde; He, Wenchao; Liang, Dong; Bai, Chenguang

2017-10-01

The effect of Al2O3 and Al2O3/SiO2 ratio on the sulfide capacity of the molten aluminosilicate CaO-SiO2-Al2O3-MgO-TiO2 slag system with high Al2O3 content was measured at 1773 K (1500 °C) using a metal-slag equilibration method. The sulfide capacity between silicate-based and aluminate-based slag was also compared based on the thermodynamic analysis and structural characteristics of melts. At a fixed CaO/SiO2 ratio of 1.20, the sulfide capacity decreases with increasing Al2O3 content primarily due to the decrease of free oxygen (FO) and the activity of O2-. Increasing the Al2O3/SiO2 ratio from 0.47 to 0.79 causes a significant increase in the sulfide capacity of the slags, and a slight increase is found when the Al2O3/SiO2 ratio is more than 0.79. The effect of the substitution of silica by alumina on the sulfide capacity of the slags was not only due to an increase in the activity of basic oxides ( a_{{{O}^{2 - } }} ) but also to a decrease in the stability of sulfide ( γ_{{{S}^{2 - } }} ). Moreover, a_{{{O}^{2 - } }} and γ_{{{S}^{2 - } }} increase in a similar degree, and the weaker binding electronegativity of Al3+ with oxygen atoms results in a slight increase in the final sulfide capacity in the aluminate-based slag system with Al2O3 ↔ SiO2 substitution. Five different sulfide capacity models were employed to predict the sulfide capacity, and the iso-sulfide capacity distribution diagram based on the Young's model was obtained in the high Al2O3 corner of the diagram.

A Reaction Involving Oxygen and Metal Sulfides.

ERIC Educational Resources Information Center

Hill, William D. Jr.

1986-01-01

Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

Quantitative determination of polysulfide in albumins, plasma proteins and biological fluid samples using a novel combined assays approach.

PubMed

Ikeda, Mayumi; Ishima, Yu; Shibata, Akitomo; Chuang, Victor T G; Sawa, Tomohiro; Ihara, Hideshi; Watanabe, Hiroshi; Xian, Ming; Ouchi, Yuya; Shimizu, Taro; Ando, Hidenori; Ukawa, Masami; Ishida, Tatsuhiro; Akaike, Takaaki; Otagiri, Masaki; Maruyama, Toru

2017-05-29

Hydrogen sulfide (H 2 S) signaling involves polysulfide (RSS n SR') formation on various proteins. However, the current lack of sensitive polysulfide detection assays poses methodological challenges for understanding sulfane sulfur homeostasis and signaling. We developed a novel combined assay by modifying Sulfide Antioxidant Buffer (SAOB) to produce an "Elimination Method of Sulfide from Polysulfide" (EMSP) treatment solution that liberates sulfide, followed with methylene blue (MB) sulfide detection assay. The combined EMSP-MB sulfide detection assay performed on low molecular weight sulfur species showed that sulfide was produced from trisulfide compounds such as glutathione trisulfide and diallyl trisulfide, but not from the thiol compounds such as cysteine, cystine and glutathione. In the case of plasma proteins, this novel combined detection assay revealed that approximately 14.7, 1.7, 3.9, 3.7 sulfide mol/mol released from human serum albumin, α 1 -anti-trypsin, α 1 -acid glycoprotein and ovalbumin, respectively, suggesting that serum albumin is a major pool of polysulfide in human blood circulation. Taken together with the results of albumins of different species, the liberated sulfide has a good correlation with cysteine instead of methionine, indicating the site of incorporation of polysulfide is cysteine. With this novel sulfide detention assay, approximately 8,000, 120 and 1100 μM of polysulfide concentrations was quantitated in human healthy plasma, saliva and tear, respectively. Our promising polysulfide specific detection assay can be a very important tool because quantitative determination of polysulfide sheds light on the functional consequence of protein-bound cysteine polysulfide and expands the research area of reactive oxygen to reactive polysulfide species. Copyright © 2017 Elsevier B.V. All rights reserved.

Textural, mineralogical and stable isotope studies of hydrothermal alteration in the main sulfide zone of the Great Dyke, Zimbabwe and the precious metals zone of the Sonju Lake Intrusion, Minnesota, USA

USGS Publications Warehouse

Li, C.; Ripley, E.M.; Oberthur, T.; Miller, J.D.; Joslin, G.D.

2008-01-01

Stratigraphic offsets in the peak concentrations of platinum-group elements (PGE) and base-metal sulfides in the main sulfide zone of the Great Dyke and the precious metals zone of the Sonju Lake Intrusion have, in part, been attributed to the interaction between magmatic PGE-bearing base-metal sulfide assemblages and hydrothermal fluids. In this paper, we provide mineralogical and textural evidence that indicates alteration of base-metal sulfides and mobilization of metals and S during hydrothermal alteration in both mineralized intrusions. Stable isotopic data suggest that the fluids involved in the alteration were of magmatic origin in the Great Dyke but that a meteoric water component was involved in the alteration of the Sonju Lake Intrusion. The strong spatial association of platinum-group minerals, principally Pt and Pd sulfides, arsenides, and tellurides, with base-metal sulfide assemblages in the main sulfide zone of the Great Dyke is consistent with residual enrichment of Pt and Pd during hydrothermal alteration. However, such an interpretation is more tenuous for the precious metals zone of the Sonju Lake Intrusion where important Pt and Pd arsenides and antimonides occur as inclusions within individual plagioclase crystals and within alteration assemblages that are free of base-metal sulfides. Our observations suggest that Pt and Pd tellurides, antimonides, and arsenides may form during both magmatic crystallization and subsolidus hydrothermal alteration. Experimental studies of magmatic crystallization and hydrothermal transport/deposition in systems involving arsenides, tellurides, antimonides, and base metal sulfides are needed to better understand the relative importance of magmatic and hydrothermal processes in controlling the distribution of PGE in mineralized layered intrusions of this type. ?? Springer-Verlag 2007.

Lifting of Administrative Stay for Hydrogen Sulfide

EPA Pesticide Factsheets

EPA lifted the Administrative Stay of the TRI reporting requirements for hydrogen sulfide. Hydrogen sulfide can reasonably be anticipated to cause chronic health effects in humans and significant adverse effects in aquatic organisms.

Production and Preservation of Sulfide Layering in Mercury's Magma Ocean

NASA Astrophysics Data System (ADS)

Boukare, C.-E.; Parman, S. W.; Parmentier, E. M.; Anzures, B. A.

2018-05-01

Mercury's magma ocean (MMO) would have been sulfur-rich. At some point during MMO solidification, it likely became sulfide saturated. Here we present physiochemical models exploring sulfide layer formation and stability.

Influence of sulfides on the tribological properties of composites produced by pulse electric current sintering

NASA Astrophysics Data System (ADS)

Kim, Seung Ho

2014-01-01

Self-lubricating Al2O3-15wt% ZrO2 composites with sulfides, such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) serving as solid lubricants, were fabricated by using the pulse electric current sintering (PECS) technique. The coefficient of friction (COF) of the Al2O3-15wt% ZrO2 composite without/with sulfides was in the range of 0.37-0.48 and 0.27-0.49, respectively. As the amount of sulfides increased, the COF and the wear rate decreased. The reduction in COF and wear rate of the sulfide-containing composite is caused by a reduction in shear stresses between the specimen and the tribological medium due to the formation of a lubricating film resulting from the lamellar structure of sulfides located on the worn surface.

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

USGS Publications Warehouse

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

2016-01-01

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

Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

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

Gevertz, D.; Zimmerman, S.; Jenneman, G.E.

1995-12-31

The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfidemore » oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.« less

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

Technetium Reduction and Permanent Sequestration by Abiotic and Biotic Formation of Low-Solubility Sulfide Mineral Phases

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

Tratnyek, Paul G.; Tebo, Bradley M.; Fan, Dimin

One way to minimize the mobility of the Tc VII oxyanion pertechnetate (TcO 4 -) is to effect reduction under sulfidogenic conditions (generated abiotically by Fe 0 or biotically) to form TcS x, which is significantly slower to oxidize than Tc IVO 2. In sediment systems, TcS x and other precipitates may oxidize more slowly due to oxygen diffusion limitations to these low permeability precipitate zones. In addition, the TcO 4 - reduction rate may be more rapid in the presence of sediment because of additional reductive surface phases. This project aims to provide a fundamental understanding of the feasibilitymore » of immobilization of TcO 4 - as TcS x in the vadose zone or groundwater by application nano zero-valent iron (nZVI), and sulfide or sulfate. Biotic batch experiments have used the sulfate-reducing bacterium (SRB) Desulfotomaculum reducens. The iron sulfide mineral mackinawite was generated under these conditions, while vivianite was formed in nZVI only controls. The sulfide/bacteria-containing system consistently reduced aqueous pertechnetate rapidly (> 95% in the first hour), a rate similar to that for the sulfide-free, nZVI only system. Reduced Tc (aged for 3 months) generated in both SRB/nZVI systems was highly resistant to reoxidation. In reduced samples, Tc was found associated with solid phases containing Fe and S (D. reducens/nZVI) or Fe (nZVI only). Experiments using D. reducens without nZVI provided some additional insights. Firstly, stationary phase cultures were able to slowly reduce pertechnetate. Secondly, addition of pertechnetate at the beginning of cell growth (lag phase) resulted in a faster rate of Tc reduction, possibly indicating a direct (e.g. enzymatic) role for D. reducens in Tc reduction. Abiotic batch experiments were conducted with Na 2S as the sulfide source. Pertechnetate reduction was rapid in the presence of sulfide and nZVI, although the rate was suppressed at the higher S/Fe ratios tested. This suppression appeared to be due to the formation of Tc-containing colloids. As with the biotic experiments, pertechnetate reduced under sulfidic conditions was highly resistant to reoxidation. The microscopic morphology of abiotically-transformed nZVI particles varied significantly with those in the biotic experiment, although mackinawite was formed in both systems (as indicated by μXRD and Mössbauer spectroscopy). Preliminary XAS analysis pointed to a mixture of Tc-O and Tc-S binding in the abiotic sulfide/nZVI system, while the major reduced solids under non-sulfidic conditions were TcO 2•nH 2O. The presence of sediment and advective flow to the TcO 4 -/nZVI/sulfide system results in additional processes occurring. Although the natural Hanford sediment used has sufficient available ferrous iron to slowly reduce TcO 4 -, under anaerobic conditions, that rate is orders of magnitude slower than reduction by nZVI/sulfide. Batch and 1-D column experiments showed that the TcO 4 - reduction rate increased with the sediment surface area (with the same nZVI mass). As in batch systems, column studies showed that the presence of sulfide with TcO 4 - at low (2-5 mM) concentrations increased the TcO 4 - reduction rate and high (10-30 mM) sulfide decreased the rate. This change is attributed to the formation of sulfide precipitates on the nZVI and sediment surfaces. Injection of low and high sulfide (i.e. pretreatment) prior to TcO 4 -/sulfide injection also greatly decreased the TcO 4 - reduction rate, likely decreasing the generation of ferrous iron from the nZVI. Although the high sulfide systems have slower Tc reduction rates, 190 times more Tc mass precipitated than in the low sulfide systems and the highest fraction of Tc mass remained immobilized.« less

DISSOLUTION OF PLUTONIUM CONTAINING CARRIER PRECIPITATE BY CARBONATE METATHESIS AND SEPARATION OF SULFIDE IMPURITIES THEREFROM BY SULFIDE PRECIPITATION

DOEpatents

Duffield, R.B.

1959-07-14

A process is described for recovering plutonium from foreign products wherein a carrier precipitate of lanthanum fluoride containing plutonium is obtained and includes the steps of dissolving the carrier precipitate in an alkali metal carbonate solution, adding a soluble sulfide, separating the sulfide precipitate, adding an alkali metal hydroxide, separating the resulting precipitate, washing, and dissolving in a strong acid.

Acid Volatile Sulfides and Simultaneously Extracted Copper, Lead, and Zinc in Sediments of Sinclair Inlet, Washington

DTIC Science & Technology

1993-09-01

to Doug Vaught, J. Towell, and Eric Schlierman of Puget Sound Naval Shipyard for providing laboratory space, equipment, and logistical support for the...availability and mobility of toxic metal contamination in the sediments of Sinclair Inlet, Puget Sound , Washington, acid volatile sulfide (AVS) and... Puget Sound , Washington ........ 1 2. Apparatus used for measuring acid volatile sulfides ........................... 5 3. Sulfide electrode

Measurement of plasma hydrogen sulfide in vivo and in vitro

PubMed Central

Shen, Xinggui; Pattillo, Christopher B.; Pardue, Sibile; Bir, Shyamal C.; Wang, Rui; Kevil, Christopher G.

2015-01-01

The gasotransmitter hydrogen sulfide is known to regulate multiple cellular functions during normal and pathophysiological states. However, a paucity of concise information exists regarding quantitative amounts of hydrogen sulfide involved in physiological and pathological responses. This is primarily due to disagreement among various methods employed to measure free hydrogen sulfide. In this article, we describe a very sensitive method of measuring the presence of H2S in plasma down to nanomolar levels, using monobromobimane (MBB). The current standard assay using methylene blue provides erroneous results that do not actually measure H2S. The method presented herein involves derivatization of sulfide with excess MBB in 100 mM Tris–HCl buffer (pH 9.5, 0.1 mM DTPA) for 30 min in 1% oxygen at room temperature. The fluorescent product sulfide-dibimane (SDB) is analyzed by RP-HPLC using an eclipse XDB-C18 (4.6×250 mm) column with gradient elution by 0.1% (v/v) trifluoroacetic acid in acetonitrile. The limit of detection for sulfide-dibimane is 2 nM and the SDB product is very stable over time, allowing batch storage and analysis. In summary, our MBB method is suitable for sensitive quantitative measurement of free hydrogen sulfide in multiple biological samples such as plasma, tissue and cell culture lysates, or media. PMID:21276849

Porous, S-bearing silica in metal-sulfide nodules and in the interchondrule clastic matrix in two EH3 chondrites

NASA Astrophysics Data System (ADS)

Lehner, S. W.; Németh, P.; Petaev, M. I.; Buseck, P. R.

2017-11-01

Two new occurrences of porous, S-bearing, amorphous silica are described within metal-sulfide nodules (MSN) and as interchondrule patches in EH3 chondrites SAH 97072 and ALH 84170. This porous amorphous material, which was first reported from sulfide-bearing chondrules, consists of sinewy SiO2-rich areas containing S with minor Na or Ca as well as Fe, Mg, and Al. Some pores contain minerals including pyrite, pyrrhotite, and anhydrite. Most pores appear vacant or contain unidentified material that is unstable under analytical conditions. Niningerite, olivine, enstatite, albite, and kumdykolite occur enclosed within porous silica patches. Porous silica is commonly interfingered with cristobalite suggesting its amorphous structure resulted from high-temperature quenching. We interpret the S-bearing porous silica to be a product of silicate sulfidation, and the Na, Ca, Fe, Mg, and Al detectable within this material are chemical residues of sulfidized silicates and metal. The occurrence of porous silica in the cores of MSN, which are considered to be pre-accretionary objects, suggests the sulfidizing conditions occurred prior to final parent-body solidification. Ubiquitous S-bearing porous silica among sulfide-bearing chondrules, MSN, and in the interchondrule clastic matrix, suggests that similar sulfidizing conditions affected all the constituents of these EH3 chondrites.

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

2008-01-01

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

PubMed

Khanal, Samir Kumar; Huang, Ju-Chang

2006-04-01

A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.

Sulfide toxicity: Mechanical ventilation and hypotension determine survival rate and brain necrosis

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

Baldelli, R.J.; Green, F.H.Y.; Auer, R.N.

1993-09-01

Occupational exposure to hydrogen sulfide is one of the leading causes of sudden death in the workplace, especially in the oil and gas industry. High-dose exposure causes immediate neurogenic apnea and death; lower doses cause [open quotes]knockdown[close quotes] (transient loss of consciousness, with apnea). Because permanent neurological sequelae have been reported, the authors sought to determine whether sulfide can directly kill central nervous system neurons. Ventilated and unventilated rats were studied to allow administration of higher doses of sulfide and to facilitate physiological monitoring. It was extremely difficult to produce cerebral necrosis with sulfide. Only one of eight surviving unventilatedmore » rats given high-dose sulfide (a dose that was lethal in [ge]50% of animals) showed cerebral necrosis. Mechanical ventilation shifted the dose that was lethal in 50% of the animals to 190 mg/kg from 94 mg/kg in the unventilated rats. Sulfide was found to potently depress blood pressure. Cerebral necrosis was absent in the ventilated rats (n = 11), except in one rat that showed profound and sustained hypotension to [le]35 Torr. Electroencephalogram activity ceased during exposure but recovered when the animals regained consciousness. The authors conclude that very-high-dose sulfide is incapable of producing cerebral necrosis by a direct histotoxic effect. 32 refs., 5 figs.« less

Prevention of sulfide oxidation in sulfide-rich waste rock

NASA Astrophysics Data System (ADS)

Nyström, Elsa; Alakangas, Lena

2015-04-01

The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

Effects of sulfide concentration and dissolved organic matter characteristics on the structure of nanocolloidal metacinnabar

USGS Publications Warehouse

Poulin, Brett; Gerbig, Chase A.; Kim, Christopher S.; Stegemeier, John P.; Ryan, Joseph N.; Aiken, George R.

2017-01-01

Understanding the speciation of divalent mercury (Hg(II)) in aquatic systems containing dissolved organic matter (DOM) and sulfide is necessary to predict the conversion of Hg(II) to bioavailable methylmercury. We used X-ray absorption spectroscopy to characterize the structural order of mercury in Hg(II)–DOM–sulfide systems for a range of sulfide concentration (1–100 μM), DOM aromaticity (specific ultraviolet absorbance (SUVA254)), and Hg(II)–DOM and Hg(II)–DOM–sulfide equilibration times (4–142 h). In all systems, Hg(II) was present as structurally disordered nanocolloidal metacinnabar (β-HgS). β-HgS nanocolloids were significantly smaller or less ordered at lower sulfide concentration, as indicated by under-coordination of Hg(II) in β-HgS. The size or structural order of β-HgS nanocolloids increased with increasing sulfide abundance and decreased with increasing SUVA254 of the DOM. The Hg(II)–DOM or Hg(II)–DOM–sulfide equilibration times did not significantly influence the extent of structural order in nanocolloidal β-HgS. Geochemical factors that control the structural order of nanocolloidal β-HgS, which are expected to influence nanocolloid surface reactivity and solubility, should be considered in the context of mercury bioavailability.

Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition.

PubMed

Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

2010-07-15

The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed. 2010 Elsevier B.V. All rights reserved.

Corrosion Behavior of Cu40Zn in Sulfide-Polluted 3.5% NaCl Solution

NASA Astrophysics Data System (ADS)

Song, Q. N.; Xu, N.; Bao, Y. F.; Jiang, Y. F.; Gu, W.; Yang, Z.; Zheng, Y. G.; Qiao, Y. X.

2017-10-01

The corrosion behavior of a duplex-phase brass Cu40Zn in clean and sulfide-polluted 3.5% NaCl solutions was investigated by conducting electrochemical and gravimetric measurements. The corrosion product films were analyzed by scanning electron microscopy, energy-dispersive spectroscopy and x-ray diffraction. The presence of sulfide shifted the corrosion potential of Cu40Zn toward a more negative value by 100 mV and increased the mass loss rate by a factor of 1.257 compared with the result in the clean solution. The corrosion product film in the clean solution was thin and compact; it mainly consisted of oxides, such as ZnO and Cu2O. By contrast, the film in the sulfide-polluted solution was thick and porous. It mainly contained sulfides and zinc hydroxide chloride (i.e., Zn5(OH)8Cl2·H2O). The presence of sulfide ions accelerated the corrosion damage of Cu40Zn by hindering the formation of protective oxides and promoting the formation of a defective film which consisted of sulfides and hydroxide chlorides.

Occurrence model for magmatic sulfide-rich nickel-copper-(platinum-group element) deposits related to mafic and ultramafic dike-sill complexes: Chapter I in Mineral deposit models for resource assessment

USGS Publications Warehouse

Schulz, Klaus J.; Woodruff, Laurel G.; Nicholson, Suzanne W.; Seal, Robert R.; Piatak, Nadine M.; Chandler, Val W.; Mars, John L.

2014-01-01

The sulfides in magmatic Ni-Cu deposits generally constitute a small volume of the host rock(s) and tend to be concentrated in the lower parts of the mafic and/or ultramafic bodies, often in physical depressions or areas marking changes in the geometry of the footwall topography. In most deposits, the sulfide mineralization can be divided into disseminated, matrix or net, and massive sulfide, depending on a combination of the sulfide content of the rock and the silicate texture. The major Ni-Cu sulfide mineralogy typically consists of an intergrowth of pyrrhotite (Fe7S8), pentlandite ([Fe, Ni]9S8), and chalcopyrite (FeCuS2). Cobalt, PGE, and gold (Au) are extracted from most magmatic Ni-Cu ores as byproducts, although such elements can have a significant impact on the economics in some deposits, such as the Noril’sk-Talnakh deposits, which produce much of the world’s palladium. In addition, deposits may contain between 1 and 15 percent magnetite associated with the sulfides.

Al/sub 2/S/sub 3/ preparation and use in electrolysis process for aluminum production

DOEpatents

Hsu, C.C.; Loutfy, R.O.; Yao, N.P.

A continuous process for producing aluminum sulfide and for electrolyzing the aluminum sulfide to form metallic aluminum in which the aluminum sulfide is produced from aluminum oxide and COS or CS/sub 2/ in the presence of a chloride melt which also serves as the electrolysis bath. Circulation between the reactor and electrolysis cell is carried out to maintain the desired concentration of aluminum sulfide in the bath.

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides.

PubMed

Jood, Priyanka; Ohta, Michihiro

2015-03-16

Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS₂-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS₂ sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor.

The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

PubMed Central

Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

2013-01-01

Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

Iron and sulfur in the pre-biologic ocean

NASA Technical Reports Server (NTRS)

Walker, J. C.; Brimblecombe, P.

1985-01-01

Tentative geochemical cycles for the pre-biologic Earth are developed by comparing the relative fluxes of oxygen, dissolved iron, and sulfide to the atmosphere and ocean. The flux of iron is found to exceed both the oxygen and the sulfide fluxes. Because of the insolubility of iron oxides and sulfides the implication is that dissolved iron was fairly abundant and that oxygen and sulfide were rare in the atmosphere and ocean. Sulfate, produced by the oxidation of volcanogenic sulfur gases, was the most abundant sulfur species in the ocean, but its concentration was low by modern standards because of the absence of the river-borne flux of dissolved sulfate produced by oxidative weathering of the continents. These findings are consistent with the geologic record of the isotopic composition of sedimentary sulfates and sulfides. Except in restricted environments, the sulfur metabolism of the earliest organisms probably involved oxidized sulfur species not sulfide.

Phase relations in the Fe-Ni-Cr-S system and the sulfidation of an austenitic stainless steel

NASA Technical Reports Server (NTRS)

Jacob, K. T.; Rao, D. B.; Nelson, H. G.

1977-01-01

The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr and Fe-Cr-Ni alloys were developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary system were displayed on plots of log P sub S sub 2 versus the conjugate extensive variable which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase diagram data of geophysical literature. These constructed stability field diagrams were in excellent agreement with the sulfide phases and compositions determined during a sulfidation experiment.

Synthesis and Optical Properties of MnS–ZnS and MnS–CdS Nanoparticles in Montmorillonite.

PubMed

Kabilaphat, Jirabhorn; Poosimma, Poonsuk; Khaorapapong, Nithima; Intachai, Sonchai; Ogawa, Makoto

2017-02-01

The incorporation of metal sulfide mixture, manganese sulfide and zinc sulfide (MnS–ZnS) or manganese sulfide and cadmium sulfide (MnS–CdS), in two types of montmorillonites (sodium montmorillonite and cetyltrimethylammonium modified montmorillonite) was investigated. The hybrids were characterized by powder X-ray diffraction, thermogravimetric-differential thermal analysis, transmission electron microscopy (TEM), and Raman, UV-visible and photoluminescence spectroscopies. The experimental evidences such as the expansion of the interlayer spaces and the presence of the absorption and photoluminescence due to MnS, ZnS and/or CdS revealed that the mixed metal sulfides formed in the interlayer space of montmorillonites. TEM images of the hybrids showed diskor plate-shaped nanoparticles with a mean diameter of ca. 2 nm. The increase of the luminescence intensities of the hybrids was assumed to be caused by quantum confinement effect in the interlayer space of montmorillonite.

Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

PubMed Central

Jood, Priyanka; Ohta, Michihiro

2015-01-01

Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS2-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS2 sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor. PMID:28787992

Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

NASA Technical Reports Server (NTRS)

Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III

1993-01-01

A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

Response of gut health and microbiota to sulfide exposure in Pacific white shrimp Litopenaeus vannamei.

PubMed

Suo, Yantong; Li, Erchao; Li, Tongyu; Jia, Yongyi; Qin, Jian G; Gu, Zhimin; Chen, Liqiao

2017-04-01

Sulfide is a natural and widely distributed toxicant. It can be commonly found on the interface between water and sediment in the aquatic environment. The Pacific white shrimp Litopenaeus vannamei starts life in the benthic zone soon after the mysis stage, an early stage of post larvae. Therefore, L. vannamei is inevitably affected by exposure to sulfide released from pond sediment. This study explored the toxicant effect of different concentrations of sulfide on the intestinal health and microbiota of Pacific white shrimp by monitoring the change of expression of inflammatory, immune related cytokines, and the structure of the intestinal microbiota. The gut histology, expressions of inflammatory and immune related cytokines (tumor necrosis factor-alpha, C-type lectin 3, myostatin and heat shock transcription factor 1), and the microbiota were determined in L. vannamei after exposure to 0 (control), 425.5 (1/10 LC 50-96 h), and 851 μg/L (1/5 LC 50-96 h) of sulfide for 21 days. With the increase of sulfide concentration, intestinal injury was aggravated and the inflammatory and immune related cytokines generated a range of reactions. The expression of myostatin (MSTN) was significantly down-regulated by the concentration of sulfide exposure. No difference in the expression of heat shock transcription factor 1 (HSF1) was found between the control and shrimp exposed to 425.5 μg/L, but significantly higher HSF1 expression was found in shrimp exposed to 851 μg/L of sulfide. Significantly higher values of tumor necrosis factor-alpha (TNF-α) and C-type lectin 3 (CTL3) were found in the shrimp exposed to 425.5 μg/L of sulfide compared to the control, but a lower value was found in the shrimp exposed to 851 μg/L (P < 0.05). Sulfide also changed the intestinal microbial communities. The abundance of pathogenic bacteria, such as Cyanobacteria, Vibrio and Photobacterium, increased significantly with exposure to the increasing concentration of sulfide. The abundance of some anti-stress bacteria, such as Chlorobi and Fusobacterium, increased. Nitrospirae which can alleviate nitrite toxicity decreased. Microbacterium, Parachlamydia, and Shewanella were all commonly found and down-regulated in both sulfide groups, which is associated with an adaptation to sulfide stimulation. This study indicates that chronic exposure to sub-lethal levels of sulfide could lead to damage of the gut structure, stimulate the response of the inflammatory and immune systems, and shape the structure of the gut microbiota in L. vannamei. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ecological release and niche partitioning under stress: Lessons from dorvilleid polychaetes in sulfidic sediments at methane seeps

NASA Astrophysics Data System (ADS)

Levin, Lisa A.; Ziebis, Wiebke; Mendoza, Guillermo F.; Bertics, Victoria J.; Washington, Tracy; Gonzalez, Jennifer; Thurber, Andrew R.; Ebbe, Brigitte; Lee, Raymond W.

2013-08-01

Organisms inhabiting methane seep sediments are exposed to stress in the form of high levels of hydrogen sulfide, which result mainly from sulfate reduction coupled to anaerobic methane oxidation. Dorvilleidae (Polychaeta) have successfully invaded this ecosystem, and multiple species in divergent genetic clades co-occur at high densities. At methane seeps in the NE Pacific off California and Oregon, the genera Ophryotrocha, Parougia and Exallopus are especially well represented. To test the hypothesis that dorvilleid coexistence is facilitated by niche partitioning through sulfide tolerance and trophic patterns, we examined dorvilleid species-specific patterns of occurrence and nutrition at methane seeps off Eel R. [ER] on the Californian continental slope and at Hydrate Ridge [HR] on the Oregon continental slope, and in two habitats (clam bed and microbial mat) characterized by lower and higher hydrogen sulfide levels, respectively. Microelectrode measurements of hydrogen sulfide enabled characterization of environmental sulfide levels for species sampled in background sediment cores and in colonization trays. Dorvilleids tolerated H2S levels from 10 μM to over 2.6 mM, with the majority of species inhabiting sediments with similar environmental H2S concentrations (median 85-100 μM). Dorvilleid species richness was greater at HR than ER, but did not differ between clam bed and microbial mat habitats. Species distribution patterns reflected preferences for ER clam bed (lower sulfide levels), ER mat and HR clam bed (moderate sulfide levels), or HR mat (very high sulfide levels). Nutritional patterns, including trophic diversity and functional similarity, were examined using community stable isotope metrics based on δ15N and δ13C. Within each region, dorvilleid species exhibited multiple trophic strategies. Co-existing congeners typically exhibited distinct isotope signatures, suggesting trophic partitioning. Trophic diversity and δ15N range for whole assemblages (measured by Total Hull Area and Standard Elliptical Area using species averages) and functional redundancy or species packing (measured as distance to nearest neighbor) among species and individuals were generally higher at ER, where sulfide levels were lower than at HR. In contrast, average trophic diversity among individuals within a species was greater at HR than ER. In colonization experiments involving agar-based manipulations of sulfide in tray sediments that mimicked clam bed and mat conditions, dorvilleids comprised 68% and 48% of colonists at ER and HR, respectively. Dorvilleid species richness was higher in trays that were initially more sulfidic. However, habitat exerted stronger influence on the composition of colonizing dorvilleids than did sulfide additions. In the NE Pacific, regional, habitat and vertical (down-core) variation in hydrogen sulfide creates complex environmental heterogeneity at methane seeps, promoting high diversity of stress-tolerant taxa such as dorvilleid polychaetes.

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

Sulfur isotope patterns of iron sulfide and barite nodules in the Upper Cretaceous Chalk of England and their regional significance in the origin of coloured chalks

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Turchyn, Alexandra V.; Hu, Xu-Fang

2016-06-01

The relationship between the development of iron sulfide and barite nodules in the Cenomanian Chalk of England and the presence of a red hematitic pigment has been investigated using sulfur isotopes. In southern England where red and pink chalks are absent, iron sulfide nodules are widespread. Two typical large iron sulfide nodules exhibit δ34S ranging from -48.6‰ at their core to -32.6‰ at their outer margins. In eastern England, where red and pink chalks occur in three main bands, there is an antipathetic relationship between the coloured chalks and the occurrence of iron sulfide or barite nodules. Here iron sulfide, or its oxidised remnants, are restricted to two situations: (1) in association with hard grounds that developed originally in chalks that contained the hematite pigment or its postulated precursor FeOH3, or (2) in regional sulfidization zones that cut across the stratigraphy. In the Cenomanian Chalk exposed in the cliffs at Speeton, Yorkshire, pyrite and marcasite (both iron sulfide) nodules range in δ34S from -34.7‰ to +40.0‰. In the lower part of the section δ34S vary from -34.8‰ to +7.8‰, a single barite nodule has δ34S between +26.9‰ and +29.9‰. In the middle part of the section δ34S ranges from +23.8‰ to +40.0‰. In the sulfidization zones that cut across the Cenomanian Chalk of Lincolnshire the iron sulfide nodules are typically heavily weathered but these may contain patches of unoxidised pyrite. In these zones, δ34S ranges from -32.9‰ to +7.9‰. The cross-cutting zones of sulfidization in eastern England are linked to three basement faults - the Flamborough Head Fault Zone, the Caistor Fault and the postulated Wash Line of Jeans (1980) - that have affected the deposition of the Chalk. It is argued that these faults have been both the conduits by which allochthonous fluids - rich in hydrogen sulfide/sulfate, hydrocarbons and possibly charged with sulfate-reducing bacteria - have penetrated the Cenomanian Chalk as the result of movement during the Late Cretaceous or Cenozoic. These invasive fluids are associated with (1) the reduction of the red hematite pigment or its praecursor, (2) the subsequent development of both iron sulfides and barite, and (3) the loss of overpressure in the Cenomanian Chalk and its late diagenetic hardening by anoxic cementation. Evidence is reviewed for the origin of the red hematite pigment of the coloured chalks and for the iron involved in the development of iron sulfides, a hydrothermal or volcanogenic origin is favoured.

Dechlorination of chloropicrin and 1,3-dichloropropene by hydrogen sulfide species: redox and nucleophilic substitution reactions.

PubMed

Zheng, Wei; Yates, Scott R; Papiernik, Sharon K; Guo, Mingxin; Gan, Jianying

2006-03-22

The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.

Hydrogen sulfide measurement using sulfide dibimane: critical evaluation with electrospray ion trap mass spectrometry

PubMed Central

Shen, Xinggui; Chakraborty, Sourav; Dugas, Tammy R; Kevil, Christopher G

2015-01-01

Accurate measurement of hydrogen sulfide bioavailability remains a technical challenge due to numerous issues involving sample processing, detection methods used, and actual biochemical products measured. Our group and others have reported that reverse phase HPLC detection of sulfide dibimane (SDB) product from the reaction of H2S/HS− with monobromobimane allows for analytical detection of hydrogen sulfide bioavailability in free and other biochemical forms. However, it remains unclear whether possible interfering contaminants may contribute to HPLC SDB peak readings that may result in inaccurate measurements of bioavailable sulfide. In this study, we critically compared hydrogen sulfide dependent SDB detection using reverse phase HPLC (RP-HPLC) versus quantitative SRM electrospray ionization mass spectrometry (ESI/MS) to obtain greater clarity into the validity of the reverse phase HPLC method for analytical measurement of hydrogen sulfide. Using an LCQ-deca ion-trap mass spectrometer, SDB was identified by ESI/MS positive ion mode, and quantified by selected reaction monitoring (SRM) using hydrocortisone as an internal standard. Collision induced dissociation (CID) parameters were optimized at MS2 level for SDB and hydrocortisone. ESI/MS detection of SDB standard was found to be a log order more sensitive than RP-HPLC with a lower limit of 0.25 nM. Direct comparison of tissue and plasma SDB levels using RP-HPLC and ESI/MS methods revealed comparable sulfide levels in plasma, aorta, heart, lung and brain. Together, these data confirm the use of SDB as valid indicator of H2S bioavailability and highlights differences between analytical detection methods. PMID:24932544

Polysulfides as Intermediates in the Oxidation of Sulfide to Sulfate by Beggiatoa spp.

PubMed Central

Schwedt, Anne; Kreutzmann, Anne-Christin; Kuypers, Marcel M. M.; Milucka, Jana

2014-01-01

Zero-valent sulfur is a key intermediate in the microbial oxidation of sulfide to sulfate. Many sulfide-oxidizing bacteria produce and store large amounts of sulfur intra- or extracellularly. It is still not understood how the stored sulfur is metabolized, as the most stable form of S0 under standard biological conditions, orthorhombic α-sulfur, is most likely inaccessible to bacterial enzymes. Here we analyzed the speciation of sulfur in single cells of living sulfide-oxidizing bacteria via Raman spectroscopy. Our results showed that under various ecological and physiological conditions, all three investigated Beggiatoa strains stored sulfur as a combination of cyclooctasulfur (S8) and inorganic polysulfides (Sn2−). Linear sulfur chains were detected during both the oxidation and reduction of stored sulfur, suggesting that Sn2− species represent a universal pool of bioavailable sulfur. Formation of polysulfides due to the cleavage of sulfur rings could occur biologically by thiol-containing enzymes or chemically by the strong nucleophile HS− as Beggiatoa migrates vertically between oxic and sulfidic zones in the environment. Most Beggiatoa spp. thus far studied can oxidize sulfur further to sulfate. Our results suggest that the ratio of produced sulfur and sulfate varies depending on the sulfide flux. Almost all of the sulfide was oxidized directly to sulfate under low-sulfide-flux conditions, whereas only 50% was oxidized to sulfate under high-sulfide-flux conditions leading to S0 deposition. With Raman spectroscopy we could show that sulfate accumulated in Beggiatoa filaments, reaching intracellular concentrations of 0.72 to 1.73 M. PMID:24212585

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture.

PubMed

Chen, Ying-xu; Yin, Jun; Fang, Shi

2004-01-01

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m3 x d) and 230 gNH3/(m3 x d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.

Preparation of silver-activated zinc sulfide thin films

NASA Technical Reports Server (NTRS)

Feldman, C.; Swindells, F. E.

1968-01-01

Silver improves luminescence and reduces contamination of zinc sulfide phosphors. The silver is added after the zinc sulfide phosphors are deposited in thin films by vapor evaporation, but before calcining, by immersion in a solution of silver salt.

Sulfate-reducing bacteria influence the nucleation and growth of mackinawite and greigite

NASA Astrophysics Data System (ADS)

Picard, Aude; Gartman, Amy; Clarke, David R.; Girguis, Peter R.

2018-01-01

Sedimentary iron sulfide minerals play a key role in maintaining the oxygenation of Earth's atmosphere over geological timescales; they also record critical geochemical information that can be used to reconstruct paleo-environments. On modern Earth, sedimentary iron sulfide mineral formation takes places in low-temperature environments and requires the production of free sulfide by sulfate-reducing microorganisms (SRM) under anoxic conditions. Yet, most of our knowledge on the properties and formation pathways of iron sulfide minerals, including pyrite, derives from experimental studies performed in abiotic conditions, and as such the role of biotic processes in the formation of sedimentary iron sulfide minerals is poorly understood. Here we investigate the role of SRM in the nucleation and growth of iron sulfide minerals in laboratory experiments. We set out to test the hypothesis that SRM can influence Fe-S mineralization in ways other than providing sulfide through the comparison of the physical properties of iron sulfide minerals precipitated in the presence and in the absence of the sulfate-reducing bacterium Desulfovibrio hydrothermalis AM13 under well-controlled conditions. X-ray diffraction and microscopy analyses reveal that iron sulfide minerals produced in the presence of SRM exhibit unique morphology and aggregate differently than abiotic minerals formed in media without cells. Specifically, mackinawite growth is favored in the presence of both live and dead SRM, when compared to the abiotic treatments tested. The cell surface of live and dead SRM, and the extracellular polymers produced by live cells, provide templates for the nucleation of mackinawite and favor mineral growth. The morphology of minerals is however different when live and dead cells are provided. The transformation of greigite from mackinawite occurred after several months of incubation only in the presence of live SRM, suggesting that SRM might accelerate the kinetics of greigite formation under strict anoxic conditions. Pyrite formation was not observed in any experiments. While SRM provide nearly all the sulfide to the Fe-S system at low temperatures, we also posit that SRM play an additional formative role in the size, morphology and potentially the mineralogy of iron sulfide minerals in sedimentary environments, therefore potentially influencing their reactivity. Attempting to reconstruct modern and ancient biogeochemical cycles based on the geochemistry of iron sulfide minerals formed under purely abiotic conditions should be therefore done with caution.

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, Franklin C.; Battles, James E.

1983-01-01

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutetic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

Formation of Copper Sulfide Precipitate in Solid Iron

NASA Astrophysics Data System (ADS)

Urata, Kentaro; Kobayashi, Yoshinao

The growth rate of copper sulfide precipitates has been measured in low carbon steel samples such as Fe-0.3mass%Cu-0.03mass%S-0.1mass%C and Fe-0.1mass%Cu-0.01mass%S- 0.1mass%C. Heat-treatment of the samples was conducted at 1273, 1423 and 1573 K for 100 s - 14.4 ks for precipitation of copper sulfides and then the samples were observed by a scanning electron microscope and a transmission electron microscope to measure the diameter of copper sulfides precipitated in the samples. The growth rate of copper sulfide has been found to be well described by the Ostwald growth model, as follows: R\

Nanostructured silver sulfide: synthesis of various forms and their application

NASA Astrophysics Data System (ADS)

Sadovnikov, S. I.; Rempel, A. A.; Gusev, A. I.

2018-04-01

The results of experimental studies on nanostructured silver sulfide are analyzed and generalized. The influence of small particle size on nonstoichiometry of silver sulfide is discussed. Methods for the synthesis of various forms of nanostructured Ag2S including nanopowders, stable colloidal solutions, quantum dots, core–shell nanoparticles and heteronanostructures are described. The advantages and drawbacks of different synthetic procedures are analyzed. Main fields of application of nanostructured silver sulfide are considered. The bibliography includes 184 references.

Formation of selenide, sulfide or mixed selenide-sulfide films on metal or metal coated substrates

DOEpatents

Eser, Erten; Fields, Shannon

2012-05-01

A process and composition for preventing cracking in composite structures comprising a metal coated substrate and a selenide, sulfide or mixed selenide sulfide film. Specifically, cracking is prevented in the coating of molybdenum coated substrates upon which a copper, indium-gallium diselenide (CIGS) film is deposited. Cracking is inhibited by adding a Se passivating amount of oxygen to the Mo and limiting the amount of Se deposited on the Mo coating.

The formation of ReS(2) inorganic fullerene-like structures containing Re(4) parallelogram units and metal-metal bonds.

PubMed

Coleman, Karl S; Sloan, Jeremy; Hanson, Neal A; Brown, Gareth; Clancy, Gerald P; Terrones, Mauricio; Terrones, Humberto; Green, Malcolm L H

2002-10-02

The encapsulation of ReO(x) within ReS(2) inorganic fullerene-like cages is described for the first time. The encapsulate was prepared by the sulfidization of both hand-milled and ball-milled samples of ReO(2); partial conversion of the oxide to the sulfide was achieved with the degree of sulfidization depending on the exposure to the sulfidizing agent, H(2)S.

Using a portable sulfide monitor as a motivational tool: a clinical study.

PubMed

Uppal, Ranjit Singh; Malhotra, Ranjan; Grover, Vishakha; Grover, Deepak

2012-01-01

Bad breath has a significant impact on daily life of those who suffer from it. Oral malodor may rank only behind dental caries and periodontal disease as the cause of patient's visit to dentist. An aim of this study was to use a portable sulfide monitor as a motivational tool for encouraging the patients towards the better oral hygiene by correlating the plaque scores with sulfide monitor scores, and comparing the sulfide monitor scores before and after complete prophylaxis and 3 months after patient motivation. 30 patients with chronic periodontitis, having chief complaint of oral malodor participated in this study. At first visit, the plaque scores (P1) and sulfide monitor scores before (BCR1) and after complete oral prophylaxis (BCR2) were taken. Then the patients were motivated towards the better oral hygiene. After 3 months, plaque scores (P2) and sulfide monitor scores (BCR3) were recorded again. It was done using SPSS (student package software for statistical analysis). Paired sample test was performed. Statistically significant reduction in sulfide monitor scores was reported after the complete oral prophylaxis and 3 months after patient motivation. Plaque scores were significantly reduced after a period of 3 months. Plaque scores and breathchecker scores were positively correlated. An intensity of the oral malodor was positively correlated with the plaque scores. The portable sulfide monitor was efficacious in motivating the patients towards the better oral hygiene.

A paradox resolved: Sulfide acquisition by roots of seep tubeworms sustains net chemoautotrophy

PubMed Central

Freytag, John K.; Girguis, Peter R.; Bergquist, Derk C.; Andras, Jason P.; Childress, James J.; Fisher, Charles R.

2001-01-01

Vestimentiferan tubeworms, symbiotic with sulfur-oxidizing chemoautotrophic bacteria, dominate many cold-seep sites in the Gulf of Mexico. The most abundant vestimentiferan species at these sites, Lamellibrachia cf. luymesi, grows quite slowly to lengths exceeding 2 meters and lives in excess of 170–250 years. L. cf. luymesi can grow a posterior extension of its tube and tissue, termed a “root,” down into sulfidic sediments below its point of original attachment. This extension can be longer than the anterior portion of the animal. Here we show, using methods optimized for detection of hydrogen sulfide down to 0.1 μM in seawater, that hydrogen sulfide was never detected around the plumes of large cold-seep vestimentiferans and rarely detectable only around the bases of mature aggregations. Respiration experiments, which exposed the root portions of L. cf. luymesi to sulfide concentrations between 51–561 μM, demonstrate that L. cf. luymesi use their roots as a respiratory surface to acquire sulfide at an average rate of 4.1 μmol⋅g−1⋅h−1. Net dissolved inorganic carbon uptake across the plume of the tubeworms was shown to occur in response to exposure of the posterior (root) portion of the worms to sulfide, demonstrating that sulfide acquisition by roots of the seep vestimentiferan L. cf. luymesi can be sufficient to fuel net autotrophic total dissolved inorganic carbon uptake. PMID:11687647

Structural effects of naphthalimide-based fluorescent sensor for hydrogen sulfide and imaging in live zebrafish

NASA Astrophysics Data System (ADS)

Choi, Seon-Ae; Park, Chul Soon; Kwon, Oh Seok; Giong, Hoi-Khoanh; Lee, Jeong-Soo; Ha, Tai Hwan; Lee, Chang-Soo

2016-05-01

Hydrogen sulfide (H2S) is an important biological messenger, but few biologically-compatible methods are available for its detection in aqueous solution. Herein, we report a highly water-soluble naphthalimide-based fluorescent probe (L1), which is a highly versatile building unit that absorbs and emits at long wavelengths and is selective for hydrogen sulfide over cysteine, glutathione, and other reactive sulfur, nitrogen, and oxygen species in aqueous solution. We describe turn-on fluorescent probes based on azide group reduction on the fluorogenic ‘naphthalene’ moiety to fluorescent amines and intracellular hydrogen sulfide detection without the use of an organic solvent. L1 and L2 were synthetically modified to functional groups with comparable solubility on the N-imide site, showing a marked change in turn-on fluorescent intensity in response to hydrogen sulfide in both PBS buffer and living cells. The probes were readily employed to assess intracellular hydrogen sulfide level changes by imaging endogenous hydrogen sulfide signal in RAW264.7 cells incubated with L1 and L2. Expanding the use of L1 to complex and heterogeneous biological settings, we successfully visualized hydrogen sulfide detection in the yolk, brain and spinal cord of living zebrafish embryos, thereby providing a powerful approach for live imaging for investigating chemical signaling in complex multicellular systems.

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.

Geologic setting, sedimentary architecture, and paragenesis of the Mesoproterozoic sediment-hosted Sheep Creek Cu-Co-Ag deposit, Helena embayment, Montana

USGS Publications Warehouse

Graham, Garth; Hitzman, Murray W.; Zieg, Jerry

2012-01-01

The northern margin of the Helena Embayment contains extensive syngenetic to diagenetic massive pyrite horizons that extend over 25 km along the Volcano Valley-Buttress fault zone and extend up to 8 km basinward (south) within the Mesoproterozoic Newland Formation. The Sheep Creek Cu-Co deposit occurs within a structural block along a bend in the fault system, where replacement-style chalcopyrite mineralization is spatially associated mostly with the two stratigraphically lowest massive pyrite zones. These mineralized pyritic horizons are intercalated with debris flows derived from synsedimentary movement along the Volcano Valley-Buttress fault zone. Cominco American Inc. delineated a geologic resource of 4.5 Mt at 2.5% Cu and 0.1% Co in the upper sulfide zone and 4 Mt at 4% Cu within the lower sulfide zone. More recently, Tintina Resources Inc. has delineated an inferred resource of 8.48 Mt at 2.96% Cu, 0.12% Co, and 16.4 g/t Ag in the upper sulfide zone. The more intact upper sulfide zone displays significant thickness variations along strike thought to represent formation in at least three separate subbasins. The largest accumulation of mineralized sulfide in the upper zone occurs as an N-S–trending body that thickens southward from the generally E trending Volcano Valley Fault and probably occupies a paleograben controlled by normal faults in the hanging wall of the Volcano Valley Fault. Early microcrystalline to framboidal pyrite was accompanied by abundant and local barite deposition in the upper and lower sulfide zones, respectively. The sulfide bodies underwent intense (lower sulfide zone) to localized (upper sulfide zone) recrystallization and overprinting by coarser-grained pyrite and minor marcasite that is intergrown with and replaces dolomite. Silicification and paragenetically late chalcopyrite, along with minor tennantite in the upper sulfide zone, replaces fine-grained pyrite, barite, and carbonate. The restriction of chalcopyrite to inferred synsedimentary E- and northerly trending faults and absence of definitive zonation with respect to the Laramide Volcano Valley Fault in the lower sulfide zone suggest a diagenetic age related to basin development for the Sheep Creek Cu-Co-Ag deposit.

Characteristics of vesicomyid clams and their environment at the Blake Ridge cold seep, South Carolina, USA

USGS Publications Warehouse

Heyl, Taylor P.; Gilhooly, William P.; Chambers, Randolph M.; Gilchrist, George W.; Macko, Stephen A.; Ruppel, Carolyn D.; Van Dover, Cindy L.

2007-01-01

Spatial distributions and patchiness of dominant megafaunal invertebrates in deep-sea seep environments may indicate heterogeneities in the flux of reduced chemical compounds. At the Blake Ridge seep off South Carolina, USA, the invertebrate assemblage includes dense populations of live vesicomyid clams (an undescribed species) as well as extensive clam shell beds (i.e. dead clams). In the present study, we characterized clam parameters (density, size-frequency distribution, reproductive condition) in relation to sulfur chemistry (sulfide and sulfate concentrations and isotopic compositions, pyrite and elemental sulfur concentrations) and other sedimentary metrics (grain size, organic content). For clams >5 mm, clam density was highest where the total dissolved sulfide concentration at 10 cm depth (ΣH2S10cm) was 0.4 to 1.1 mmol l–1; juvenile clams (2S10cm was lowest. Clams were reproductively capable across a broad range of ΣH2S10cm (0.1 to 6.4 mmol l–1), and females in the sampled populations displayed asynchronous gametogenesis. Sulfide concentrations in porewaters at the shell–sediment interface of cores from shell beds were high, 3.3 to 12.1 mmol l–1, compared to –1 sulfide concentrations at the clam–sediment interface in live clam beds. Concentration profiles for sulfide and sulfate in shell beds were typical of those expected where there is active microbial sulfate reduction. In clam beds, profiles of sulfide and sulfate concentrations were also consistent with rapid uptake of sulfide by the clams. Sulfate in shell beds was systematically enriched in 34S relative to that in clam beds due to microbial fractionation during sulfate reduction, but in clam beds, sulfate δ34S matched that of seawater (~20‰). Residual sulfide values in clam and shell beds were correspondingly depleted in 34S. Based on porewater sulfide concentrations in shell beds at the time of sampling, we suggest that clam mortality may have been due to an abrupt increase in sulfide concentration and sulfide toxicity, but other alternatives cannot be eliminated.

Iron-Nickel Sulfide Compositional Ranges in CM Chondrites: No Simple Plan

NASA Technical Reports Server (NTRS)

Zolensky, Michael; Le, Loan

2003-01-01

Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite this ubiquity, they have only just begun the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe(1-x)S) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2S-containing environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process, due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution, something not encountered in terrestrial rocks. Each sulfide has its own particular stability conditions, which have been determined for most phases. The long-term objective of our research is to characterize sulfides in chondritic materials in order to better establish the conditions under which they formed, and the subsequent processes they experienced. Ultimately, it will be possible to infer whether the sulfides in the chondrites were formed in the solar nebula or on asteroids, and if formed on the asteroids, deduce how much alteration has occurred there. Here we explore the relationships between the finest grain size portions of carbonaceous chondrites, these being matrix and chondrule rims; fine-grained materials are the most sensitive to their environment. This abstract is one of a series reporting results for chondrites, earlier work reported results for a much more limited set of CMs, as well as for CVs and CIs.

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

Bioremediation of uranium contamination with enzymatic uranium reduction

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

Enzymatic uranium reduction by Desulfovibrio desulfuricans readily removed uranium from solution in a batch system or when D. desulfuricans was separated from the bulk of the uranium-containing water by a semipermeable membrane. Uranium reduction continued at concentrations as high as 24 mM. Of a variety of potentially inhibiting anions and metals evaluated, only high concentrations of copper inhibited uranium reduction. Freeze-dried cells, stored aerobically, reduced uranium as fast as fresh cells. D. desulfuricans reduced uranium in pH 4 and pH 7.4 mine drainage waters and in uraniumcontaining groundwaters from a contaminated Department of Energy site. Enzymatic uranium reduction has several potential advantages over other bioprocessing techniques for uranium removal, the most important of which are as follows: the ability to precipitate uranium that is in the form of a uranyl carbonate complex; high capacity for uranium removal per cell; the formation of a compact, relatively pure, uranium precipitate.

Process for removing technetium from iron and other metals

DOEpatents

Leitnaker, J.M.; Trowbridge, L.D.

1999-03-23

A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag. 4 figs.

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Os and S isotope studies of ultramafic rocks in the Duke Island Complex, Alaska: variable degrees of crustal contamination of magmas in an arc setting and implications for Ni-Cu-PGE sulfide mineralization

NASA Astrophysics Data System (ADS)

Stifter, Eric C.; Ripley, Edward M.; Li, Chusi

2016-10-01

The Duke Island Complex is one of the several "Ural-Alaskan" intrusions of Cretaceous age that occur along the coast of SE Alaska. Significant quantities of magmatic Ni-Cu-PGE sulfide mineralization are locally found in the complex, primarily within olivine clinopyroxenites. Sulfide mineralization is Ni-poor, consistent with petrologic evidence which indicates that sulfide saturation was reached after extensive olivine crystallization. Olivine clinopyroxenites were intruded by magmas that produced sulfide-poor, adcumulate dunites. As part of a study to investigate the potential for Ni-rich sulfide mineralization in association with the dunites, a Re-Os and S isotope study of the dunites, as well as sulfide mineralization in the olivine clinopyroxenites, was initiated. Importantly, recent drilling in the complex identified the presence of sulfidic and carbonaceous country rocks that may have been involved in the contamination of magmas and generation of sulfide mineralization. γOs (110 Ma) values of two sulfidic country rocks are 1022 and 2011. δ34S values of the country rocks range from -2.6 to -16.1 ‰. 187Os/188Os ratios of sulfide minerals in the mineralization hosted by olivine clinopyroxenites are variable and high, with γOs (110 Ma) values between 151 and 2059. Extensive interaction with Re-rich sedimentary country rocks is indicated. In contrast, γOs (110 Ma) values of the dunites are significantly lower, ranging between 2 and 16. 187Os/188Os ratios increase with decreasing Os concentration. This inverse relation is similar to that shown by ultramafic rocks from several arc settings, as well as altered abyssal dunites and peridotites. The relation may be indicative of magma derivation from a sub-arc mantle that had experienced metasomatism via slab-derived fluids. Alternatively, the relation may be indicative of minor contamination of magma by crustal rocks with low Os concentrations but high 187Os/188Os ratios. A third alternative is that the low Os concentrations and elevated 187Os/188Os ratios denote subsolidus interaction with seawater or meteoric water. δ34S values of the dunites range between -6.4 and 6.6 ‰, and are consistent with the addition of S during fluid-rock interaction and serpentinization. The sharp contrast between the Os isotope ratios of the dunites and those of the sulfide mineralization illustrate that magmas that were spatially part of the same intrusive system may have experienced very different histories of interaction with country rocks. An important corollary is that because of the concentrations of Os and S, elevated Os isotope ratios (a function of high Re concentrations) and variable sulfur isotope ratios of sulfidic and carbonaceous country rocks, both S and Os isotope data from the olivine clinopyroxenite-hosted sulfide mineralization, are consistent with less than ˜2 % of bulk rock contamination. Even lower fractional abundance values may be indicated if the contaminant was a S-C-Os-rich fluid or partial melt derived from the sulfidic-carbonaceous metasedimentary country rocks. Despite the low degrees of contamination, the amounts of Os and S in the sulfide mineralization that may have been derived from country rocks often exceed 50 %.

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

NASA Astrophysics Data System (ADS)

Luguet, Ambre; Lorand, Jean-Pierre; Seyler, Monique

2003-04-01

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd N/Ir N (<0.5) for variable Pt N/Ir N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd N/Ir N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt N/Ir N ≤ 1.24) and Rh (Rh N/Ir N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.

Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

PubMed

Sun, Jing; Pikaar, Ilje; Sharma, Keshab Raj; Keller, Jürg; Yuan, Zhiguo

2015-03-15

Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated. Copyright © 2015 Elsevier Ltd. All rights reserved.

Native gold and gold-rich sulfide deposits in a submarine basaltic caldera, Higashi-Aogashima hydrothermal field, Izu-Ogasawara frontal arc, Japan

NASA Astrophysics Data System (ADS)

Iizasa, Kokichi; Asada, Akira; Mizuno, Katsunori; Katase, Fuyuki; Lee, Sangkyun; Kojima, Mitsuhiro; Ogawa, Nobuhiro

2018-04-01

Sulfide deposits with extremely high Au concentrations (up to 275 ppm; avg. 102 ppm, n = 15), high Au/Ag ratios (0.24, n = 15), and low Cu/(Cu + Zn) ratios (0.03, n = 15) were discovered in 2015 in active hydrothermal fields at a water depth of 760 m in a basalt-dominated submarine caldera in the Izu-Ogasawara frontal arc, Japan. Native gold grains occur in massive sulfide fragments, concretions, and metalliferous sediments from a sulfide mound (40 m across and 20 m high) with up to 30-m-high black smoker chimneys. Tiny native gold grains up to 14 μm in diameter are mainly present in sulfide fallouts from chimney orifices and plumes. Larger native gold grains up to 150 μm long occur mostly as discrete particles and/or with amorphous silica and sulfides. The larger gold grains are interpreted to represent direct precipitation from Au-bearing hydrothermal fluids circulating in and/or beneath the unconsolidated sulfide mound deposits. Sulfur isotope compositions from a limited number of sulfide separates (n = 4) range from 4.3 to 5.8‰ δ34S, similar to the quaternary volcanic rocks of the arc. Barite separates have values of 22.2 and 23.1‰, close to modern seawater values, and indicate probable seawater sulfate origin. The Cu, Zn, and Pb concentrations in bulk samples of sulfide-rich rocks are similar to those of volcanogenic massive sulfides formed in continental crustal environments. The gold is interpreted to have formed by low-temperature hydrothermal activity, perhaps genetically different from systems with documented magmatic contributions or from seafloor hydrothermal systems in other island arc settings. Its presence suggests that basalt-dominated submarine calderas situated on relatively thick continental crust in an intraoceanic arc setting such as the Higashi-Aogashima knoll caldera may be perspective for gold mineralization.

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

PubMed

Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

2017-07-18

This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an exciting model organism in which to study the physiology of this process. Copyright © 2017 Thorup et al.

Numerical modelling of erosion and assimilation of sulfur-rich substrate by martian lava flows: Implications for the genesis of massive sulfide mineralization on Mars

NASA Astrophysics Data System (ADS)

Baumgartner, Raphael J.; Baratoux, David; Gaillard, Fabrice; Fiorentini, Marco L.

2017-11-01

Mantle-derived volcanic rocks on Mars display physical and chemical commonalities with mafic-ultramafic ferropicrite and komatiite volcanism on the Earth. Terrestrial komatiites are common hosts of massive sulfide mineralization enriched in siderophile-chalcophile precious metals (i.e., Ni, Cu, and the platinum-group elements). These deposits correspond to the batch segregation and accumulation of immiscible sulfide liquids as a consequence of mechanical/thermo-mechanical erosion and assimilation of sulfur-rich bedrock during the turbulent flow of high-temperature and low-viscosity komatiite lava flows. This study adopts this mineralization model and presents numerical simulations of erosion and assimilation of sulfide- and sulfate-rich sedimentary substrates during the dynamic emplacement of (channelled) mafic-ultramafic lava flows on Mars. For sedimentary substrates containing adequate sulfide proportions (e.g., 1 wt% S), our simulations suggest that sulfide supersaturation in low-temperature (< 1350 °C) flows could be attained at < 200 km distance, but may be postponed in high-temperature lavas flows (> 1400 °C). The precious-metals tenor in the derived immiscible sulfide liquids may be significantly upgraded as a result of their prolonged equilibration with large volumes of silicate melts along flow conduits. The influence of sulfate assimilation on sulfide supersaturation in martian lava flows is addressed by simulations of melt-gas equilibration in the Csbnd Hsbnd Osbnd S fluid system. However, prolonged sulfide segregation and deposit genesis by means of sulfate assimilation appears to be limited by lava oxidation and the release of sulfur-rich gas. The identification of massive sulfide endowments on Mars is not possible from remote sensing data. Yet the results of this study aid to define regions for the potential occurrence of such mineral systems, which may be the large canyon systems Noctis Labyrinthus and Valles Marineris, or the Hesperian channel systems of Mars' highlands (e.g., Kasei Valles), most of which have been periodically draped by mafic-ultramafic lavas.

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

PubMed Central

Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

2016-01-01

This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

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.

Measurement of H2S in Crude Oil and Crude Oil Headspace Using Multidimensional Gas Chromatography, Deans Switching and Sulfur-selective Detection

PubMed Central

Heshka, Nicole E.; Hager, Darcy B.

2015-01-01

A method for the analysis of dissolved hydrogen sulfide in crude oil samples is demonstrated using gas chromatography. In order to effectively eliminate interferences, a two dimensional column configuration is used, with a Deans switch employed to transfer hydrogen sulfide from the first to the second column (heart-cutting). Liquid crude samples are first separated on a dimethylpolysiloxane column, and light gases are heart-cut and further separated on a bonded porous layer open tubular (PLOT) column that is able to separate hydrogen sulfide from other light sulfur species. Hydrogen sulfide is then detected with a sulfur chemiluminescence detector, adding an additional layer of selectivity. Following separation and detection of hydrogen sulfide, the system is backflushed to remove the high-boiling hydrocarbons present in the crude samples and to preserve chromatographic integrity. Dissolved hydrogen sulfide has been quantified in liquid samples from 1.1 to 500 ppm, demonstrating wide applicability to a range of samples. The method has also been successfully applied for the analysis of gas samples from crude oil headspace and process gas bags, with measurement from 0.7 to 9,700 ppm hydrogen sulfide. PMID:26709594

Nanoengineering of 2D tin sulfide nanoflake arrays incorporated on polyaniline nanofibers with boosted capacitive behavior

NASA Astrophysics Data System (ADS)

Wang, Huanhuan; Chao, DongLiang; Liu, Jilei; Lin, Jianyi; Shen, Ze Xiang

2018-07-01

Nanoscale engineering plays an important role in designing novel electrode architecture and boosting energy storage in supercapacitors. Herein, we demonstrate the fabrication of freestanding tin sulfide based supercapacitor electrode using facile nucleation substrate control, i.e. polyaniline network. This is the first time that tin sulfide based material is fabricated as a binder-free electrode for supercapacitors. The first combination of tin sulfide and polyaniline also evokes synergistic effect to enhance the performance as the polyaniline nanofibers facilitate the growth of tin sulfide flakes in nanosize which is further proved helpful for improving the capacity and stability of the electrode. The as-obtained electrode of tin sulfide nanoflake arrays incorporated on polyaniline nanofibers (365 F g‑1 at 10 mV s‑1) exhibits superior electrochemical performance compared with micro-scaled tin sulfide (32 F g‑1 at 10 mV s‑1). The significantly improved pseudocapacitive and diffusive contributions of polyaniline nanofibers incorporated electrode are identified by quantitative kinetics analysis due to greatly decreased particle size and introduced mesopores, nanoclusters, and exposed edges. Profited from effective nanostructure engineering, a Na+ intercalation mechanism is also pointed out in boosting the electrochemical performance.

Petrogenesis of the Ni-Cu-PGE sulfide-bearing Tamarack Intrusive Complex, Midcontinent Rift System, Minnesota

NASA Astrophysics Data System (ADS)

Taranovic, Valentina; Ripley, Edward M.; Li, Chusi; Rossell, Dean

2015-01-01

The Tamarack Intrusive Complex (TIC, 1105.6 ± 1.2 Ma) in NE Minnesota, was emplaced during the early stages of the development of the Midcontinent Rift System (MRS, "Early Stage": 1110-1106 Ma). Country rocks of the TIC are those of the Paleoproterozoic Thomson Formation, part of the Animikie Group including sulfide-bearing metasedimentary black shale. The magmatic system is composed of at least two principal mafic-ultramafic intrusive sequences: the sulfide-barren Bowl Intrusion in the south and the "dike" area intrusions in the north which host Ni-Cu-Platinum Group Elements (PGE) mineralization with up to 2.33% Ni, 1.24% Cu, 0.34 g/t Pt, 0.23 g/t Pd and 0.18 g/t Au. Two distinct intrusive units in the "dike" area are the CGO (coarse-grained olivine-bearing) Intrusion, a sub-vertical dike-like body, and the overlying sub-horizontal FGO (fine-grained olivine-bearing) Intrusion. Both intrusions comprise peridotite, feldspathic peridotite, feldspathic pyroxenite, melatroctolite and melagabbro. Massive sulfides are volumetrically minor and mainly occur as lenses emplaced into the country rocks associated with both intrusions. Semi-massive (net-textured) sulfides are distributed at the core of the CGO Intrusion, surrounded by a halo of the disseminated sulfides. Disseminated sulfides also occur in lenses along the base of the FGO Intrusion. Olivine compositions in the CGO Intrusion are between Fo89 and Fo82 and in the FGO Intrusion from Fo84 to Fo82. TIC intrusions have more primitive olivine compositions than that of olivine in the sheet-like intrusions in the Duluth Complex (below Fo70), as well as olivine from the smaller, conduit-related, Eagle and East Eagle Intrusions in Northern Michigan (Fo86 to Fo75). The FeO/MgO ratios of the CGO and FGO Intrusion parental magmas, inferred from olivine compositions, are similar to those of picritic basalts erupted during the early stages of the MRS formation. Trace element ratios differ slightly from other intrusions in the MRS, and are indicative of significant crustal contamination. Differences in textures, whole-rock and mineral compositions, and sulfide distribution are consistent with the emplacement of at least two distinct sulfide saturated magmatic pulses. Ni-enrichment in the TIC indicates that sulfide saturation was attained prior to the sequestration of major proportions of Ni by olivine, possibly at a deeper chamber in the magmatic system. The addition of crustal S from the Thomson Formation sulfidic country rocks is thought to have been the principal process which drove the early attainment of sulfide saturation in the magmas. The CGO Intrusion carried the greater abundance of sulfide liquid, but both the CGO and FGO intrusive sequences represent the accumulation of dense silicate minerals and sulfide liquid in a conduit system. The genetic processes that were operative in the formation of Ni-Cu-PGE mineralization in the Tamarack Intrusive Complex appear to be typical of conduit-style magmatic sulfide deposits associated with large continental basaltic provinces.

Atacamite and paratacamite from the ultramafic-hosted Logatchev seafloor vent field (14°45′N, Mid-Atlantic Ridge)

USGS Publications Warehouse

Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Petersen, Sven; Billstrom, Kjell; Stummeyer, Jens; Kamenov, G.; Shanks, W.

2011-01-01

Atacamite and paratacamite are ubiquitous minerals associated with Cu-rich massive sulfides at the Logatchev hydrothermal field (Mid-Atlantic Ridge). In this work we provide new details on the mineralogy and geochemistry of these basic cupric chlorides. Our data support the notion that atacamite and paratacamite formation at submarine vent fields is an alteration process of hydrothermal Cu-sulfides. Secondary Cu-sulfides (bornite, covellite) are unstable at ambient seawater conditions and will dissolve. Dissolution is focused at the sulfide–seawater contact, leading to release of Fe2+ and Cu+ and formation of residual chalcocite through an intermediate Cu5S4 phase. Most of the released Fe2+ oxidizes immediately and precipitates as FeOOH directly on the chalcocite rims whereas Cu as chloride complexes (CuCl2−, CuCl32-) remains in solution at the same Eh. Cuprous–chloride complexes migrate from the reaction zone and upon increasing Eh precipitate as Cu2Cl(OH)3. As a consequence of this, the sulfide–seawater reaction interface is clearly marked by thin chalcocite–FeOOH bands and the entire assemblage is mantled by atacamite (or paratacamite). Our mineralogical, petrographic, geochemical and isotopic studies suggest that there are two types of atacamite (and/or paratacamite) depending on their mode of precipitation. Type 1 atacamite precipitated directly on the parent sulfides as evidenced by mantling of the sulfides, absence of detrital mineral grains, a preserved conspicuous positive Eu anomaly and a negligible negative Ce anomaly similar to those of the parent sulfide. In addition, Au concentrations are slightly lower than those of the parent sulfides, which suggest minimal transport of Au-ions after their release from the sulfides. Furthermore, the low content of the rare earth elements implies short contact time with the ambient seawater. The Sr–Nd–Pb-isotopic signatures of type 1 atacamite confirm the genetic association with the parent sulfides and indicate formation spatially very close to the latter. Type 2 atacamite precipitated at some distance from the parent sulfides, which means that the cuprous–chloride complexes have moved away from the sulfide alteration zone before precipitation. The evidence for this is absence of direct association of atacamite with sulfides. In addition, this atacamite contains a substantial proportion of detrital minerals, which implies precipitation in the sediments, distal to the parent sulfides. As a consequence of the detrital impurities the contents of elements like Cr, Cs, Hf, Nb, Rb, Th and Zr are higher than in type 1 atacamite (and/or paratacamite). Au contents are lower than those of type 1 atacamite (and/or paratacamite) which implies prolonged Au transport in solution before precipitation. Furthermore, the rare earth element distribution patterns have no positive Eu anomaly suggesting that the positive Eu anomaly of the parent sulfide has been erased after dissolution and prolonged contact of the fluid with ambient seawater (with negative Eu anomaly). Finally, the Sr–Nd-isotope signature differs from that of the parent sulfide and indicates a considerable terrigenous input.

VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

EPA Science Inventory

Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

Raman spectra and cross sections of ammonia, chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400 1400 cm 1

DTIC Science & Technology

2015-11-24

ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400... ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint...sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint

Raman Spectra and Cross Sections of Ammonia, Chlorine, Hydrogen Sulfide, Phosgene, and Sulfur Dioxide Toxic Gases in the Fingerprint Region 400-1400 cm-1

DTIC Science & Technology

2015-12-14

ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400... ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint...sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint region

A fuel-cell-assisted iron redox process for simultaneous sulfur recovery and electricity production from synthetic sulfide wastewater.

PubMed

Zhai, Lin-Feng; Song, Wei; Tong, Zhong-Hua; Sun, Min

2012-12-01

Sulfide present in wastewaters and waste gases should be removed due to its toxicity, corrosivity, and malodorous property. Development of effective, stable, and feasible methods for sulfur recovery from sulfide attains a double objective of waste minimization and resource recovery. Here we report a novel fuel-cell-assisted iron redox (FC-IR) process for simultaneously recovering sulfur and electricity from synthetic sulfide wastewater. The FC-IR system consists of an oxidizing reactor where sulfide is oxidized to elemental sulfur by Fe(III), and a fuel cell where Fe(III) is regenerated from Fe(II) concomitantly with electricity producing. The oxidation of sulfide by Fe(III) is significantly dependent on solution pH. Increasing the pH from 0.88 to 1.96 accelerates the oxidation of sulfide, however, lowers the purity of the produced elemental sulfur. The performance of fuel cell is also a strong function of solution pH. Fe(II) is completely oxidized to Fe(III) when the fuel cell is operated at a pH above 6.0, whereas only partially oxidized below pH 6.0. At pH 6.0, the highest columbic efficiency of 75.7% is achieved and electricity production maintains for the longest time of 106 h. Coupling operation of the FC-IR system obtains sulfide removal efficiency of 99.90%, sulfur recovery efficiency of 78.6 ± 8.3%, and columbic efficiency of 58.6 ± 1.6%, respectively. These results suggest that the FC-IR process is a promising tool to recover sulfur and energy from sulfide. Copyright © 2012 Elsevier B.V. All rights reserved.

In situ Fe-sulfide coating for arsenic removal under reducing conditions

NASA Astrophysics Data System (ADS)

Xie, Xianjun; Liu, Yaqing; Pi, Kunfu; Liu, Chongxuan; Li, Junxia; Duan, Mengyu; Wang, Yanxin

2016-03-01

An in situ Fe-sulfide coating approach has been developed for As-contaminated groundwater remediation. Alternate injection of Fe(II), O2-free water and S2- can realize Fe-sulfide coating onto quartz sands with minor changes in porosity. As(III) uptake experiment indicated that the retardation factor for As(III) was 37 and dynamic retention capacity was 44.94 mg As(III)/g Fe, which was much higher than the maximum adsorption capacity for As(III) by FeS and FeS2. This result indicated that adsorption cannot be the only mechanism for As(III) uptake by Fe-sulfide coating layer. The SEM image and FTIR spectra results suggested that interaction between As(III) and Fe-sulfides and formation of As-sulfide precipitates could significantly contribute to As(III) uptake by Fe-sulfide coating layer. Alternate injection of Fe(II) + As(III) and S2- was conducted to simulate in situ As immobilization from real groundwater. The SEM image showed that the quartz sands were mainly covered by crystalline framboidal pyrite after such amendment. The breakthrough of As(III) was not observed during this experiment and the removal capacity for As(III) was 109.7 mg As/g Fe. The As(III) immobilization mechanism during alternate injection of Fe(II) + As(III) and S2- was significantly different from that of As(III) uptake by Fe-sulfide coating. The direct interaction between As(III) and S2- produced As-sulfides contributed to the high As(III) removal capacity during alternate injection of Fe(II) + As(III) and S2-. This result indicated that alternate injection of Fe(II) and S2- approach has an attractive application for As-contaminated groundwater remediation under strongly reducing environment.

Reduced Expression of Hydrogen Sulfide-Generating Enzymes Down-Regulates 15-Hydroxyprostaglandin Dehydrogenase in Chorion during Term and Preterm Labor.

PubMed

Sun, Qianqian; Chen, Zixi; He, Ping; Li, Yuan; Ding, Xiaoying; Huang, Ying; Gu, Hang; Ni, Xin

2018-01-01

Chorionic NAD-dependent 15-hydroxyprostaglandin dehydrogenase (PGDH) plays a pivotal role in controlling the amount of prostaglandins in the uterus and has been implicated in the process of labor. Prior studies identified hydrogen sulfide-generating enzymes cystathionine-β-synthetase (CBS) and cystathionine-γ-lyase (CSE) in fetal membranes. We investigated whether hydrogen sulfide is involved in the regulation of PGDH expression in the chorion during labor. The chorionic tissues were obtained from pregnant women at preterm in labor and at term in labor or not in labor at term. Levels of CSE and CBS and hydrogen sulfide production rate were down-regulated in term in labor and preterm in labor groups compared with not in labor at term group. The CBS level correlated to PGDH expression in the chorion. Hydrogen sulfide donor NaHS and precursor l-cysteine dose-dependently stimulated PGDH expression and activity in cultured chorionic trophoblasts. The effect of l-cysteine was blocked by CBS inhibitor and CBS siRNA but not by CSE inhibitor and CSE siRNA. Hydrogen sulfide treatment suppressed miR-26b and miR-199a expression in chorionic trophoblasts. miR-26b and miR-199a mimics blocked hydrogen sulfide upregulation of PGDH expression. Our results indicate that hydrogen sulfide plays pivotal roles in maintenance of PGDH expression in the chorion during human pregnancy. Reduced expression of hydrogen sulfide-generating enzymes contributes to an increased amount of prostaglandins in the uterus during labor. Copyright © 2018 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

Sulfide-dependent photosynthetic electron flow coupled to proton translocation in thylakoids of the cyanobacterium Oscillatoria limnetica.

PubMed

Shahak, Y; Arieli, B; Binder, B; Padan, E

1987-12-01

Light-induced proton translocation coupled to sulfide-dependent electron transport has been studied in isolated thylakoids of the cyanobacterium Oscillatoria limnetica. The thylakoids are obtained by osmotic shock of washed spheroplasts, prepared with glycine-betaine as the osmotic stabilizer. 13C NMR studies suggests that betaine is the major osmoregulator in O. limnetica. Thylakoid preparations obtained from both sulfide-induced anoxygenic cells and noninduced oxygenic cells are capable of proton pumping coupled to phenazinemethosulfate-mediated cyclic electron flow. However, only in the induced thylakoids can sulfide-dependent proton gradient (delta pH) formation be measured, using either NADP or methyl viologen as the terminal acceptor. Sulfide-dependent delta pH formation correlates with a high-affinity electron donation site (apparent Km 44 microM at pH 7.9). This site is not lost upon washing of the thylakoids. In addition, both sulfide-dependent electron transport and delta pH formation are sensitive to inhibitors of the cytochrome b6f complex such as 2-n-nonyl-4-hydroxyquinoline-N-oxide, 2,4-dinitrophenyl ether of 2-iodo-4-nitrothymol, or stigmatellin. Sulfide-dependent NADP photoreduction of low affinity (which does not saturate by as much as 7 mM sulfide) is detected in both induced and noninduced thylakoids, but this activity is insensitive to the inhibitors and is not coupled to proton transport. It is suggested that the adaptation of O. limnetica to anoxygenic photosynthesis involves the induction of a thylakoid factor(s) which creates a high-affinity site for sulfide, and the transfer of its electrons via the cytochrome b6f complex, coupled to proton translocation.

Identification of Bacteria Potentially Responsible for Oxic and Anoxic Sulfide Oxidation in Biofilters of a Recirculating Mariculture System

PubMed Central

Cytryn, Eddie; van Rijn, Jaap; Schramm, Andreas; Gieseke, Armin; de Beer, Dirk; Minz, Dror

2005-01-01

Bacteria presumably involved in oxygen- or nitrate-dependent sulfide oxidation in the biofilters of a recirculating marine aquaculture system were identified using a new application of reverse transcription-PCR denaturing gradient gel electrophoresis (DGGE) analysis termed differential-transcription (DT)-DGGE. Biofilter samples were incubated in various concentrations of sulfide or thiosulfate (0 to 5 mM) with either oxygen or nitrate as the sole electron acceptor. Before and after short-term incubations (10 to 20 h), total DNA and RNA were extracted, and a 550-bp fragment of the 16S rRNA genes was PCR amplified either directly or after reverse transcription. DGGE analysis of DNA showed no significant change of the original microbial consortia upon incubation. In contrast, DGGE of cDNA revealed several phylotypes whose relative band intensities markedly increased or decreased in response to certain incubation conditions, indicating enhanced or suppressed rRNA transcription and thus implying metabolic activity under these conditions. Specifically, species of the gammaproteobacterial genus Thiomicrospira and phylotypes related to symbiotic sulfide oxidizers could be linked to oxygen-dependent sulfide oxidation, while members of the Rhodobacteraceae (genera Roseobacter, Rhodobacter, and Rhodobium) were putatively active in anoxic, nitrate-dependent sulfide oxidation. For all these organisms, the physiology of their closest cultured relatives matches their DT-DGGE-inferred function. In addition, higher band intensities following exposure to 5 mM sulfide and nitrate were observed for Thauera-, Hydrogenophaga-, and Dethiosulfovibrio-like phylotypes. For these genera, nitrate-dependent sulfide oxidation has not been documented previously and therefore DT-DGGE might indicate a higher relative tolerance to high sulfide concentrations than that of other community members. We anticipate that DT-DGGE will be of general use in tracing functionally equivalent yet phylogenetically diverse microbial populations in nature. PMID:16204531

Electrochemical oxidation of iron and alkalinity generation for efficient sulfide control in sewers.

PubMed

Lin, Hui-Wen; Kustermans, Caroline; Vaiopoulou, Eleni; Prévoteau, Antonin; Rabaey, Korneel; Yuan, Zhiguo; Pikaar, Ilje

2017-07-01

The addition of iron salts is one of the most commonly used dosing strategies for sulfide control in sewers. However, iron salts decrease the sewage pH which not only reduces the effectiveness of sulfide precipitation but also enhances the release of residual sulfide to the sewer atmosphere. Equally important, concentrated iron salt solutions are corrosive and their frequent transport, handling, and on-site storage often come with Occupational Health and Safety (OH&S) concerns. Here, we experimentally demonstrated a novel sulfide control approach using electrochemical systems with parallel placed iron electrodes. This enabled combining anodic dissolved iron species release with cathodic hydroxyl anion production, which alleviates all the aforementioned concerns. A long-term experiment was successfully carried out achieving an average sulfide removal efficiency of 95.4 ± 4.4% at low voltage input of 2.90 ± 0.54 V over the course of 8 weeks. This electrochemical method was demonstrated to successfully achieve efficient sulfide control. In addition, it increases the sewage pH, thereby overcoming the drawbacks associated with the pH decrease in the case of conventional iron salt dosing. Ferrous ions were produced at an overall coulombic efficiency (CE) of 98.2 ± 1.2%, whereas oxygen evolution and direct sulfide oxidation were not observed. Short-term experiments showed that increasing either inter-electrode gap or current density increased the cell voltage associated with the increase in the ohmic drop of the system. Overall, this study highlights the practical potential of in-situ generation of dissolved iron species and simultaneous hydroxyl anion generation for efficient sulfide control in sewers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selenium speciation in Lower Cambrian Se-enriched strata in South China and its geological implications

NASA Astrophysics Data System (ADS)

Fan, Haifeng; Wen, Hanjie; Hu, Ruizhong; Zhao, Hui

2011-12-01

To understand the impact of Selenium (Se) into the biogeochemical cycle and implications for palaeo-redox environment, a sequential extraction method was utilized for samples including black shales, cherts, a Ni-Mo-Se sulfide layer, K-bentonite and phosphorite from Lower Cambrian Se-enriched strata in southern China. Seven species (water-soluble, phosphate exchangeable, base-soluble, acetic acid-soluble, sulfide/selenide associated, residual Se) and different oxidation states (selenate Se(VI), selenite Se(IV), organic Se, Se (0) and mineral Se(-II)) were determinated in this study. We found that the Ni-Mo-Se sulfide layer contained a significantly greater amount of Se(-II) associated with sulfides/selenides than those in host black shales and cherts. Furthermore, a positive correlation between the degree of sulfidation of iron (DOS) and the percentage of the sulfide/selenide-associated Se(-II) was observed for samples, which suggests the proportion of sulfide/selenide-associated Se(-II) could serve as a proxy for palaeo-redox conditions. In addition, the higher percentage of Se(IV) in K-bentonite and phosphorite was found and possibly attributed to the adsorption of Se by clay minerals, iron hydroxide surfaces and organic particles. Based on the negative correlations between the percentage of Se(IV) and that of Se(-II) in samples, we propose that the K-bentonite has been altered under the acid oxic conditions, and the most of black shale (and cherts) and the Ni-Mo-Se sulfide layer formed under the anoxic and euxinic environments, respectively. Concerning Se accumulation in the Ni-Mo-Se sulfide layer, the major mechanism can be described by (1) biotic and abiotic adsorption and further dissimilatory reduction from oxidized Se(VI) and Se(IV) to Se(-II), through elemental Se, (2) contribution of hydrothermal fluid with mineral Se(-II).

Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

NASA Technical Reports Server (NTRS)

Rao, D. B.; Nelson, H. G.

1977-01-01

The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

Chemical Bonding in Sulfide Minerals

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

Vaughan, David J.; Rosso, Kevin M.

An understanding of chemical bonding and electronic structure in sulfide minerals is central to any attempt at understanding their crystal structures, stabilities and physical properties. It is also an essential precursor to understanding reactivity through modeling surface structure at the molecular scale. In recent decades, there have been remarkable advances in first principles (ab initio) methods for the quantitative calculation of electronic structure. These advances have been made possible by the very rapid development of high performance computers. Several review volumes that chart the applications of these developments in mineralogy and geochemistry are available (Tossell and Vaughan, 1992; Cygan andmore » Kubicki, 2001). An important feature of the sulfide minerals is the diversity of their electronic structures, as evidenced by their electrical and magnetic properties (see Pearce et al. 2006, this volume). Thus, sulfide minerals range from insulators through semiconductors to metals, and exhibit every type of magnetic behavior. This has presented problems for those attempting to develop bonding models for sulfides, and also led to certain misconceptions regarding the kinds of models that may be appropriate. In this chapter, chemical bonding and electronic structure models for sulfides are reviewed with emphasis on more recent developments. Although the fully ab initio quantitative methods are now capable of a remarkable degree of sophistication in terms of agreement with experiment and potential to interpret and predict behavior with varying conditions, both qualitative and more simplistic quantitative approaches will also be briefly discussed. This is because we believe that the insights which they provide are still helpful to those studying sulfide minerals. In addition to the application of electronic structure models and calculations to solid sulfides, work on sulfide mineral surfaces (Rosso and Vaughan 2006a,b) and solution complexes and clusters (Rickard and Luther, 2006) are discussed in detail later in this volume.« less

The Search for Interstellar Sulfide Grains

NASA Technical Reports Server (NTRS)

Keller, Lindsay P.; Messenger, Scott

2010-01-01

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

In situ Fe-sulfide coating for arsenic removal under reducing conditions

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

Xie, Xianjun; Liu, Yaqing; Pi, Kunfu

2016-03-01

An in situ Fe-sulfide coating approach has been developed for As-contaminated groundwater remediation. Alternate injection of Fe(II), O 2-free water and S 2$-$ can realize Fe-sulfide coating onto quartz sands with minor changes in porosity. As(III) uptake experiment indicated that the retardation factor for As(III) was 37 and dynamic retention capacity was 44.94 mg As(III)/g Fe, which was much higher than the maximum adsorption capacity for As(III) by FeS and FeS 2. This result indicated that adsorption cannot be the only mechanism for As(III) uptake by Fe-sulfide coating layer. The SEM image and FTIR spectra results suggested that interaction betweenmore » As(III) and Fe-sulfides and formation of As-sulfide precipitates could significantly contribute to As(III) uptake by Fe-sulfide coating layer. Alternate injection of Fe(II) + As(III) and S 2$-$ was conducted to simulate in situ As immobilization from real groundwater. The SEM image showed that the quartz sands were mainly covered by crystalline framboidal pyrite after such amendment. The breakthrough of As(III) was not observed during this experiment and the removal capacity for As(III) was 109.7 mg As/g Fe. The As(III) immobilization mechanism during alternate injection of Fe(II) + As(III) and S 2$-$ was significantly different from that of As(III) uptake by Fe-sulfide coating. The direct interaction between As(III) and S 2$-$ produced As-sulfides contributed to the high As(III) removal capacity during alternate injection of Fe(II) + As(III) and S 2$-$. This result indicated that alternate injection of Fe(II) and S 2$-$ approach has an attractive application for As-contaminated groundwater remediation under strongly reducing environment.« less

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring

PubMed Central

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-01-01

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ. PMID:27297893

The origin of Cu/Au ratios in porphyry-type ore deposits.

PubMed

Halter, Werner E; Pettke, Thomas; Heinrich, Christoph A

2002-06-07

Microanalysis of major and trace elements in sulfide and silicate melt inclusions by laser-ablation inductively coupled plasma mass spectrometry indicates a direct link between a magmatic sulfide liquid and the composition of porphyry-type ore deposits. Copper (Cu), gold (Au), and iron (Fe) are first concentrated in a sulfide melt during magmatic evolution and then released to an ore-forming hydrothermal fluid exsolved late in the history of a magma chamber. The composition of sulfide liquids depends on the initial composition and source of the magma, but it also changes during the evolution of the magma in the crust. Magmatic sulfide melts may exert the dominant direct control on the economic metal ratios of porphyry-type ore deposits.

Method of forming components for a high-temperature secondary electrochemical cell

DOEpatents

Mrazek, F.C.; Battles, J.E.

1981-05-22

A method of forming a component for a high-temperature secondary electrochemical cell having a positive electrode including a sulfide selected from the group consisting of iron sulfides, nickel sulfides, copper sulfides and cobalt sulfides, a negative electrode including an alloy of aluminum and an electrically insulating porous separator between said electrodes is described. The improvement comprises forming a slurry of solid particles dispersed in a liquid electrolyte such as the lithium chloride-potassium chloride eutectic, casting the slurry into a form having the shape of one of the components and smoothing the exposed surface of the slurry, cooling the cast slurry to form the solid component, and removing same. Electrodes and separators can be thus formed.

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring.

PubMed

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-06-25

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ.

Contaminant dispersion at the rehabilitated Mary Kathleen uranium mine, Australia

NASA Astrophysics Data System (ADS)

Lottermoser, B. G.; Ashley, P. M.; Costelloe, M. T.

2005-09-01

This study reports on the transfer of contaminants from waste rock dumps and mineralised ground into soils, sediments, waters and plants at the rehabilitated Mary Kathleen uranium mine in semi-arid northwest Queensland. Numerous waste rock dumps were partly covered with benign soil and the open pit mine was allowed to flood. The mineralised and waste calc-silicate rock in the open pit and dumps has major (>1 wt%) Ca, Fe and Mg, minor (>1,000 ppm) Ce, La, Mn, P and S, subminor (>100 ppm) Ba, Cu, Th and U, and trace (<100 ppm) As, Ni, Pb, Y and Zn values. Consequently, chemical and physical weathering processes have acted on waste rock and on rock faces within the open pit, mobilising many elements and leading to their dispersion into soils, stream sediments, pit water and several plant species. Chemical dispersion is initiated by sulfide mineral breakdown, generation of sulfuric acid and formation of several soluble, transient sulfate minerals as evaporative efflorescent precipitates. Radiation doses associated with the open pit average 5.65 mSv year-1; waste dumps commonly have lower values, especially where soil-covered. Surface pit water is slightly acid, with high sulfate values accompanied by levels of U, Cu and Ni close to or above Australian water guideline values for livestock. Dispersion of U and related elements into soils and stream sediments occurs by physical (erosional) processes and from chemical precipitation. Plants growing in the mine void, on waste dumps and contaminated soil display evidence of biological uptake of U, LREE, Cu and Th and to a lesser degree of As, Ni, Pb, Y and Zn, with values being up to 1-2 orders of magnitude above background sites for the same species. Although rehabilitation procedures have been partly successful in reducing dispersion of U and related elements into the surrounding environment, it is apparent that 20 years after rehabilitation, there is significant physical and chemical mobility, including transfer into plants.

Geology of the Wood and East Calhoun mines, Central City District, Gilpin County, Colorado

USGS Publications Warehouse

Drake, Avery Ala

1955-01-01

The Wood-East Calhoun mine area is underlain by complexly folded Precambrian gneiss and pegmatite. The major fold in the area is an anticline that trends about N. 60° E. The Precambrian rocks are intruded by bostonite porphyry dikes of Tertiary age. All the rocks are cut by east- to northeast - trending faults that have been filled by precious metal-sulfide veins which have been worked chiefly for gold. The Wood vein occurs in an east-trending fault; the Calhoun vein occurs in a northeast-trending fault. Much of the uranium production of the Central City district has come from the Wood vein on Quartz Hill. The veins consist chiefly of quartz; pyrite is the chief metallic mineral and chalcopyrite is next in abundance. Sphalerite, galena, tetrahedrite-tennantite, and pitchblende are locally present. Deposition began with alteration-stage quartz and pyrite followed in order by pitchblend, light-yellow pyrite, massive quartz, yellow pyrite, shalerite, comb quartz, chalcopyrite, tetrahedrite-tennantite, galena, chalcopyrite, pyrite, and gray to light-brown fine-grained quartz. The veins of the Central City district are zoned, with quartz-pyrite veins near the center and galena-sphalerite veins on the periphery. The known pitchblende bodies are in the transition between these, but paragenetically, the pitchblende is earlier than all other metallic minerals. A trace element study of the ore indicates an association of zirconium and molybdenum with uranium, of bismuth, antimony, and arsenic with copper, and of cadmium with zinc. The pitchblende and other ore minerals are concentrated in ore shoots. The shoots are in open spaces controlled by the competency of the wall rocks, the presence of a prevailing direction of weakness in the rocks, and changes in strike and dip of the vein. The pitchblende is thought to be a local constituent of the quartz-pyrite ores and to owe its origin to residual solutions from the quartz bostonite magma.

PRODUCTION OF URANIUM METAL BY CARBON REDUCTION

DOEpatents

Holden, R.B.; Powers, R.M.; Blaber, O.J.

1959-09-22

The preparation of uranium metal by the carbon reduction of an oxide of uranium is described. In a preferred embodiment of the invention a charge composed of carbon and uranium oxide is heated to a solid mass after which it is further heated under vacuum to a temperature of about 2000 deg C to produce a fused uranium metal. Slowly ccoling the fused mass produces a dendritic structure of uranium carbide in uranium metal. Reacting the solidified charge with deionized water hydrolyzes the uranium carbide to finely divide uranium dioxide which can be separated from the coarser uranium metal by ordinary filtration methods.

ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

EPA Science Inventory

Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixed methyltin mercaptoester sulfides... Substances § 721.5075 Mixed methyltin mercaptoester sulfides. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as mixed methyltin mercaptoester...

30 CFR 250.808 - Hydrogen sulfide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, REGULATION, AND ENFORCEMENT, DEPARTMENT OF THE... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen...

IRON SULFIDES IN THE ENVIRONMENT: FORMATION, FATE, AND SIGNIFICANCE TO CONTAMINANT BEHAVIOR

EPA Science Inventory

This seminar will cover aspects of the geochemistry of iron sulfides, their formation in sedimentary and aquifer environments, and their roles in sequestering and releasing contaminants. A special emphasis will be placed on the interactions between iron sulfides and arsenic.

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.

Preliminary results of sulfide melt/silicate wetting experiments in a partially melted ordinary chondrite

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1994-01-01

Recently, mechanisms for core formation in planetary bodies have received considerable attention. Most current theories emphasize the need for large degrees of silicate partial melting to facilitate the coalescence and sinking of sulfide-metal liquid blebs through a low strength semi-crystalline silicate mush. This scenario is based upon observations that sulfide-metal liquid tends to form circular blebs in partially molten meteorites during laboratory experiments. However, recent experimental work by Herpfer and Larimer indicates that some sulfide-Fe liquids have wetting angles at and slightly below 60 deg in an olivine aggregate, implying an interconnected melt structure at any melt fraction. Such melt interconnectivity provides a means for gravitational compaction and extraction of the majority of a sulfide liquid phase in small planetary bodies without invoking large degrees of silicate partial melting. Because of the important ramifications of these results, we conducted a series of experiments using H-chondrite starting material in order to evaluate sulfide-liquid/silicate wetting behavior in a more complex natural system.

Insights into solar nebula formation of pyrrhotite from nanoscale disequilibrium phases produced by H2S sulfidation of Fe metal

DOE PAGES

Gainsforth, Z; Lauretta, DS; Tamura, N; ...

2017-09-01

© 2017 by Walter de Gruyter Berlin/Boston. Lauretta (2005) produced sulfide in the laboratory by exposing canonical nebular metal analogs to H 2 S gas under temperatures and pressures relevant to the formation of the Solar System. The resulting reactions produced a suite of sulfides and nanophase materials not visible at the microprobe scale, but which we have now analyzed by TEM for comparison with interplanetary dust samples and comet Wild 2 samples returned by the Stardust mission. We find the unexpected result that disequilibrium formation favors pyrrhotite over troilite and also produces minority schreibersite, daubréelite, barringerite, taenite, oldhamite, andmore » perryite at the metal-sulfide interface. TEM identification of nanophases and analysis of pyrrhotite superlattice reflections illuminate the formation pathway of disequilibrium sulfide. We discuss the conditions under which such disequilibrium can occur, and implications for formation of sulfide found in extraterrestrial materials.« less

Geology of the Brick Flat massive sulfide body, Iron Mountain cluster, West Shasta district, California ( USA).

USGS Publications Warehouse

Albers, J.P.

1985-01-01

The Brick Flat massive sulfide body is one of a group of 8 individual bodies that constitute the Iron Mountain cluster in the S part of the West Shasta district. Before they were separated by postmineral faulting, 5 of the 8 sulfide bodies formed a single large deposit about 1375 m long with a mass of some 23 million metric tons. The pyritic Brick Flat sulfide body is one of the 5 faulted segements of this deposit. The Brick Flat massive sulfide lies within medium phenocryst rhyolite that is characteristic of the ore-bearing middle unit of the Balaklala Rhyolite. It is interpreted to be downfaulted a vertical distance of 75 to 85 m from the Old Mine sulfide-gossan orebody along the N-dipping Camden South fault. It is bounded in turn on its N side by another parallel fault, the Camden North, which drops the orebody down another 75 m to the level of the Richmond orebody. -from Author

Selective Sulfidation of Lead Smelter Slag with Pyrite and Flotation Behavior of Synthetic ZnS

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Zhang, Tianfu; Qin, Wenqing

2016-08-01

The selective sulfidation of lead smelter slag with pyrite in the presence of carbon and Na salts, and the flotation behavior of synthetic ZnS were studied. The effects of temperature, time, pyrite dosage, Na salts, and carbon additions were investigated based on thermodynamic calculation, and correspondingly, the growth mechanism of ZnS particles was studied at high temperatures. The results indicated that the zinc in lead smelter slag was selectively converted into zinc sulfides by sulfidation roasting. The sulfidation degree of zinc was increased until the temperature, time, pyrite, and carbon dosages reached their optimum values, under which it was more than 95 pct. The growth of ZnS particles largely depended upon roasting temperature, and the ZnS grains were significantly increased above 1373 K (1100 °C) due to the formation of a liquid phase. After the roasting, the zinc sulfides generated had a good floatability, and 88.34 pct of zinc was recovered by conventional flotation.

Radioactive mineral spring precipitates, their analytical and statistical data and the uranium connection

USGS Publications Warehouse

Cadigan, R.A.; Felmlee, J.K.

1982-01-01

Major radioactive mineral springs are probably related to deep zones of active metamorphism in areas of orogenic tectonism. The most common precipitate is travertine, a chemically precipitated rock composed chiefly of calcium carbonate, but also containing other minerals. The mineral springs are surface manifestations of hydrothermal conduit systems which extend downward many kilometers to hot source rocks. Conduits are kept open by fluid pressure exerted by carbon dioxide-charged waters rising to the surface propelled by heat and gas (CO2 and steam) pressure. On reaching the surface, the dissolved carbon dioxide is released from solution, and calcium carbonate is precipitated. Springs also contain sulfur species (for example, H2S and HS-), and radon, helium and methane as entrained or dissolved gases. The HS- ion can react to form hydrogen sulfide gas, sulfate salts, and native sulfur. Chemical salts and native sulfur precipitate at the surface. The sulfur may partly oxidize to produce detectable sulfur dioxide gas. Radioactivity is due to the presence of radium-226, radon-222, radium-228, and radon-220, and other daughter products of uranium-238 and thorium-232. Uranium and thorium are not present in economically significant amounts in most radioactive spring precipitates. Most radium is coprecipitated at the surface with barite. Barite (barium sulfate) forms in the barium-containing spring water as a product of the oxidation of sulfur species to sulfate ions. The relatively insoluble barium sulfate precipitates and removes much of the radium from solution. Radium coprecipitates to a lesser extent with manganese-barium- and iron-oxy hydroxides. R-mode factor analysis of abundances of elements suggests that 65 percent of the variance of the different elements is affected by seven factors interpreted as follows: (1) Silica and silicate contamination and precipitation; (2) Carbonate travertine precipitation; (3) Radium coprecipitation; (4) Evaporite precipitation; (5) Hydrous limonite precipitation and coprecipitated elements including uranium; (6) Rare earth elements deposited with detrital contamination (?); (7) Metal carbonate adsorption and precipitation. Economically recoverable minerals occurring at some localities in spring precipitates are ores of iron, manganese, sulfur, tungsten and barium and ornamental travertine. Continental radioactive mineral springs occur in areas of crustal thickening caused by overthrusting of crustal plates, and intrusion and metamorphism. Sedimentary rocks on the lower plate are trapped between the plates and form a zone of metamorphism. Connate waters, carbonate rocks and organic-carbon-bearing rocks react to extreme pressure and temperature to produce carbon dioxide, and steam. Fractures are forced open by gas and fluid pressures. Deep-circulating meteoric waters then come in contact with the reactive products, and a hydrothermal cell forms. When hot mineral-charged waters reach the surface they form the familiar hot mineral springs. Hot springs also occur in relation to igneous intrusive action or volcanism both of which may be products of the crustal plate overthrusting. Uranium and thorium in the sedimentary rocks undergoing metamorphism are sometimes mobilized, but mobilization is generally restricted to an acid hydrothermal environment; much is redeposited in favorable environments in the metamorphosed sediments. Radium and radon, which are highly mobile in both acid and alkaline aqueous media move upward into the hydrothermal cell and to the surface.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

Process for electroslag refining of uranium and uranium alloys

DOEpatents

Lewis, P.S. Jr.; Agee, W.A.; Bullock, J.S. IV; Condon, J.B.

1975-07-22

A process is described for electroslag refining of uranium and uranium alloys wherein molten uranium and uranium alloys are melted in a molten layer of a fluoride slag containing up to about 8 weight percent calcium metal. The calcium metal reduces oxides in the uranium and uranium alloys to provide them with an oxygen content of less than 100 parts per million. (auth)

Detection of depleted uranium in urine of veterans from the 1991 Gulf War.

PubMed

Gwiazda, R H; Squibb, K; McDiarmid, M; Smith, D

2004-01-01

American soldiers involved in "friendly fire" accidents during the 1991 Gulf War were injured with depleted-uranium-containing fragments or possibly exposed to depleted uranium via other routes such as inhalation, ingestion, and/or wound contamination. To evaluate the presence of depleted uranium in these soldiers eight years later, the uranium concentration and depleted uranium content of urine samples were determined by inductively coupled plasma mass spectrometry in (a) depleted uranium exposed soldiers with embedded shrapnel, (b) depleted uranium exposed soldiers with no shrapnel, and (c) a reference group of deployed soldiers not involved in the friendly fire incidents. Uranium isotopic ratios measured in many urine samples injected directly into the inductively coupled plasma mass spectrometer and analyzed at a mass resolution m/delta m of 300 appeared enriched in 235U with respect to natural abundance (0.72%) due to the presence of an interference of a polyatomic molecule of mass 234.81 amu that was resolved at a mass resolution m/delta m of 4,000. The 235U abundance measured on uranium separated from these urines by anion exchange chromatography was clearly natural or depleted. Urine uranium concentrations of soldiers with shrapnel were higher than those of the two other groups, and 16 out of 17 soldiers with shrapnel had detectable depleted uranium in their urine. In depleted uranium exposed soldiers with no shrapnel, depleted uranium was detected in urine samples of 10 out of 28 soldiers. The median uranium concentration of urines with depleted uranium from soldiers without shrapnel was significantly higher than in urines with no depleted uranium, though substantial overlap in urine uranium concentrations existed between the two groups. Accordingly, assessment of depleted uranium exposure using urine must rely on uranium isotopic analyses, since urine uranium concentration is not an unequivocal indicator of depleted uranium presence in soldiers with no embedded shrapnel.

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

Dissimilatory arsenate reduction with sulfide as electron donor: Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate respirer

USGS Publications Warehouse

Hoeft, S.E.; Kulp, T.R.; Stolz, J.F.; Hollibaugh, J.T.; Oremland, R.S.

2004-01-01

Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3- into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the ??-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

Kinetics of sulfate reduction and sulfide precipitation rates in sediments of a bar-built estuary (Pescadero, California).

PubMed

Richards, Chandra M; Pallud, Céline

2016-05-01

The bar-built Pescadero Estuary in Northern California is a major fish rearing habitat, though recently threatened by near-annual fish kill events, which occur when the estuary transitions from closed to open state. The direct and indirect effects of hydrogen sulfide are suspected to play a role in these mortalities, but the spatial variability of hydrogen sulfide production and its link to fish kills remains poorly understood. Using flow-through reactors containing intact littoral sediment slices, we measured potential sulfate reduction rates, kinetic parameters of microbial sulfate reduction (Rmax, the maximum sulfate reduction rate, and Km, the half-saturation constant for sulfate), potential sulfide precipitation rates, and potential hydrogen sulfide export rates to water at four sites in the closed and open states. At all sites, the Michaelis-Menten kinetic rate equation adequately describes the utilization of sulfate by the complex resident microbial communities. We estimate that 94-96% of hydrogen sulfide produced through sulfate reduction precipitates in the sediment and that only 4-6% is exported to water, suggesting that elevated sulfide concentrations in water, which would affect fish through toxicity and oxygen consumption, cannot be responsible for fish deaths. However, the indirect effects of sulfide precipitates, which chemically deplete, contaminate, and acidify the water column during sediment re-suspension and re-oxidation in the transition from closed to open state, can be implicated in fish mortalities at Pescadero Estuary. Published by Elsevier Ltd.

Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

NASA Astrophysics Data System (ADS)

Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

1998-02-01

The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

Redox processes as revealed by voltammetry in the surface sediments of the Gotland Basin, Baltic Sea

NASA Astrophysics Data System (ADS)

Yücel, Mustafa; Dale, Andy; Sommer, Stefan; Pfannkuche, Olaf

2014-05-01

Sulfur cycling in marine sediments undergoes dramatic changes with changing redox conditions of the overlying waters. The upper sediments of the anoxic Gotland Basin, central Baltic Sea represent a dynamic redox environment with extensive mats of sulfide oxidizing bacteria covering the seafloor beneath the chemocline. In order to investigate sulfur redox cycling at the sediment-water interface, sediment cores were sampled over a transect covering 65 - 174 m water depth in August-September 2013. High resolution (0.25 mm minimum) vertical microprofiles of electroactive redox species including dissolved sulfide and iron were obtained with solid state Au-Hg voltammetric microelectrodes. This approach enabled a fine-scale comparison of porewater profiles across the basin. The steepest sulfide gradients (i.e. the highest sulfide consumption) occurred within the upper 10 mm in sediments covered by surficial mats (2.10 to 3.08 mmol m-2 day-1). In sediments under permanently anoxic waters (>140m), voltammetric signals for Fe(II) and aqueous FeS were detected below a subsurface maximum in dissolved sulfide, indicating a Fe flux originating from older, deeper sedimentary layers. Our results point to a unique sulfur cycling in the Gotland basin seafloor where sulfide accumulation is moderated by sulfide oxidation at the sediment surface and by FeS precipitation in deeper sediment layers. These processes may play an important role in minimizing benthic sulfide fluxes to bottom waters around the major basins of the Baltic Sea.

Evaluation of feed COD/sulfate ratio as a control criterion for the biological hydrogen sulfide production and lead precipitation.

PubMed

Velasco, Antonio; Ramírez, Martha; Volke-Sepúlveda, Tania; González-Sánchez, Armando; Revah, Sergio

2008-03-01

The ability of sulfate-reducing bacteria to produce hydrogen sulfide and the high affinity of sulfide to react with divalent metallic cations represent an excellent option to remove heavy metals from wastewater. Different parameters have been proposed to control the hydrogen sulfide production by anaerobic bacteria, such as the organic and sulfate loading rates and the feed COD/SO4(2-) ratio. This work relates the feed COD/SO4(2-) ratio with the hydrogen sulfide production and dissolved lead precipitation, using ethanol as carbon and energy source in an up-flow anaerobic sludge blanket reactor. A maximum dissolved sulfide concentration of 470+/-7 mg S/L was obtained at a feed COD/SO4(2-) ratio of 2.5, with sulfate and ethanol conversions of approximately 94 and 87%, respectively. The lowest dissolved sulfide concentration (145+/-10 mg S/L) was observed with a feed COD/SO4(2-) ratio of 0.67. Substantial amounts of acetate (510-1730 mg/L) were produced and accumulated in the bioreactor from ethanol oxidation. Although only incomplete oxidation of ethanol to acetate was observed, the consortium was able to remove 99% of the dissolved lead (200 mg/L) with a feed COD/SO4(2-) ratio of 1.5. It was found that the feed COD/SO4(2-) ratio could be an adequate parameter to control the hydrogen sulfide production and the consequent precipitation of dissolved lead.

21 CFR 872.1870 - Sulfide detection device.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Sulfide detection device. 872.1870 Section 872.1870 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Diagnostic Devices § 872.1870 Sulfide detection device. (a) Identification...

Formation of unequilibrated R chondrite chondrules and opaque phases

NASA Astrophysics Data System (ADS)

Miller, K. E.; Lauretta, D. S.; Connolly, H. C.; Berger, E. L.; Nagashima, K.; Domanik, K.

2017-07-01

Sulfide assemblages are commonly found in chondritic meteorites as small inclusions in the matrix or in association with chondrules. These assemblages are widely hypothesized to form through pre-accretionary corrosion of metal by H2S gas or through parent body processes. We report here on two unequilibrated R chondrite samples that contain large, chondrule-sized sulfide nodules in the matrix. Both samples are from Mount Prestrud (PRE) 95404. Chemical maps and spot and broad-beam electron microprobe analyses (EMPA) were used to assess the distribution, stoichiometry, and bulk composition of sulfide nodules and silicate chondrules in the clasts. Oxygen isotope data were collected via secondary ion mass spectrometry (SIMS) to assess the relationship of chondrules to other chondrite groups. Scanning electron microscopy (SEM), focused ion beam (FIB), and transmission electron microscopy (TEM) analyses were used to assess fine-scale features and identify crystal structures in sulfide assemblages. Thermodynamic models were used to assess the temperature, sulfur fugacity (fS2), total pressure, dust-to-gas ratio, and oxygen fugacity (fO2) conditions during sulfide nodule and chondrule formation. The unequilibrated clasts include a mixture of type I and type II chondrules, as well as non-porphyritic chondrules. Chondrule oxygen isotopes overlap with ordinary-chondrite chondrules. Sulfide nodules average 200 μm in diameter, have rounded shapes, and are primarily composed of pyrrhotite, pentlandite, and magnetite. Some are deformed around chondrules in a petrologic relationship similar in appearance to compound chondrules. Both nodules and sulfides in chondrules include phosphate inclusions and Cu-rich lamellae, which suggests a genetic relationship between sulfides in chondrules and in the matrix. Ni/Co ratios for matrix and chondrule sulfides are solar, while Fe and Ni are non-solar and inversely related. We hypothesize that sulfide nodules formed via pre-accretionary melt processes. During chondrule formation, precursors composed of a mixture of silicate and sulfide material were heated to form immiscible melt droplets, which separated and cooled to form Si-rich chondrules and S-rich nodules. Sulfide melt was stabilized by a high total pressure (∼1 atm) in a dust- or ice-enriched environment. Heating of this material contributed to a high fS2 (2 × 10-3 atm at 1138 °C), and high fO2 (IW - 1 to IW - 4), in an environment with peak temperatures between 1539 °C and 1750 °C. Oxygen isotopic compositions in this region were similar to those recorded by the LL-chondrite chondrules.

Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

NASA Astrophysics Data System (ADS)

Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

2016-12-01

Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated that magma ascent velocities at Piton de la Fournaise are high enough to counterbalance the settling velocities of millimeter-size sulfides. Despite their high density, sulfide liquids are thus transferred upward during eruptions and their destabilization contributes to SO2 emanations. Assimilation of foreign sulfides from the lithosphere can explain why SO2 emissions sometimes (e.g., during the April 2007 eruption) exceed those predicted from the S content of melt inclusions.

Process for electrolytically preparing uranium metal

DOEpatents

Haas, Paul A.

1989-01-01

A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

Process for electrolytically preparing uranium metal

DOEpatents

Haas, Paul A.

1989-08-01

A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

Decontamination of uranium-contaminated waste oil using supercritical fluid and nitric acid.

PubMed

Sung, Jinhyun; Kim, Jungsoo; Lee, Youngbae; Seol, Jeunggun; Ryu, Jaebong; Park, Kwangheon

2011-07-01

The waste oil used in nuclear fuel processing is contaminated with uranium because of its contact with materials or environments containing uranium. Under current law, waste oil that has been contaminated with uranium is very difficult to dispose of at a radioactive waste disposal site. To dispose of the uranium-contaminated waste oil, the uranium was separated from the contaminated waste oil. Supercritical R-22 is an excellent solvent for extracting clean oil from uranium-contaminated waste oil. The critical temperature of R-22 is 96.15 °C and the critical pressure is 49.9 bar. In this study, a process to remove uranium from the uranium-contaminated waste oil using supercritical R-22 was developed. The waste oil has a small amount of additives containing N, S or P, such as amines, dithiocarbamates and dialkyldithiophosphates. It seems that these organic additives form uranium-combined compounds. For this reason, dissolution of uranium from the uranium-combined compounds using nitric acid was needed. The efficiency of the removal of uranium from the uranium-contaminated waste oil using supercritical R-22 extraction and nitric acid treatment was determined.

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass.

PubMed

Duquène, L; Vandenhove, H; Tack, F; Van Hees, M; Wannijn, J

2010-02-01

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C(DGT)) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO(2)(2+), uranyl carbonate complexes and UO(2)PO(4)(-). The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants. Copyright 2009 Elsevier Ltd. All rights reserved.

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

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

None

Films of cadmium sulfide and cadmium telluride have been produced by screen printing and sintering. Cadmium sulfide films ten microns thick had a resistivity in the 10 ohm-cm range. A technique was developed for forming a cadmium telluride layer on top of a cadmium sulfide layer. Process control and device preparation are areas requiring further study.

Growth Kinetics and Modeling of ZnO Nanoparticles

ERIC Educational Resources Information Center

Hale, Penny S.; Maddox, Leone M.; Shapter, Joe G.; Voelcker, Nico H.; Ford, Michael J.; Waclawik, Eric R.

2005-01-01

The technique for producing quantum-sized zinc oxide (ZnO) particles is much safer than a technique that used hydrogen sulfide gas to produce cadmium sulfide and zinc sulfide nanoparticles. A further advantage of this method is the ability to sample the solution over time and hence determine the growth kinetics.

Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products

EPA Science Inventory

The formation of nickel sulfides has been examined experimentally over the temperature range from 25 to 60°C. At all conditions studied, hexagonal (α-NiS) was the initial precipitate from solution containing Ni2+ and dissolved sulfide. The formation of millerite (β- NiS, rhombo...

ELEVATED DISSOLVED SULFIDES IN SURFICIAL SEDIMENTS OF YAQUINA BAY ESTUARY, OREGON

EPA Science Inventory

Dissolved sulfide concentrations were measured in porewater of surficial sediments collected from two exposed intertidal sites in Yaquina Bay, Oregon. Idaho Pt. (IP) is an area where drift green macroalgae is known to accumulate, and the odor of hydrogen sulfide gas (H2S) on th...

21 CFR 73.2995 - Luminescent zinc sulfide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity...

Optimization of the superconducting phase of hydrogen sulfide

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Masur, E. A.

2015-12-01

The electron and phonon spectra, as well as the densities of electron and phonon states of the SH3 phase and the stable orthorhombic structure of hydrogen sulfide SH2, are calculated for the pressure interval 100-225 GPa. It is found that the I4/ mmm phase can be responsible for the superconducting properties of metallic hydrogen sulfide along with the SH3 phase. Sequential stages for obtaining and conservation of the SH2 phase are proposed. The properties of two (SH2 and SH3) superconducting phases of hydrogen sulfide are compared.

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, J.B.L.; Gorski, A.J.; Daniels, E.J.

1993-05-18

A process is described for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is [dis]associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Hydrogen and sulfur recovery from hydrogen sulfide wastes

DOEpatents

Harkness, John B. L.; Gorski, Anthony J.; Daniels, Edward J.

1993-01-01

A process for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

Integrated thin film cadmium sulfide solar cell module

NASA Technical Reports Server (NTRS)

Mickelsen, R. A.; Abbott, D. D.

1971-01-01

The design, development, fabrication and tests of flexible integrated thin-film cadmium sulfide solar cells and modules are discussed. The development of low cost and high production rate methods for interconnecting cells into large solar arrays is described. Chromium thin films were applied extensively in the deposited cell structures as a means to: (1) achieve high adherence between the cadmium sulfide films and the vacuum-metallized copper substrates, (2) obtain an ohmic contact to the cadmium sulfide films, and (3) improve the adherence of gold films as grids or contact areas.

Fossils of hydrothermal vent worms from Cretaceous sulfide ores of the Samail ophiolite, Oman

USGS Publications Warehouse

Haymon, R.M.; Koski, R.A.; Sinclair, C.

1984-01-01

Fossil worm tubes of Cretaceous age preserved in the Bayda massive sulfide deposit of the Samail ophiolite, Oman, are apparently the first documented examples of fossils embedded in massive sulfide deposits from the geologic record. The geologic setting of the Bayda deposit and the distinctive mineralogic and textural features of the fossiliferous samples suggest that the Bayda sulfide deposit and fossil fauna are remnants of a Cretaceous sea-floor hydrothermal vent similar to modern hot springs on the East Pacific Rise and the Juan de Fuca Ridge.

A kuroko-type polymetallic sulfide deposit in a submarine silicic caldera

PubMed

Iizasa; Fiske; Ishizuka; Yuasa; Hashimoto; Ishibashi; Naka; Horii; Fujiwara; Imai; Koyama

1999-02-12

Manned submersible studies have delineated a large and actively growing Kuroko-type volcanogenic massive sulfide deposit 400 kilometers south of Tokyo in Myojin Knoll submarine caldera. The sulfide body is located on the caldera floor at a depth of 1210 to 1360 meters, has an area of 400 by 400 by 30 meters, and is notably rich in gold and silver. The discovery of a large Kuroko-type polymetallic sulfide deposit in this arc-front caldera raises the possibility that the numerous unexplored submarine silicic calderas elsewhere might have similar deposits.

Optimization of biological sulfide removal in a CSTR bioreactor.

PubMed

Roosta, Aliakbar; Jahanmiri, Abdolhossein; Mowla, Dariush; Niazi, Ali; Sotoodeh, Hamidreza

2012-08-01

In this study, biological sulfide removal from natural gas in a continuous bioreactor is investigated for estimation of the optimal operational parameters. According to the carried out reactions, sulfide can be converted to elemental sulfur, sulfate, thiosulfate, and polysulfide, of which elemental sulfur is the desired product. A mathematical model is developed and was used for investigation of the effect of various parameters on elemental sulfur selectivity. The results of the simulation show that elemental sulfur selectivity is a function of dissolved oxygen, sulfide load, pH, and concentration of bacteria. Optimal parameter values are calculated for maximum elemental sulfur selectivity by using genetic algorithm as an adaptive heuristic search. In the optimal conditions, 87.76% of sulfide loaded to the bioreactor is converted to elemental sulfur.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1995-04-11

A process is described for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal. 2 figures.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1994-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to exposure additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties

PubMed Central

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-01-01

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu–Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu–Co sulfide vulcanized from precursor (P–Cu–Co sulfide) is able to deliver superior specific capacitance of 592 F g−1 at 1 A g−1 and 518 F g−1 at 10 A g−1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu–Co oxide electrode, respectively. At the same time, excellent cycling stability of P–Cu–Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g−1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P–Cu–Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future. PMID:28590417

Predator avoidance in extremophile fish.

PubMed

Bierbach, David; Schulte, Matthias; Herrmann, Nina; Zimmer, Claudia; Arias-Rodriguez, Lenin; Indy, Jeane Rimber; Riesch, Rüdiger; Plath, Martin

2013-02-06

Extreme habitats are often characterized by reduced predation pressures, thus representing refuges for the inhabiting species. The present study was designed to investigate predator avoidance of extremophile populations of Poecilia mexicana and P. sulphuraria that either live in hydrogen sulfide-rich (sulfidic) springs or cave habitats, both of which are known to have impoverished piscine predator regimes. Focal fishes that inhabited sulfidic springs showed slightly weaker avoidance reactions when presented with several naturally occurring predatory cichlids, but strongest differences to populations from non-sulfidic habitats were found in a decreased shoaling tendency with non-predatory swordtail (Xiphophorus hellerii) females. When comparing avoidance reactions between P. mexicana from a sulfidic cave (Cueva del Azufre) and the adjacent sulfidic surface creek (El Azufre), we found only slight differences in predator avoidance, but surface fish reacted much more strongly to the non-predatory cichlid Vieja bifasciata. Our third experiment was designed to disentangle learned from innate effects of predator recognition. We compared laboratory-reared (i.e., predator-naïve) and wild-caught (i.e., predator-experienced) individuals of P. mexicana from a non-sulfidic river and found no differences in their reaction towards the presented predators. Overall, our results indicate (1) that predator avoidance is still functional in extremophile Poecilia spp. and (2) that predator recognition and avoidance reactions have a strong genetic basis.

Coenzyme Q deficiency causes impairment of the sulfide oxidation pathway.

PubMed

Ziosi, Marcello; Di Meo, Ivano; Kleiner, Giulio; Gao, Xing-Huang; Barca, Emanuele; Sanchez-Quintero, Maria J; Tadesse, Saba; Jiang, Hongfeng; Qiao, Changhong; Rodenburg, Richard J; Scalais, Emmanuel; Schuelke, Markus; Willard, Belinda; Hatzoglou, Maria; Tiranti, Valeria; Quinzii, Catarina M

2017-01-01

Coenzyme Q (CoQ) is an electron acceptor for sulfide-quinone reductase (SQR), the first enzyme of the hydrogen sulfide oxidation pathway. Here, we show that lack of CoQ in human skin fibroblasts causes impairment of hydrogen sulfide oxidation, proportional to the residual levels of CoQ. Biochemical and molecular abnormalities are rescued by CoQ supplementation in vitro and recapitulated by pharmacological inhibition of CoQ biosynthesis in skin fibroblasts and ADCK3 depletion in HeLa cells. Kidneys of Pdss2 kd/kd mice, which only have ~15% residual CoQ concentrations and are clinically affected, showed (i) reduced protein levels of SQR and downstream enzymes, (ii) accumulation of hydrogen sulfides, and (iii) glutathione depletion. These abnormalities were not present in brain, which maintains ~30% residual CoQ and is clinically unaffected. In Pdss2 kd/kd mice, we also observed low levels of plasma and urine thiosulfate and increased blood C4-C6 acylcarnitines. We propose that impairment of the sulfide oxidation pathway induced by decreased levels of CoQ causes accumulation of sulfides and consequent inhibition of short-chain acyl-CoA dehydrogenase and glutathione depletion, which contributes to increased oxidative stress and kidney failure. © 2016 The Authors. Published under the terms of the CC BY 4.0 license.

Convergent life-history shifts: toxic environments result in big babies in two clades of poeciliids

NASA Astrophysics Data System (ADS)

Riesch, Rüdiger; Plath, Martin; García de León, Francisco J.; Schlupp, Ingo

2010-02-01

The majority of studies on ecological speciation in animals have investigated the divergence caused by biotic factors like divergent food sources or predatory regimes. Here, we examined a system where ecological speciation can clearly be ascribed to abiotic environmental gradients of naturally occurring toxic hydrogen sulfide (H2S). In southern Mexico, two genera of livebearing fishes (Poeciliidae: Poecilia and Gambusia) thrive in various watercourses with different concentrations of H2S. Previous studies have revealed pronounced genetic differentiation between different locally adapted populations in one species ( Poecilia mexicana), pointing towards incipient speciation. In the present study, we examined female reproductive life-history traits in two species pairs: Gambusia sexradiata (from a nonsulfidic and a sulfidic habitat) and Gambusia eurystoma (sulfide-endemic), as well as P. mexicana (nonsulfidic and sulfidic) and Poecilia sulphuraria (sulfide endemic). We found convergent divergence of life-history traits in response to sulfide; most prominently, extremophile poeciliids exhibit drastically increased offspring size coupled with reduced fecundity. Furthermore, within each genus, this trend increased with increasing sulfide concentrations and was most pronounced in the two endemic sulfur-adapted species. We discuss the adaptive significance of large offspring size in toxic environments and propose that divergent life-history evolution may promote further ecological divergence through isolation by adaptation.

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties.

PubMed

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-06-07

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu-Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu-Co sulfide vulcanized from precursor (P-Cu-Co sulfide) is able to deliver superior specific capacitance of 592 F g -1 at 1 A g -1 and 518 F g -1 at 10 A g -1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu-Co oxide electrode, respectively. At the same time, excellent cycling stability of P-Cu-Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g -1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P-Cu-Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future.

Predator Avoidance in Extremophile Fish

PubMed Central

Bierbach, David; Schulte, Matthias; Herrmann, Nina; Zimmer, Claudia; Arias-Rodriguez, Lenin; Indy, Jeane Rimber; Riesch, Rüdiger; Plath, Martin

2013-01-01

Extreme habitats are often characterized by reduced predation pressures, thus representing refuges for the inhabiting species. The present study was designed to investigate predator avoidance of extremophile populations of Poecilia mexicana and P. sulphuraria that either live in hydrogen sulfide-rich (sulfidic) springs or cave habitats, both of which are known to have impoverished piscine predator regimes. Focal fishes that inhabited sulfidic springs showed slightly weaker avoidance reactions when presented with several naturally occurring predatory cichlids, but strongest differences to populations from non-sulfidic habitats were found in a decreased shoaling tendency with non-predatory swordtail (Xiphophorus hellerii) females. When comparing avoidance reactions between P. mexicana from a sulfidic cave (Cueva del Azufre) and the adjacent sulfidic surface creek (El Azufre), we found only slight differences in predator avoidance, but surface fish reacted much more strongly to the non-predatory cichlid Vieja bifasciata. Our third experiment was designed to disentangle learned from innate effects of predator recognition. We compared laboratory-reared (i.e., predator-naïve) and wild-caught (i.e., predator-experienced) individuals of P. mexicana from a non-sulfidic river and found no differences in their reaction towards the presented predators. Overall, our results indicate (1) that predator avoidance is still functional in extremophile Poecilia spp. and (2) that predator recognition and avoidance reactions have a strong genetic basis. PMID:25371337

Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

PubMed Central

Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

2014-01-01

Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, James W.

1995-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Formation of mercury sulfide from Hg(II)−thiolate complexes in natural organic matter

USGS Publications Warehouse

Alain Manceau,; Cyprien Lemouchi,; Mironel Enescu,; Anne-Claire Gaillot,; Martine Lanson,; Valerie Magnin,; Pieter Glatzel,; Poulin, Brett; Ryan, Joseph N.; Aiken, George R.; Isabelle Gautier-Lunea,; Kathryn L. Nagy,

2015-01-01

Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, TN, in the United States. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury–sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury–sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.

Persistency-field Eh-pH diagrams for sulfides and their application to supergene oxidation and enrichment of sulfide ore bodies

USGS Publications Warehouse

Sato, M.

1992-01-01

At temperatures prevailing near the Earth's surface, metastable co-existence of chemical substances is common because chemical reactions that would directly lead to the attainment of thermody-namically most stable equilibria are often blocked by high activation energy barriers. The persistency of a metastable assemblage is then governed by alternative reaction paths that provide lower activation energy barriers. Comparison of observed mineral assemblages in the supergene oxidized and enriched sulfide ores with corresponding stability Eh-pH diagrams reveals that the supergene assemblages are mostly metastable due primarily to the persistency of sulfide minerals beyond stability boundaries. A new set of diagrams called persistency-field Eh-pH diagrams has been constructed for binary metal sulfides on the basis of electrochemical and other experimental data. Each diagram delineates the persistency field, which is a combined field of thermodynamic stability and reaction path-controlled metastability, for a specific sulfide mineral. When applied to the supergene assemblages, these new diagrams show much better correspondence to the field observations. Although there may still be room for further refinement, the new diagrams appear to provide a strong visual aid to the understanding of the behavior of sulfide minerals in the supergene conditions. ?? 1992.

Mercury's Magma Ocean

NASA Astrophysics Data System (ADS)

Parman, S. W.; Parmentier, E. M.; Wang, S.

2016-12-01

The crystallization of Mercury's magma ocean (MMO) would follow a significantly different path than the terrestrial or lunar magma ocean. Evidence from the MESSENGER mission [1] indicates that Mercury's interior has an oxygen fugacity (fO2) orders of magnitude lower any other terrestrial planet (3-8 log units below the iron-wustite buffer = IW-3 to IW-8; [2]). At these conditions, silicate melts and minerals have negligible Fe contents. All Fe is present in sulfides or metal. Thus, the build up of Fe in the last dregs of the lunar magma ocean, that is so important to its evolution, would not happen in the MMO. There would be no overturn or plagioclase flotation crust. Sulfur solubility in silicate melts increases dramatically at low fO2, from 1 wt% at IW-3 to 8wt% at IW-8 [3]. Thus it is possible, perhaps probable, that km-thick layers of sulfide formed during MMO crystallization. Some of the sulfides (e.g. CaS) have high partition coefficients for trace elements and so could control the spatial distribution of radioactive heat producing elements such as U, Th and K. This in turn would have first order effects on the thermal and chemical evolution of the planet. The distribution of the sulfide layers depend upon the density of the sulfides that form in the MMO. At such low fO2, S forms compounds with a range of elements not typical for other planets: Ca, Mg, Na, K. The densities of these sulfides vary widely, with Mg and Ca-rich sulfides being more dense than estimated MMO densities, and Na and K-rich sulfides being less dense than the MMO. Thus sulfide sinking and floating may produce substantial chemical layering on Mercury, potentially including an Mg-Ca rich deep layer and a Na-K rich shallow layer or possibly floatation crust. The total amount of S in the MMO depends on the fO2 and the bulk S content of Mercury, both of which are poorly constrained. In the most extreme case, if the MMO had an fO2of IW-8 and was sulfide saturated from the start, a total equivalent layer of sulfide up to 50 km could form (Figure 1). [1] Nittler et al (2011) Science 333: 847-1850., [2] Zolotov et al (2013), JGR 118: 138-146. [3] Berthet et al (2009) GCA 73: 6402-6420.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore deposits.

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 results of spectral induced polarization measurements, Wadi Bidah District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Smith, Bruce D.; Tippens, C.L.; Flanigan, V.J.; Sadek, Hamdy

1983-01-01

Laboratory spectral induced polarization (SIP) measurements on 29 carbonaceous schist samples from the Wadi Bidah district show that most are associated with very long polarization decays or, equivalently, large time constants. In contrast, measurements on two massive sulfide samples indicate shorter polarization decays or smaller time constants. This difference in time constants for the polarization process results in two differences in the phase spectra in the frequency range of from 0.06 to 1Hz. First, phase values of carbonaceous rocks generally decrease as a function of increasing frequency. Second, phase values of massive sulfide-bearing rocks increase as a function of increasing frequency. These results from laboratory measurements agree well with those from other reported SIP measurements on graphites and massive sulfides from the Canadian Shield. Four SIP lines, measured by using a 50-m dipole-dipole array, were surveyed at the Rabathan 4 prospect to test how well the results of laboratory sample measurements can be applied to larger scale field measurements. Along one line, located entirely over carbonaceous schists, the phase values decreased as a function of increasing frequency. Along a second line, located over both massive sulfides and carbonaceous schists as defined by drilling, the phase values measured over carbonaceous schists decreased as a function of increasing frequency, whereas those measured over massive sulfides increased. In addition, parts of two lines were surveyed down the axes of the massive sulfide and carbonaceous units. The phase values along these lines showed similar differences between the carbonaceous schists and massive sulfides. To date, the SIP survey and the SIP laboratory measurements have produced the only geophysical data that indicate an electrical difference between the massive sulfide-bearing rocks and the surrounding carbonaceous rocks in the Wadi Bidah district. However, additional sample and field measurements in areas of known mineralization would fully evaluate the SIP method as applied to various geologic environments and styles of massive sulfide mineralization. Additionally, the efficiency of SIP surveys in delineating areas of sulfide mineralization might be improved by surveying lines down the axes of known electrical conductors. An evaluation of the applied research done on the SIP method to date suggests that this technique offers significant exploration applications to massive sulfide exploration in the Kingdom of Saudi Arabia.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Sulfide in the core and the composition of the silicate Earth

NASA Astrophysics Data System (ADS)

Burton, K. W.

2015-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive 'chondritic' meteorites. It now appears, however, that the silicate Earth is not 'chondritic', but depleted in incompatible elements, including refractory lithophile and heat-producing elements. Either Earth lost material during planet-building due to collisional erosion or else internal differentiation processes produced a hidden reservoir deep in the early Earth. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [1]. Pioneering work using the short-lived 146Sm-142Nd system strongly suggests that Earth's silicate mantle is non-chondritic [e.g. 2]. The drawback of such radiogenic isotope systems is that it is not possible to distinguish the fractionation of Sm/Nd that occurs during silicate melting from that occurring during the segregation of a sulfide-melt to form the core. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavy values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd Stable isotope data for chondritic meteorites and mantle rocks, are consistent with the segregation of sulfide to the core. [1] Wohlers &Wood, Nature 520, 337 (2015) [2] Boyet & Carlson, Science 309, 576 (2005)

Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

2018-04-01

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Optimum reaction ratio of coal fly ash to blast furnace cement for effective removal of hydrogen sulfide.

PubMed

Asaoka, Satoshi; Okamura, Hideo; Kim, Kyunghoi; Hatanaka, Yuzuru; Nakamoto, Kenji; Hino, Kazutoshi; Oikawa, Takahito; Hayakawa, Shinjiro; Okuda, Tetsuji

2017-02-01

Reducing hydrogen sulfide concentration in eutrophic marine sediments is crucial to maintaining healthy aquatic ecosystems. Managing fly ash, 750 million tons of which is generated annually throughout the world, is another serious environmental problem. In this study, we develop an approach that addresses both these issues by mixing coal fly ash from coal-fired power plants with blast furnace cement to remediate eutrophic sediments. The purpose of this study is to optimize the mixing ratio of coal fly ash and blast furnace cement to improve the rate of hydrogen sulfide removal based on scientific evidence obtained by removal experiments and XAFS, XRD, BET, and SEM images. In the case of 10 mg-S L -1 of hydrogen sulfide, the highest removal rate of hydrogen sulfide was observed for 87 wt% of coal fly ash due to decreased competition of adsorption between sulfide and hydroxyl ions. Whereas regarding 100 mg-S L -1 , the hydrogen sulfide removal rate was the highest for 95 wt% of coal fly ash. However, for both concentrations, the removal rate obtained by 87 wt% and 95 wt% were statistically insignificant. The crushing strength of the mixture was over 1.2 N mm -2 when the coal fly ash mixing ratio was less than 95 wt%. Consequently, the mixing ratio of coal fly ash was optimized at 87 wt% in terms of achieving both high hydrogen sulfide removal rate and sufficient crushing strength. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dissimilatory arsenate reduction with sulfide as the electron donor--Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate-respirer

USGS Publications Warehouse

Hoeft, Shelley E.; Kulp, Thomas R.; Stolz, John F.; Hollibaugh, James T.; Oremland, Ronald S.

2004-01-01

Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3− into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the δ-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

Trace hydrogen sulfide gas sensor based on tungsten sulfide membrane-coated thin-core fiber modal interferometer

NASA Astrophysics Data System (ADS)

Deng, Dashen; Feng, Wenlin; Wei, Jianwei; Qin, Xiang; Chen, Rong

2017-11-01

A novel fiber-optic hydrogen sulfide sensor based on a thin-core Mach-Zehnder fiber modal interferometer (TMZFI) is demonstrated and fabricated. This in-line interferometer is composed of a short section of thin-core fiber sandwiched between two standard single mode fibers, and the fast response to hydrogen sulfide is achieved via the construction of tungsten sulfide film on the outside surface of the TMZFI using the dip-coating and calcination technique. The fabricated sensing nanofilm is characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) spectrometer, Fourier transform infrared (FTIR) and spectroscopic analysis technology, etc. Experimental results showed that the WS2 sensing film has a hexagonal structure with a compact and porous morphology. The XPS and FTIR indicate that the existence of two elements (W and S) is demonstrated. With the increasing concentration of hydrogen sulfide, the interference spectra appear blue shift. In addition, a high sensitivity of 18.37 pm/ppm and a good linear relationship are obtained within a measurement range from 0 to 80 ppm. In addition, there is an excellent selectivity for H2S, which has also been proved by the surface adsorption energy results of tungsten sulfide with four gases (H2S, N2, O2 and CO2) by using the density functional theory calculations. This interferometer has the advantages of simple structure, high sensitivity and easy manufacture, and could be used in the safety monitoring field of hydrogen sulfide gas.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Metal-saturated sulfide assemblages in NWA 2737: Evidence for impact-related sulfur devolatilization in Martian meteorites

NASA Astrophysics Data System (ADS)

Lorand, Jean-Pierre; Barrat, Jean-Alix; Chevrier, Vincent; Sautter, Violaine; Pont, Sylvain

2012-11-01