Precipitation Of Sulfide Minerals Research Articles

Identifying redox transition zones in the subsurface of a site with historical contamination

Reactive iron mineral coatings found throughout reduction-oxidation (redox) transition zones play an important role in contaminant transformation processes. This research focuses on demonstrating a process for effectively delineating redox transition zones at a site with historical contamination. An 18.3 meter core was collected, subsampled, and preserved under anoxic conditions to maintain its original redox status. To ensure a high vertical resolution, sampling increments of 5.08 cm in length were analyzed for elemental concentrations with X-ray fluorescence (XRF), sediment pH, sediment oxidation-reduction potential (ORP), total volatile organic carbon (TVOC) concentration in the sample headspace, and abundant bacteria (16S rRNA sequencing). Over the core's length, gradients observed ranged from 3.74 to 8.03 for sediment pH, −141.4 mV to +651.0 mV for sediment ORP, and from below detection to a maximum of 9.6 ppm TVOC concentration (as chlorobenzene) in the headspace. The Fe and S gradients correlated with the presence of Fe and S reducing bacteria. S concentrations peaked in the Upper Zone and Zone 1 where Desulfosporosinus was abundant, suggesting precipitation of iron sulfide minerals. In Zone 2, Fe concentrations decreased where Geobacter was abundant, potentially resulting in Fe reduction, dissolution, and precipitation of minerals with increased solubility compared to the Fe(III) minerals. Using complementary geochemical and microbial data, five redox transition zones were delineated in the core collected. This research demonstrates a systematic approach to characterizing redox transition zones in a contaminated environment.

Geochemical transformations beneath man-made ponds: Implications for arsenic mobilization in South Asian aquifers

The role of man-made ponds on arsenic mobilization was examined in Bangladesh. Here, we describe a field experiment that shows how recharge from a newly constructed pond creates a reactive front that moves downward into the underlying aquifer, but only advances slowly, less than 8 cm/year. We found that pond recharge introduces organic carbon that likely drives the reduction of sulfate and solid-phase iron. However, over the six-year period of the study the pond did not drive arsenic contamination of the underlying groundwater. An electron balance indicates that significant precipitation of ferrous iron and sulfide minerals may immobilize arsenic despite the shift towards more reducing conditions, explaining the very low observed aqueous arsenic concentrations. We additionally found that the amount of solid-phase electron acceptors available in the shallow sediments strongly retards the advance of a reduced sediment front. Our results suggest that labile organic carbon introduced by man-made ponds is efficiently mineralized in the sediments immediately below the pond bottom and thus is unlikely to drive arsenic mobilization deeper within the aquifer. We suggest that the excavation of man-made ponds removes young surficial sediments, leaving aged and less reactive sediments beneath the pond, so that recharge through excavated ponds does not mobilize arsenic at the high rates observed in recharge through natural wetlands and river banks.

Competitive adsorption between phosphate and arsenic in soil containing iron sulfide: XAS experiment and DFT calculation approaches

The competitive adsorption between phosphate and arsenic (As) in natural soil and mineral systems is important for controlling subsurface contaminants. Phosphate is known to adsorb more strongly than As in Fe(III) oxide-based mineral systems. Here, X-ray absorption spectroscopy (XAS) and density functional theory (DFT) were employed to understand the fundamental reaction mechanisms of As and phosphate on an FeS surface. The competitive effect of phosphate in As(V)-contaminated soil systems differed with changing FeS concentrations. In soil batches with high FeS contents, As(V) was more strongly adsorbed than phosphate, and no additional As release was observed in the aqueous phase, in the presence of phosphate. Through the XAS measurement of laboratory batch samples, the reaction mechanisms could be comprehensively understood, including the reduction of As(V) to As(III), the secondary precipitation of sulfide minerals, and the adsorption mechanism of As(V) on the surface of FeS. The DFT calculations revealed the relative adsorption strengths on the FeS surface were As(V) > phosphate > As(III). Comparing the adsorption energies revealed that As(V) reacted more strongly with FeS than phosphate and As(III), and that the effect of phosphate co-occurrence was negligible in the FeS–As system, in line with the experimental measurements.

Benthic alkalinity and dissolved inorganic carbon fluxes in the Rhône River prodelta generated by decoupled aerobic and anaerobic processes

Abstract. Estuarine regions are generally considered a major source of atmospheric CO2, as a result of the high organic carbon (OC) mineralization rates in their water column and sediments. Despite this, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites near the sediment–water interface controls the flux of benthic alkalinity. This alkalinity may partially buffer metabolic CO2 generated by benthic OC respiration in sediments. Thus, sediments with high anaerobic respiration rates could contribute less to local acidification than previously thought. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lion, northwestern Mediterranean) in late summer to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH micro-profiles, voltammetric profiles and pore water composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. Benthic TA and DIC fluxes to the water column, ranging between 14 and 74 and 18 and 78 mmol m−2 d−1, respectively, were up to 8 times higher than dissolved oxygen uptake (DOU) rates (10.4±0.9 mmol m−2 d−1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. In the zone close to the river mouth, pore water redox species indicated that TA and DIC were mainly produced by microbial sulfate and iron reduction. Despite the complete removal of sulfate from pore waters, dissolved sulfide concentrations were low and significant concentrations of FeS were found, indicating the precipitation and burial of iron sulfide minerals with an estimated burial flux of 12.5 mmol m−2 d−1 near the river mouth. By preventing reduced iron and sulfide reoxidation, the precipitation and burial of iron sulfide increases the alkalinity release from the sediments during the spring and summer months. Under these conditions, the sediment provides a net source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters and weakens the partial pressure of CO2 increase in the bottom waters that would occur if only DIC was produced.

A Quantitative Framework for Comparing Observed and Simulated Pit-Lake Geochemistry

Pit lakes are commonly studied using advanced geochemical models. However, quantitative post-audits of these studies to assess the degree of agreement with observations are rare. This study used a quantitative evaluator (error variance parameter; Δ) to compare predicted and observed geochemistry of nine pit lakes across three continents and five ore-deposit types. The compiled modeling studies applied a variety of methods to incorporate geochemical (sulfide oxidation and mineral precipitation) and hydrologic processes (groundwater flow and hydrodynamics). Several common ions (Ca, Mg, SO4) and pH were shown to compare well with observations. In contrast, comparisons of model simulations and observations for trace metals and metalloids such as Fe and As were less congruent. The discrepancies for these and other species is potentially linked to inappropriate application of equilibrium thermodynamics and temporal model discretization. Model complexity was also shown to be related to the reproducibility of observed geochemistry. Quantitative analysis using Δ in a wider range of studies may increase understanding of prevalent geochemical processes invoked in pit-lake modeling.

Evolution of the Igarapé Bahia Cu-Au deposit, Carajás Province (Brazil): Early syngenetic chalcopyrite overprinted by IOCG mineralization

The Igarapé Bahia IOCG Cu–Au deposit, located in the Carajás Domain, the northern part of the Carajás Province in the Amazon Craton, is one of the most economically important deposits in the province. The deposit is hosted in the metavolcanosedimentary Igarapé Bahia Group and the metasedimentary Águas Claras Formation. The Igarapé Bahia Group encompasses a lower unit with metavolcanic rocks and metagabbros, and metasedimentary rocks (metarhythmites, epiclastic rocks, and banded iron formation) of the upper unit. Epiclastic rocks are predominant in the Águas Claras Formation. Basement xenoliths within the lower unit yielded an U–Pb zircon age of 2935 ± 36 Ma, suggesting that a sialic crust was present prior to basin installation likely due to rifting. The U–Pb dating of detrital zircons yielded maximum deposition age at 2784 ± 27 Ma for the upper unit, and 2763 ± 32 Ma and 2774 ± 19 Ma for the Águas Claras Formation. Chalcopyrite nodules and layers are found within metarhythmites, concordant to primary structures, but without hydrothermal alteration halos and iron oxide. This chalcopyrite generation seems to have precipitated synchronously to the deposition of the Igarapé Bahia Group. Chalcopyrite nodules and layers show δ34SVCDT values ranging from +0.29 to +1.56‰. These data indicate that most of its sulfur is likely derived from the metavolcanic rocks of the lower unit. Host rocks and chalcopyrite nodules and layers were overprinted by the IOCG mineralization. The latter formed extensive halos of hydrothermal alteration and was accompanied by ductile deformation and hydrothermal brecciation. These processes resulted in (tourmaline)–carbonate–magnetite, (tourmaline)–carbonate–chlorite and (tourmaline)–(biotite)–chlorite mylonites and breccias. Chalcopyrite from magnetite-rich zones (i.e. IOCG mineralization) displays δ34SVCDT values from +1.36 to +5.35‰. In addition to magmatic sulfur, seawater-derived sulfate may have been incorporated in sulfides via thermochemical sulfate-reduction reactions. Trace element geochemistry in distinct copper ores (i.e. nodules and layers versus magnetite-rich) also point to different origins of both styles of mineralization. The timing of the IOCG mineralization was constrained at 2559 ± 34 Ma in the Alemão orebody. These data suggest that an IOCG-type metallogenetic event at ca. 2.5 Ga overprinted an older syngenetic-exhalative type copper mineralization. They also indicate that precipitation of early sulfide minerals within the Itacaiúnas Supergroup may have created Cu-rich sequences that could have been remobilized, generating the broad group of the IOCG deposits at Carajás.

H2-fuelled microbial metabolism in Opalinus Clay

In Switzerland, the Opalinus Clay formation is considered the most likely host rock for a deep geological repository for nuclear waste. In deep geological repositories, H2 is expected to be the most abundant gas formed from the degradation of waste and from metal corrosion. The microbial community present in Opalinus Clay is capable of utilizing H2 as an electron donor and sulfate as an electron acceptor to produce hydrogen sulfide. This could be problematic due to its potential for increasing the corrosion of metal waste canisters containing radioactive waste, however, the possible impacts of these processes on the clay rock have not been fully investigated. In this study, a series of microcosm experiments were set-up containing Opalinus Clay and porewater from the Mont Terri underground research laboratory (Switzerland) as an inoculum. Uninoculated microcosms were established to investigate abiotic processes.In the presence of clay, a higher aqueous sulfate concentration was detected than in those with only porewater present and this concentration decreased over time in the inoculated experiments. However, there was no evidence of hydrogen sulfide production in the aqueous phase. In all experiments with clay, there was an increase in aqueous Fe2+ concentrations with the highest concentrations found in uninoculated experiments. The sulfur speciation of the Opalinus Clay was analysed and the results of the inoculated sample suggested that hydrogen sulfide reacted with Fe2+, precipitating iron sulfide minerals. After the incubation period, the microbial community was dominated by the sulfate-reducing Desulfobulbaceae family.The study suggests that H2-fuelled, microbially-mediated sulfate reduction can affect the mineral composition within the Opalinus Clay due to the precipitation of iron sulfide minerals. These precipitation reactions may enhance the long-term integrity of the repository by removing corrosive hydrogen sulfide from solution when sufficient Fe2+ is available and so protecting the canisters containing the nuclear waste.

Transient early diagenetic processes in Rhône prodelta sediments revealed in contrasting flood events

Floods carry sediments to river deltas and the coastal zone, but little is known about the geochemical evolution of this particulate material deposited over a short period of time. Here, we studied two recent contrasting flood deposits in the Rhône River prodelta area (northwestern Mediterranean Sea). We monitored the porewater and solid-phase chemistry over periods ranging from a few days to 6 months after deposition. Non-steady state diagenetic processes associated with episodic deposition promote a wide spectrum of transient redox conditions in the shallow prodelta region of the Rhône. Specific attributes of diagenetic responses depend on the sources of flood material and scale (thickness) of deposition.The first flood unit of 20–30 cm was composed of light gray mud, poor in organic carbon and rich in reactive manganese oxides. The short-term responses of early diagenetic processes contrasted with a rapid consumption of O2 and NO3- over a few hours just after the deposition event, accompanied by a slower build-up of Mn2+ concentration, and a lagged response in Fe2+ concentration over a few days or weeks. This difference was due to the redox capacity of the sediment, evolving from oxidized, during the flood layer deposition, to more reducing conditions, after a few days or weeks, allowing Fe2+ to build up and remain in solution. Sulfate reduction may have started within a few days within the flood deposit and was greatly enhanced just below the former redox front due to a fresh input of organic matter (OM). This large production of H2S probably led to the precipitation of sulfide minerals in close vicinity to the former redox front, limiting the accumulation of Fe2+ and H2S. The unit was sampled repeatedly three times during the six months following the flood event, and showed that manganese oxides were reduced at a rate of 1.8 mmol m−2 d−1, whereas the iron oxide concentration did not vary substantially.The second flood unit was composed of darker sediment, rich in organic carbon and reactive manganese oxides. The first step of OM degradation was enhanced within this dark deposit with a high release of dissolved organic carbon (DOC). A peak in Mn2+ concentration was also measured in association with the peak in reactive manganese oxides, also showing the rapid reduction of manganese after an input of fresh reactive oxides, and its potential increased release into the water column. Finally, a peak in nitrate concentration appeared in the sediment porewater within this anoxic organic/manganese-rich layer, likely resulting from the anaerobic oxidation of ammonium by manganese oxides.

Reductive dissolution and sequestration of arsenic by microbial iron and thiosulfate reduction.

Iron oxide and oxy-hydroxide are commonly used for remediation and rehabilitation of arsenic (As)-contaminated soil and water. However, the stability of As sequestered by iron oxide and oxy-hydroxide under anaerobic conditions is still uncertain. Geochemical properties influence the behavior of As; in addition, microbial activities affect the mobility of sequestered As in soil and water. Microbial-mediated iron reduction can increase the mobility of As by reductive dissolution of Fe oxide; however, microbial-mediated sulfate reduction can decrease the mobility of As by sulfide mineral precipitation. This study investigated the geomicrobial impact on the behavior of As and stability of sequestered As in iron-rich sediment under anaerobic conditions. Increase in Fe(II) concentrations in water was evidence of microbial-mediated iron reduction. Arsenic concentrations increased with Fe(II) concentration; however, the thiosulfate reduction process also induced immobilization of As through the precipitation of AsFeS. Therefore, microbial-mediated iron reduction and thiosulfate reduction have opposite influences on the mobility of As under anaerobic condition.

Impacts of SO2 gas impurity within a CO2 stream on reservoir rock of a CCS pilot site: Experimental and modelling approach

In order to evaluate chemical impacts of SO2 impurity on reservoir rock during CO2 capture and storage in deep saline aquifers, several batch reactor experiments were performed on laboratory scale using core rock samples from the pilot CO2 injection site in Heletz. In this experiment, the samples were exposed to pure N2(g), pure CO2(g), and CO2(g) with an impurity of 1.5% SO2(g) under reservoir conditions for pressure and temperature (14.5 MPa, 60 °C). Based on the set-up and the obtained experimental results, a batch chemical model was established using the numerical simulation program TOUGHREACT V3.0-OMP. Comparing laboratory and simulation data provides a better understanding of the rock-brine-gas interactions. In addition, it offers an evaluation of the capability of the model to predict chemical interactions in the target injection reservoir during exposure to pure and impure CO2. The best match between the geochemical model and experimental data was achieved when the reactive surface area of minerals in the model was adjusted in order to calibrate the kinetic rates of minerals. The simulations indicated that SO2(g) tends to dissolve rather quickly and oxidizes under a kinetic control. Hence, it has a stronger effect on the acidity of the brine than pure CO2(g) and as a result, increased mineral dissolution and caused the precipitation of sulfate and sulfide minerals. Ankerite, dolomite, and siderite, the most abundant carbonates in the sandstone rock sample, are subject to stronger dissolution in the presence of SO2 gas. The performed simulations confirmed a slower dissolution rate for ankerite and siderite than for dolomite. The model reproduced the precipitation of pyrite and anhydrite as observed in the laboratory. The dissolution of dolomite observed in the batch reaction test with pure N2 is assumed to be due to slight contamination with oxygen and modelling supported this. The inclusion of SO2 increased the porosity over that of the pure CO2 case, and is thus considered to increase the permeability and injectivity of the reservoir as well. Exposure to SO2 also increased the concentration of trace elements. The calibrated kinetic parameters determined in this study will be used to model the injection and long-term behavior of CO2 at the Heletz field site, and may be used for similar geologic reservoirs.

Experimental investigation on thermochemical sulfate reduction in the presence of 1-pentanethiol at 200 and 250 °C: Implications for in situ TSR processes occurring in some MVT deposits

Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4+1-octene (C8H16), MgSO4+1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions.

In situ Pb and bulk Sr isotope analysis of the Yinchanggou Pb-Zn deposit in Sichuan Province (SW China): Constraints on the origin and evolution of hydrothermal fluids

The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11wt% Pb+Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: 206Pb/204Pb=18.17–18.24, 207Pb/204Pb=15.69–15.71, 208Pb/204Pb=38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (206Pb/204Pb=18.11–18.40, 207Pb/204Pb=15.66–15.76, 208Pb/204Pb=38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher 206Pb/204Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (206Pb/204Pb=18.17–18.19), whereas the latter has higher 208Pb/204Pb ratios (38.59–38.63) than the former (208Pb/204Pb=38.51–38.59). However, both types of galena have the same 207Pb/204Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial 87Sr/86Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected 87Sr/86Sr ratios of country sedimentary rocks (87Sr/86Sr200Ma=0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (87Sr/86Sr200Ma=0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit asa strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.

Evolution of borate minerals from contact metamorphic to hydrothermal stages: Ludwigite-group minerals and szaibélyite from the Vysoká – Zlatno skarn, Slovakia

Borate minerals of the ludwigite group (LGM) and szaibelyite in association with hydroxylclinohumite, clinochlore, a serpentine mineral, magnesian magnetite, spinel, magnesite, dolomite and sulphide minerals, occur in a magnesian exoskarn in the R-20 borehole located in the Vysoka – Zlatno Cu-Au porphyry-skarn deposit, located within the Stiavnica Neogene stratovolcano, Western Carpathians, central Slovakia. The skarn is developed along the contact of Miocene granodiorite to quartz-diorite porphyry and a Middle-Upper Triassic dolomite-shale-psammite-anhydrite sedimentary sequence. The boron minerals were investigated by electron probe micro-analyser (EPMA) and micro-Raman techniques. The source of boron could have been from the granodiorite/quartz diorite intrusion; however some supply of B from adjacent evaporite-bearing sediments is also possible. Based on textural and compositional data, the minerals originated during two stages. (1) An early high-temperature, contact-metamorphic and metasomatic stage comprises coarse-crystalline aggregate of LGM (types 1 to 3) in association with hydroxylclinohumite, magnetite, and rarely spinel inclusions in LGM. Compositional variations of LGM show a crystallization sequence from early azoproite [≤17 wt% TiO2; ~0.40 atoms pre formula unit (apfu) Ti, which correspond to ≤79 mol% of the Mg2(Mg0.5Ti0.5)O2(BO3) end-member], Ti-Al-rich members of LGM, “aluminoludwigite “[≤14 wt% Al2O3; ≤0.53 apfu, ≤53 mol% of Mg2AlO2(BO3) end-member] and Al-rich ludwigite in the central zone of crystals, to Ti-Al-poor ludwigite in outer parts of crystals. (2) Minerals of the late retrograde serpentinization and hydrothermal stage form irregular veinlets and aggregates, including partial alteration of hydroxylclinohumite to the serpentine-group mineral and clinochlore, replacement of LGM by szaibelyite, formation of the latest generation of Fe-rich, Ti-Al poor ludwigite in veinlets (type 4), and precipitation of dolomite, magnesite and sulphide minerals (valleriite, sphalerite, chalcopyrite). The distinct compositional zoning of the LGM documents a complex evolution of the skarn beginning with a high-temperature stage 1 and ending with a low-temperature overprint, stage 2.

Sulfur Isotope Fractionation as an Indicator of Biogeochemical Processes in an AMD Passive Bioremediation System

Sulfate, the main dissolved contaminant in acid mine drainage (AMD), is ubiquitous in watersheds affected by coal and metal mining operations worldwide. Engineered passive bioremediation systems (PBS) are low-cost technologies that remediate sulfate contamination by promoting (1) precipitation of sulfate-bearing compounds, such as schwertmannite and gypsum; and (2) microbially-mediated sulfate reduction (BSR) to sulfide with subsequent precipitation of sulfide minerals. In this study, chemical and sulfur isotopic data are used to infer multiple pathways for sulfate sequestration in the Tab-Simco PBS. By simultaneously monitoring sulfate concentrations and δ34SSO4 values at four sampling points across the PBS, we (1) identified that the organic layer within the bioreactor was the primary site of BSR processes contributing to sulfate sequestration; (2) observed seasonal variations of BSR processes; (3) estimated that initially the BSR processes contributed up to 30% to sulfate sequestration in the Tab-Simco bioreactor; and (4) determined that BSR contribution to sulfate sequestration continuously declined over the PBS operational lifetime. Together, our results highlight the utility of combining geochemical and microbial fingerprinting techniques to decipher complementary processes involved in sulfur cycling in a PBS as well as the value of adding the sulfur isotope approach as an essential tool to help understand, predict, prevent and mitigate sulfate contamination in AMD-impacted systems.

STABLE ISOTOPE (δ13C, δ18O) ANALYSIS OF SULFIDE-BEARING CARBONATE SAMPLES USING LASER ABSORPTION SPECTROMETRY

Hydrothermally altered country rocks surrounding hydrothermal ore deposits are commonly characterized by altered δ 18 O and δ 13 C values relative to distal, unaltered rocks. Stable isotopes have been recognized as a powerful tool to complement traditional geochemical and geophysical approaches during mineral exploration, particularly in carbonate replacement and Carlin-type deposits. However, wall-rock alteration and carbonate veining during ore formation is often accompanied by the precipitation of sulfide minerals, complicating stable isotope analysis. The classic phosphoric acid extraction technique for carbonate minerals results in the release of additional H 2 S gas, interfering with isotope ratio mass spectrometry (IRMS), and laser absorption spectrometry (LAS) analysis of CO 2 . Here we present the first results from a novel off-axis integrated cavity output spectrometer (OA-ICOS) instrument, capable of determining the stable isotope composition ( δ 13 C, δ 18 O) of mixed CO 2 -H 2 S gas evolved from carbonate-sulfide mixtures. Instrument calibration was performed by analyzing in-house and commercially available CaCO 3 stable isotope reference materials. Analyses of mixed CO 2 -H 2 S tank gas and sulfide-spiked stable isotope reference materials containing up to 40 wt % chalcopyrite and sphalerite demonstrate that the method outlined here is capable of effectively analyzing previously problematic high sulfide samples. The analytical capabilities, together with the robust nature of the OA-ICOS instrument, may be of direct practical use for mineral exploration in carbonate-hosted hydrothermal systems including ore deposits.

In-situ incubation of iron-sulfur mineral reveals a diverse chemolithoautotrophic community and a new biogeochemical role for Thiomicrospira.

Sulfide mineral precipitation occurs at mid-ocean ridge (MOR) spreading centers, both in the form of plume particles and seafloor massive sulfide structures. A common constituent of MOR is the iron-bearing sulfide mineral pyrrhotite, which was chosen as a substrate for in-situ incubation studies in shallow waters of Catalina Island, CA to investigate the colonization of iron-oxidizing bacteria. Microbial community datasets were obtained from in-situ incubated pyrrhotite, allowing for direct comparison to microbial communities of iron-sulfides from active and inactive chimneys in deep-sea environments. Unclassified Gammaproteobacteria and Alphaproteobacteria (Magnetovibrio) largely dominated the bacterial community on pyrrhotite samples incubated in the water column while samples incubated at the surface sediment showed more even dominance by Deltaproteobacteria (Desulfobulbus), Gammaproteobacteria (Piscirickettsiaceae), Alphaproteobacteria (Rhodobacteraceae), and Bacteroidetes (Flavobacteriia). Cultivations that originated from pyrrhotite samples resulted in the enrichment of both, sheath-forming and stalk-forming Zetaproteobacteria. Additionally, a putative novel species of Thiomicrospira was isolated and shown to grow autotrophically with iron, indicating a new biogeochemical role for this ubiquitous microorganism.

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

Abstract 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.

What Do We Really Know about the Role of Microorganisms in Iron Sulfide Mineral Formation?

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.

Enhanced framboidal pyrite formation related to anaerobic oxidation of methane in the sulfate-methane transition zone of the northern South China Sea

Many studies have confirmed that size distributions of framboidal pyrite can be an effective indicator of bottom-water redox conditions in modern as well as ancient sedimentary environments. However, one environment in which production of framboidal pyrite has not been sufficiently studied to date is the sulfate-methane transition zone (SMTZ), in which anaerobic oxidation of methane (AOM) is coupled with microbial sulfate reduction (MSR) to enhance iron sulfide mineral precipitation (e.g., FeS2, FeS, and Fe3S4). Here, we document for the first time size distributions for pyrite framboids from the SMTZ, based on data from two sites in the methane hydrate-bearing region of the northern South China Sea. On the basis of framboid size, pyrite concentration, and sulfur isotope data, we propose new insights into the formation process of authigenic pyrite framboids within the SMTZ. We conclude that (1) Enhanced anaerobic oxidation of methane (AOM) not only plays a dominant role in the accumulation of 34S-enriched pyrite but also is responsible for formation of highly variable and sometimes exceptionally large pyrite framboids in the SMTZ; (2) Most framboids occur in ‘framboid clusters’ which commonly exhibit rod-like shapes, secondary overgrowths, heavier δ34S values, and unusual size distributions (e.g., mean size>20μm and standard deviation>3.0μm) in the SMTZ; (3) Pyrite framboids formed in the SMTZ, which have characteristics different from those formed in the sulfate reduction zone (SRZ), do not comment on redox conditions of the overlying water column; and (4) Framboid occurrences with similar characteristics in ancient marine deposits may be considered indicators of enhanced AOM and mark the former position of the SMTZ in the paleo-marine system. In addition, significant quantities of elemental sulfur were observed in the SMTZ, possibly related to anaerobic oxidation of hydrogen sulfide and fluctuations of the SMTZ.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

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 δ57Fe 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.