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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Deep abiotic weathering of pyrite

Pyrite is a ubiquitous iron sulfide mineral that is oxidized by trace oxygen. The mineral has been largely absent from global sediments since the rise in oxygen concentration in Earth’s early atmosphere. We analyzed weathering in shale, the most common rock exposed at Earth’s surface, with chemical and microscopic analysis. By looking across scales from 10 −9 to 10 2 meters, we determined the factors that control pyrite oxidation. Under the atmosphere today, pyrite oxidation is rate-limited by diffusion of oxygen to the grain surface and regulated by large-scale erosion and clast-scale fracturing. We determined that neither iron- nor sulfur-oxidizing microorganisms control global pyrite weathering fluxes despite their ability to catalyze the reaction. This multiscale picture emphasizes that fracturing and erosion are as important as atmospheric oxygen in limiting pyrite reactivity over Earth’s history.

58 GEOSCIENCES↗
DOE OSTI2019

Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study

To study thermal desulfurization of pyrite (FeS 2 ), we conducted in situ neutron diffraction experiments in the temperature range 298–1073 K. Additionally, on heating, pyrite remained stable up to 773 K, at which it started to decompose into pyrrhotite (Fe 1-x S) and S 2 gas. Rietveld analysis of the neutron data from 298 to 773 K allowed determination of the thermal expansion coefficient of pyrite (space group Pa$\overline{3}$) to be α V = 3.7456 × 10 -5 K -1 , which largely results from the expansion of the Fe–S bond. With further increase in temperature to 1073 K, all the pyrite transformed to pyrrhotite (Fe 1-x S) at 873 K. Unit-cell parameters of Fe 1-x S (space group P6 3 /mmc) increase on heating and decrease on cooling. However, the rates in cell expansion are larger than those in contraction. This hysteresis behavior can be attributed to continuous desulfurization of pyrrhotite (i.e., x in Fe 1-x S decreases) with increasing temperature until the stoichiometric troilite (FeS) was formed at 1073 K. On cooling, troilite underwent a magnetic transition to an orthorhombic structure (space group Pnma) between 473 and 573 K. In addition, using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) implemented with a differential scanning calorimeter, we performed kinetic measurements of pyrite decomposition. Finally, detailed peak profile and Arrhenius (k = A exp(-E a /RT)) analyses yielded an activation energy E a of 302.3 ± 28.6 kJ/mol (based on DTA data) or 302.5 ± 26.4 kJ/mol (based on TGA data) and a ln(A) of 35.3 ± 0.1.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Analysis of the Selective Flotation of Elemental Gold from Pyrite Using Diisobutyl Monothiophosphate

The gold contained in copper ores is an important resource for the gold industry. In some cases, elemental gold is present and can be recovered by selective flotation. It has been reported that the gold grade and recovery can be increased, without sacrificing the copper recovery, by replacing AERO 3477 (diisobutyl dithiophosphate (DTP)) with AERO 7249 (mixture of diisobutyl monothiophosphate (MTP) and diisobutyl dithiophosphate (DTP)) as the main collector. The fundamental understanding of the improvement in selectivity with the addition of MTP in the flotation of elemental gold from pyrite is limited and is the subject of this paper. In this regard, the hydrophobicity and selectivity of DTP and MTP in the flotation of pyrite and gold are compared and discussed. Density functional theory (DFT) was used to examine the electron density, reactivity, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) of the MTP and DTP collectors. The interaction energies for the adsorption of MTP and DTP from fresh pyrite, oxidized pyrite and gold surfaces were calculated and discussed with respect to the experimental results reported in the literature. Molecular dynamics simulation (MDS) was used to examine the adsorption state of MTP and DTP on the pyrite (100) and Au (111) surfaces.

58 GEOSCIENCES↗
DOE OSTI2019

The basis for reevaluating the reactivity of pyrite surfaces: spin states and crystal field d-orbital splitting energies of bulk, terrace, edge, and corner Fe( II ) ions

Pyrite, one of the most important minerals to catalyze redox reactions in nature and a bulk low-spin Fe mineral, needs to provide high-spin Fe on surfaces to moderate spin-forbidden transitions. In this work, the spin state of pyrite is investigated using density functional theory (DFT) calculations on cluster and periodic models. The energies of clusters Fe x S 2 x (where x = 4, 8, 16, and 32) were calculated as a function of total spin and different up/down spin configurations. The undercoordinated Fe on surfaces, edges, and corners were found to provide intermediate and high-spin Fe necessary for catalysis. Generally, the lower the crystal field splitting energy (CFSE), Δ, for a particular Fe atom, the higher is the spin density. Pyrite bulk (3D) and surfaces (2D) (+ water to mimic aqueous systems) were examined. The calculated bulk band gap (0.95 eV) is in excellent agreement with previous reports. For the surface, a conducting state is predicted. The calculated CFSE for bulk Fe( II ) in pyrite (~2.2 eV) agrees with previous CFT results; due to surface states, this CFSE decreases to ~1 eV on terraces. This study highlights the importance of accurately describing the spin state of pyrite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Pyrite shrink-film laminate as a hydroxyl radical generator

Disclosed are hydroxyl radial generating devices, comprising: a substrate layer; and a pyrite layer configured to produce hydroxyl radicals. Another aspect relates to a method for producing a hydroxyl radical generating device, comprising: providing a polymeric substrate layer; placing a layer of pyrite on a surface of the polymeric substrate layer to form a multi-layer structure; and applying heat to the multi-layer structure such that at least the surface of the polymeric substrate layer contracts; wherein the layer of pyrite contracts to a lesser extent than the surface of the polymeric substrate layer providing a textured surface comprising the pyrite layer. Also disclosed is a method of analysis, comprising: placing a solution comprising a biological substance on a sample site of a hydroxyl generating device comprising a surface of pyrite; incubating the solution; and analyzing a sample including proteolytic fragments of the biological substance.

Brenowitz, Michael David↗
DOE OSTI2015

Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Formation of pyrite (FeS{sub 2}) thin films by thermal sulfurization of dc magnetron sputtered iron

Iron films deposited by direct current magnetron sputtering onto glass substrates were converted into FeS{sub 2} films by thermal sulfurization. Experiments were carried out to optimize the sulfurization process, and the formation of FeS{sub 2} thin films was investigated under different annealing temperatures and times. High quality FeS{sub 2} films were fabricated using this process, and single phase pyrite films were obtained after sulfurization in a sulfur and nitrogen atmosphere at 450 deg. C for 1 h. Film crystallinity and phase identification were determined by using x-ray diffraction. The cubic phase pyrite films prepared were p-type, and scanning electron microscopy studies exhibited a homogeneous surface of pyrite. The authors have found that the best Ohmic contact for their pyrite thin films, using inexpensive metals, was Ni. The following were chosen for the study: Al, Mo, Fe, and Ni, and the one that led to the lowest resistance, 333 {Omega}, was Ni.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Scientific and Technological Assessment of Iron Pyrite for Use in Solar Devices

Abstract Iron pyrite (FeS 2 ) holds an enormous potential as a low cost and non‐toxic photoelectrochemical and energy‐harvesting material owing to its interesting optical, electronic, and chemical properties along with elemental abundance. In this Review, low cost and scalable processing techniques to synthesize phase‐pure pyrite thin films and nanocubes are described, and the application of this material in various energy‐harvesting devices such as dye‐sensitized solar cells, photodiodes, and heterojunction solar cells is discussed. A detailed analysis of the electron transport in single‐crystal iron pyrite is presented to shed light on its bulk‐ and surface‐conduction properties, which could be useful in designing better pyrite solar cells and could be exploited for novel device architectures. Finally, future prospects and directions are discussed.

Shukla, Sudhanshu↗
NASA NTRS2012

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Williford, K. H.↗
DOE OSTI2018

Efficient Recovery of Copper and Cobalt from the Matte–Slag Mixture of ISA Furnace by Injection of Coke and Pyrite

During ISA copper smelting process, ISASMELT furnace discharges a large amount of matte and slag mixture and the separation of them has an important influence on the recovery of valuable metals. This paper presented a reduction-sulfurization sedimentation process for recovering copper and cobalt from the matte–slag mixture of ISA furnace. Firstly, matte–slag mixture and traditional static sedimentation slag are characterized to determine their mineral composition and occurrence state. It indicates that Cu is primarily lost in slag in the form of sulfide, while Co is mostly lost in the form of oxide. With coke and pyrite as the reducing agent and vulcanizing agent, an orthogonal laboratory experiment was conducted to determine the effects of the smelting temperature and additive dosage on the recovery process. The optimum slag cleaning conditions were found to be: a coke dosage of 2 pct, a pyrite dosage of 2 pct, and a smelting temperature of 1260 °C lasting for 2 hours. In order to improve on the low utilization ratio of additives associated with the industrial sedimentation process, an innovative additive introducing method was put forward which enables the additives to mix and react with slag more adequately. A powder injection device was purpose-made to inject additives into molten slag in dispersion state, and a laboratory experiment was carried out to simulate this process. By injecting 2 pct coke and 2 pct pyrite, the contents of Cu and Co in cleaned slag decreased to 0.46 and 0.01 pct, respectively. It proves that the injection of additives into molten slag is an effective method to recover Cu and Co from the matte–slag mixture of ISA furnace.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Charge Carrier Transport in Iron Pyrite Thin Films: Disorder-Induced Variable-Range Hopping

Here, the origin of p-type conductivity and the mechanism responsible for low carrier mobility were investigated in pyrite (FeS 2 ) thin films. Temperature-dependent resistivity measurements (10-400 K) were performed on polycrystalline and nanostructured thin films prepared by three different methods: (1) spray pyrolysis, (2) hot-injection synthesized and spin-coated nanocubes, and (3) pulsed laser deposition. The films have a high hole density (10 18 -10 19 ) cm -3 and low mobility (0.1-4 cm 2 V -1 s -1 ) regardless of the method used for their preparation. The charge transport mechanism is determined to be thermally activated conduction (TAC) at near room temperature, with Mott-type variable-range hopping (VRH) of holes via localized states occurring at lower temperatures. The density functional theory (DFT) predicts that sulfur vacancy induces localized defect states within the band gap and the charge remains localized around the defect. The data indicates that the electronic properties including hopping transport in pyrite thin films can be correlated to sulfur vacancy-related defects. The results provide insights into the electronic properties of pyrite thin films and their implications for charge transport.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Electronic origins of the giant volume collapse in the pyrite mineral MnS 2

The pyrite mineral MnS 2 was recently shown to undergo a giant pressure-induced volume collapse at 12 GPa, via a disordered intermediate phase. The high pressure arsenopyrite phase is stabilised by metal-metal bonding, a mechanism now shown to be ubiquitous for Mn 2+ chalcogenides. Here we report a spectroscopic investigation of this transition up to pressures of 22 GPa. Using XANES we show that the transition does not involve a change in oxidation state, consistent with the arsenopyrite crystal structure proposed at high pressure. Notably, the XANES spectrum is almost identical in the pressure-induced disordered phase, and after crystallisation induced by laser-heating. The former is therefore a `valence bond glass', and is likely disordered due to kinetic hindrance of the phase transition. We also detect electronic changes in the compressed pyrite phase, and this is con rmed by Raman scattering which shows that the disulphide vibrations in the pyrite phase saturate before the volume collapse. Together with detailed DFT calculations, these results indicate that electronic changes precede valence bond formation between the Mn 2+ cations.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Symmetry-Defying Iron Pyrite (FeS2) Nanocrystals through Oriented Attachment

Iron pyrite (fool’s gold, FeS2) is a promising earth abundant and environmentally benign semiconductor material that shows promise as a strong and broad absorber for photovoltaics and high energy density cathode material for batteries. However, controlling FeS2 nanocrystal formation (composition, size, shape, stoichiometry, etc.) and defect mitigation still remains a challenge. These problems represent significant limitations in the ability to control electrical, optical and electrochemical properties to exploit pyrite’s full potential for sustainable energy applications. Here, we report a symmetry-defying oriented attachment FeS2 nanocrystal growth by examining the nanostructure evolution and recrystallization to uncover how the shape, size and defects of FeS2 nanocrystals changes during growth. It is demonstrated that a well-controlled reaction temperature and annealing time results in polycrystal-to-monocrystal formation and defect annihilation, which correlates with the performance of photoresponse devices. This knowledge opens up a new tactic to address pyrite’s known defect problems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Reactive sputter deposition of pyrite structure transition metal disulfide thin films: Microstructure, transport, and magnetism

Transition metal disulfides crystallizing in the pyrite structure (e.g., TMS{sub 2}, with TM = Fe, Co, Ni, and Cu) are a class of materials that display a remarkably diverse array of functional properties. These properties include highly spin-polarized ferromagnetism (in Co{sub 1-x}Fe{sub x}S{sub 2}), superconductivity (in CuS{sub 2}), an antiferromagnetic Mott insulating ground state (in NiS{sub 2}), and semiconduction with close to optimal parameters for solar absorber applications (in FeS{sub 2}). Exploitation of these properties in heterostructured devices requires the development of reliable and reproducible methods for the deposition of high quality pyrite structure thin films. In this manuscript, we report on the suitability of reactive sputter deposition from metallic targets in an Ar/H{sub 2}S environment as a method to achieve exactly this. Optimization of deposition temperature, Ar/H{sub 2}S pressure ratio, and total working gas pressure, assisted by plasma optical emission spectroscopy, reveals significant windows over which deposition of single-phase, polycrystalline, low roughness pyrite films can be achieved. This is illustrated for the test cases of the ferromagnetic metal CoS{sub 2} and the diamagnetic semiconductor FeS{sub 2}, for which detailed magnetic and transport characterization are provided. The results indicate significant improvements over alternative deposition techniques such as ex situ sulfidation of metal films, opening up exciting possibilities for all-sulfide heterostructured devices. In particular, in the FeS{sub 2} case it is suggested that fine-tuning of the sputtering conditions provides a potential means to manipulate doping levels and conduction mechanisms, critical issues in solar cell applications. Parenthetically, we note that conditions for synthesis of phase-pure monosulfides and thiospinels are also identified.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Ultrafast band-gap oscillations in iron pyrite

With its combination of favorable band gap, high absorption coefficient, material abundance, and low cost, iron pyrite, FeS2, has received a great deal of attention over the past decades as a promising material for photovoltaic applications such as solar cells and photoelectrochemical cells. Devices made from pyrite, however, exhibit open circuit voltages significantly lower than predicted, and despite a recent resurgence of interest in the material, there currently exists no widely accepted explanation for this disappointing behavior. In this paper, we show that phonons, which have been largely overlooked in previous efforts, may play a significant role. Using fully self-consistent GW calculations, we demonstrate that a phonon mode related to the oscillation of the sulfur-sulfur bond distance in the pyrite structure is strongly coupled to the energy of the conduction-band minimum, leading to an ultrafast (approximate to 100 fs) oscillation in the band gap. Depending on the coherency of the phonons, we predict that this effect can cause changes of up to +/- 0.3 eV relative to the accepted FeS2 band gap at room temperature. Harnessing this effect via temperature or irradiation with infrared light could open up numerous possibilities for novel devices such as ultrafast switches and adaptive solar absorbers.

Kolb, B↗
DOE OSTI2018

Inflexible stoichiometry in bulk pyrite FeS 2 as viewed by in situ and high-resolution X-ray diffraction

Non-stoichiometry is considered to be one of the main problems limiting iron pyrite, FeS 2 , as a photovoltaic absorber material. Although some historical diffraction experiments have implied a large solubility range of FeS 2-δ with δ up to 0.25, the current consensus based on calculated formation energies of intrinsic defects has lent support to line-compound behavior. Here it is shown that pyrite stoichiometry is relatively inflexible in both reductive conditions and in autogenous sulfur partial pressure, which produces samples with precise stoichiometry of FeS 2 even at different Fe/S ratios. By properly standardizing in situ gas-flow X-ray diffraction measurements, no significant changes in the lattice parameter of FeS 2 can be resolved, which portrays iron pyrite as prone to forming sulfur-deficient compounds, but not intrinsic defects in the manner of NiS 2-δ .

McAuliffe, Rebecca D.↗
DOE OSTI2025

Overexpression of sulfide:quinone reductase (SQR) in Acidithiobacillus ferrooxidans enhances sulfur, pyrite, and pyrrhotite oxidation

ABSTRACT Hydrogen sulfide is produced during the dissolution of some sulfidic minerals and during the microbial metabolism of reduced sulfur compounds. The sulfide:quinone reductase (SQR) enzyme is able to oxidize H 2 S, and the bioleaching cells Acidithiobacillus ferrooxidans have two SQR genes, only one of which has been characterized. We cloned and overexpressed the two SQR genes in A. ferrooxidans and show that they both have SQR activity. Both AFE_0267 and AFE_1792 are active under anaerobic conditions, but only AFE_1792 is active under aerobic conditions. The effect of the SQR overexpression and the expression of related genes on sulfur metabolism was investigated. The overexpression of SQR improved cell growth and sulfur oxidation, suggesting enhanced SQR activity led to a reduction in H 2 S toxicity as well as providing additional energy through H 2 S oxidation. Additionally, the impact on the oxidation of pyrite and pyrrhotite was investigated. The rate of oxidation of pyrite by the engineered cells was enhanced, and, furthermore, the rate of pyrrhotite oxidation was more than doubled. IMPORTANCE H 2 S is a toxic sulfur intermediate, and the SQR enzyme has evolved to oxidize H 2 S in A. ferrooxidans . In addition to detoxification, H 2 S oxidation provides energy, and overexpression of SQR enhanced aerobic and anaerobic growth on sulfur. The SQR overexpression also enhanced pyrite and pyrrhotite oxidation, which may facilitate the pyrometallurgical processing of a number of critical materials including copper, nickel, and the platinum group metals.

Jung, Heejung↗
DOE OSTI2023

Methanogens acquire and bioaccumulate nickel during reductive dissolution of nickelian pyrite

ABSTRACT Nickel (Ni) is a key component of the active site metallocofactors of numerous enzymes required for methanogenesis, including [NiFe]-hydrogenase, carbon monoxide dehydrogenase, and methyl CoM reductase, leading to a high demand for Ni among methanogens. However, methanogens often inhabit euxinic environments that favor the sequestration of nickel as metal-sulfide minerals, such as nickelian pyrite [(Ni,Fe)S 2 ], that have low solubilities and that are not considered bioavailable. Recently, however, several different model methanogens ( Methanosarcina barkeri , Methanococcus voltae , Methanococcus maripaludis ) were shown to reductively dissolve pyrite (FeS 2 ) and to utilize dissolution products to meet iron and sulfur biosynthetic demands. Here, using M. barkeri Fusaro, and laboratory-synthesized (Ni,Fe)S 2 that was physically isolated from cells using dialysis membranes, we show that trace nickel (<20 nM) abiotically solubilized from the mineral can support methanogenesis and limited growth, roughly fivefold less than the minimum concentration known to support methanogenesis. Furthermore, when provided direct contact with (Ni,Fe)S 2 , M. barkeri promoted the reductive dissolution of (Ni,Fe)S 2 and assimilated solubilized nickel, iron, and sulfur as its sole source of these elements. Cells that reductively dissolved (Ni,Fe)S 2 bioaccumulated approximately fourfold more nickel than those grown with soluble nickel and sulfide but had similar metabolic coupling efficiencies. While the mechanism for Ni uptake in archaeal methanogens is not known, homologs of the bacterial Nik uptake system were shown to be ubiquitous across methanogen genomes. Collectively, these observations indicate that (Ni,Fe)S 2 is bioavailable in anoxic environments and that methanogens can convert this mineral into nickel-, iron-, and sulfur-containing metalloenzymes to support methanogenesis and growth. IMPORTANCE Nickel is an essential metal, and its availability has changed dramatically over Earth history due to shifts in the predominant type of volcanism in the late Archean that limited its availability and an increase in euxinic conditions in the early Proterozoic that favored its precipitation as nickel sulfide minerals. Observations presented herein indicate that the methanogen, Methanosarcina barkeri , can acquire nickel at low concentration (<20 nM) from soluble and mineral sources. Furthermore, M. barkeri was shown to actively reduce nickelian pyrite; use dissolution products to meet their iron, sulfur, and nickel demands; and bioaccumulate nickel. These data help to explain how M. barkeri (and possibly other methanogens and anaerobes) can acquire nickel in contemporary and past anoxic or euxinic environments.

(NiFe)S2↗