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In this study, natural mackinawite (FeS), a chalcophilic mineral, was utilized to prepare iron/copper bimetallic oxides (CuO@FexOy) by displacement plating and calcination process. Various characterization methods prove that Cu0 is successfully coated on the surface of FeS, which were further oxidized to CuO, Fe3O4 and/or Fe2O3 during calcination process, respectively. CuO@FexOy performed highly efficient capacity to activate PMS for the degradation of various emerging pollutants including sulfamethoxazole (SMX), carbamazepine (CBZ), bisphenol A (BPA), 2,4-dichlorophenol (2,4-DCP) and diclofenac (DCF) in aqueous solution. Complete removal of the above pollutants was observed after 8 min of CuO@FexOy/PMS treatment. Taking SMX as an example, the key parameters including CuO@FexOy dosage, PMS dosage and initial pH were optimized. The results show that the catalytic system can be worked in a wide pH range (3.0-9.0). The quenching experiments and electron spin resonance (ESR) test demonstrated that the main reactive oxygen species in CuO@FexOy/PMS system were hydroxyl radicals (•OH) and sulfate radicals (SO4•¯), and SO4•¯ was the primary reactive species. Besides, the influence of coexisting anions (i.e., Cl¯, NO3¯, HCO3¯ and H2PO4¯) for the degradation of SMX was explored. CuO@FexOy/PMS system can maintain good catalytic activity and reusability in different water bodies and long-term running. This work provided a green strategy to fabricate the efficient catalyst in PMS-based advanced oxidation processes.

Nanoscale zero-valent iron (nZVI) and sulfides have been confirmed to be effective in arsenic sequestration from aqueous solution. In this study, attapulgite supported and sulfide-modified nanoscale zero-valent iron (S-nZVI@ATP) are synthesized to realize the superposition effect of enhanced arsenic sequestration. The results indicated that nZVI clusters were well disaggregated and the BET specific surface area increased from 19.61 m2·g−1 to 46.04 m2·g−1 of S-nZVI@ATP, resulting in an enhanced removal efficiency of arsenic from 51.4% to 65.1% at 20 min. The sulfides in S-nZVI@ATP mainly exist as mackinawite (FeS) and this causes the spherical nanoparticles to exhibit a larger average particle size (94.6 nm) compared to bare nZVI (66.0 nm). In addition, S-nZVI@ATP exhibited a prominent ability for arsenic sequestration over a wide pH range of 3.0–6.0. The presence of anions SO42− and Cl− can enhance the arsenic removal whereas HCO3− inhibited it. The arsenic adsorption by S-nZVI@ATP could be explained by the pseudo-second-order kinetic model and the Langmuir model, with the maximum adsorption capacity of 193.8 mg·g−1. The mechanism of As(III) sequestration by S-nZVI@ATP involved multiple processes, mainly including precipitation conversion from FeS to As2S3, surface-complexation adsorption and co-precipitation. HIGHLIGHTS S-nZVI@ATP was synthesized to superimpose the performance of nZVI and sulfides on arsenic removal.; The distribution of sulfides in S-nZVI@ATP and its role for As(III) removal were investigated.; S-nZVI@ATP showed an enlarged specific surface area and an enhanced arsenic removal efficiency.; The maximum adsorption capacity for arsenic was 193.8 mg·g−1.; The mechanism involved the combined action of Fe(0) core and sulfide shell.

In this paper, we calculate the geometry and band structure of iron sulfide (mackinawite) nanosheets. This material is one of the representatives of a new class of two-dimensional nanocatalysts for the hydrogen evolution reaction. Calculations show the absence of a band gap for model structures of crystalline and nanoscale mackinawite. In the model of oxidized nanoscale mackinawite, half of the sulfur atoms are replaced by oxygen atoms, and the band gap is 0.37 eV. The band-gap broadening can explain the appearance of catalytic activity in oxidized nanoscale mackinawite. The X-ray absorption spectra show a high sensitivity of the method to changes in the local atomic environment, especially in the first coordination sphere of iron atoms. The calculated model spectra allow determination of the features of the local atomic and electronic structure of the nanoscale mackinawite surface during the hydrogen evolution reaction.

Iron is an essential nutrient for almost all known organisms, but in aerobic, neutral pH environments, it is present primarily as precipitated oxyhydroxide minerals. In contrast, in anaerobic environments, iron can exist in its ferrous form (Fe2+) and remain soluble. In sulfide-rich, anaerobic environments, Fe2+ and sulfide react to form iron sulfide cluster complexes of the form FexSx (FeSaq), which further condense to form the mineral mackinawite, which itself is partly soluble. However, the ability of microorganisms to utilize iron sulfide as an iron source is not known. Here, we show that the anaerobic, hyperthermophilic archaeon Pyrococcus furiosus can directly assimilate the iron in dissolved iron sulfide cluster complexes (FeSaq) without further dissolution to Fe2+. Growth is only inhibited in the presence of a Fe2+-specific chelator. The FeSaq that is utilized can be formed either by reaction of chelated Fe2+ with sulfide or dissolved from mackinawite. Pyrococcus furiosus can utilize FeSaq larger than 3.5 kDa, or Fe40S40, and may actively aid in the dissolution of mackinawite to the assimilated FeSaq. A model for iron sulfide assimilation from an insoluble mineral is proposed.

Mercury (Hg) is a toxic trace element of global environmental concern which has been increasingly dispersed into the environment since the industrial revolution. In aquatic and terrestrial systems, Hg can be reduced to elemental Hg (Hg0) and escape to the atmosphere or converted to methylmercury (MeHg), a potent neurotoxin that accumulates in food webs. FeII-bearing minerals such as magnetite, green rusts, siderite, and mackinawite are recognized HgII reducers. Another potentially Hg-reducing mineral, which commonly occurs in Fe- and organic/P-rich sediments and soils, is the ferrous iron phosphate mineral vivianite (FeII3(PO4)2·8H2O), but its reaction with HgII has not been studied to date. Here, nanoparticulate vivianite (particle size ∼ 50 nm; FeII content > 98%) was chemically synthesized and characterized by a combination of chemical, spectroscopic, and microscopic analyses. Its ability to reduce HgII was investigated at circumneutral pH under anoxic conditions over a range of FeII/HgII ratios (0.1–1000). For FeII/HgII ratios ≥1, which are representative of natural environments, HgII was very quickly and efficiently reduced to Hg0. The ability of vivianite to reduce HgII was found to be similar to those of carbonate green rust and siderite, two of the most effective Hg-reducing minerals. Our results suggest that vivianite may be involved in abiotic HgII reduction in Fe and organic/P-rich soils and sediments, potentially contributing to Hg evasion while also limiting MeHg formation in these ecosystems., Environmental Science & Technology, 55 (5), ISSN:0013-936X, ISSN:1520-5851

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H+, CO2 and NO3− reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n(Fe2+S2−)(s) was found to oxidize to a Fe3+ containing FeS phase at −0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe2+, Fe3+, S2− and polysulfide (Sn2−) species, with its composition described as Fe2+1−3xFe3+2xS2−1−y(Sn2−)y. Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe2+Fe3+2S2−4) and a ligand-based oxidation path between FeS and pyrite (Fe2+(S2)2−).

Iron sulfide nanoparticles play an essential role in the global biogeochemistry sulfur cycle and the origin of life. Controlling phase and morphology is essential but a great challenge for nanomaterials. Herein, we have investigated surface energy, morphology, thermodynamic stability, and phase evolution of FexSy nanoparticles through density functional theory calculations and Wulff construction. The sulfur-rich surfaces become more stable under higher sulfur chemical potential with low temperature and high partial H2S pressure, while the trends of sulfur-poor surfaces are reversed. Thermodynamic equilibrium phase diagrams imply that the intrinsic iron is sulfurated to mackinawite (FeS) and further to the polymorphs of FeS2 when the particle size is larger than 5 nm. When the size is decreased to 2 nm, the mackinawite (FeS) could be sulfurated to pyrrhotite (Fe7S8) and greigite (Fe3S4) and finally to the pyrite (FeS2) phase.

Molybdenum (Mo) in marine sediments has been used as a paleoproxy to provide evidence for past oceanic euxinic and sulfidic conditions through its association with pyrite. Here, we examine the adso...

Schwertmannite is sensitive to changes in geochemical, thermal, and microbial conditions. Changes in aqueous pH beyond its stability, i.e. pH 2.5–4.5, triggers its transformation to jarosite or goethite in highly acidic environments (pH ≤ 2.5), depending on the availability of jarosite-directing cations (Na+, NH4+, K+, etc.), while goethite is the common stable end product at pH > 7.5. Schwertmannite with degraded morphology can stably exist for years in oxic intermediate pH environments (pH 5.5–6.5), but the presence of trace amounts of Fe(II)aq yields goethite/lepidocrocite within a few hours, especially at pH ≥ 6.5. Hematite is the sole end product at ≥ 600 °C dry heating, with goethite and ferrihydrite as intermediate phases. Siderite, maghemite, and mackinawite form in anoxic microbial conditions due to dissimilatory reduction of Fe(III) and SO42− to Fe(II) and HS−, while orpiment forms from As(V)-rich schwertmannites. Sorbed contaminants enhance schwertmannite stability by restricting Fe(II)–Fe(III) electron transfer and microbial degradation by occupying surface sites. Although Fe(III) and sorbed ion mobilization typically has negligible effects on schwertmannite transformation, complete schwertmannite-SO4 release is likely in extreme conditions, and in microbial Fe(II)aq-rich media. Dissolution–reprecipitation and solid state transformation mechanisms broadly govern schwertmannite transformation.

Although electrode materials for batteries show high energy density, sluggish kinetics originated from the diffusion-controlled charge storage mechanism result in low power density and limit potent...

Potential degradation pathways of dimethylmercury (DMHg) remain as one of the critical knowledge gaps in the marine biogeochemical cycle of mercury (Hg). Although Hg is known to be highly reactive with reduced sulfur, demethylation of DMHg in the presence of sulfide has until now remained experimentally untested. Here, we provide the first experimental support for demethylation of DMHg to monomethylmercury (MMHg) in the presence of both dissolved sulfide and mackinawite (FeS(s)m). The degradation of DMHg was shown to be pH dependent, with higher demethylation rates at pH 9 than pH 5. At room temperature and environmentally relevant DMHg to sulfide molar ratios, we observed demethylation rates up to 0.05 d–1. When comparing the number of active sites available, FeS(s)m was found to have a higher capacity to demethylate DMHg, in comparison with dissolved sulfide. Our study suggests that dissolved sulfide and FeS(s)m mediated demethylation of DMHg may act as a sink for DMHg, and a potential source of MMHg, in aquatic systems.

Iron pyrite (FeS2) is a promising lithium-ion battery cathode material because of its low cost and ultrahigh energy density (1671 Wh kg-1). However, its reaction mechanisms are still controversial. In this work, we find that different from the conventional belief that an intermediate phase Li2FeS2 is formed followed by Fe/Li2S composites at the initial discharge, it undergoes a one-step reaction (FeS2 → Fe + Li2S) or a two-step reaction (FeS2 → FeS + Li2S → Fe + Li2S), which depends on the current rate and temperature. In the charge process, it undergoes a two-step reaction: phase transition Fe + Li2S → FeS at about 1.74 V and generation of elemental sulfur (Li2S → S, 2.30 V). FeS is a mackinawite phase that is formed on the interface of Li2S via heteroepitaxial growth. Subsequent cycles involves a combination reaction of FeS and S. The reaction mechanism suggests that FeS2 suffers from the demerits of both FeS and S, such as a large volume change, voltage hysteresis, and polysulfide dissolution. These findings would help us to understand the intrinsic capacity fading of FeS2 and provide guidelines to improve its electrochemical performances.

The corrosion behavior of two types of low-carbon steel (denoted steel A and steel B) in H2S/CO2 was investigated through immersion tests, and the effect of Ti microalloying on the corrosion mechanism was analyzed. The microstructures, corrosion kinetics, corrosion surface morphologies, corrosion phases, cross-sectional morphologies and elemental distributions of the materials were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron backscatter diffraction (EBSD), energy-dispersive spectroscopy (EDS), x-ray diffraction (XRD) and electron probe microanalysis (EPMA). The results showed that the corrosion rate of steel B with Ti microalloying was lower than that of steel A; the amount and formation rate of corrosion products in these two materials were different. As the immersion time increased, the corrosion products changed from iron-rich mackinawite to sulfur-rich pyrrhotite. In the early stage of corrosion, the corrosion products were primarily mackinawite, which controlled the corrosion phase through the entire process. After 384 h of immersion, pyrrhotite was observed, which can effectively protect the steel substrate, providing excellent corrosion resistance. The corrosion products in steel B with Ti microalloying were more compact than those in steel A. Moreover, Ti enrichment in the oxide film was observed in steel B, which can further improve its corrosion resistance. The results from this study can provide an important reference for the oil and gas industry.

Iron (Fe) oxides are important host phases for antimony (Sb), a toxic metalloid of environmental concern. In wetland soils and sediments, poorly ordered Fe oxides such as ferrihydrite may undergo reductive dissolution and mineralogical transformation upon reaction with dissolved sulfide (S(-II)). The consequences of these processes for the mobility of associated Sb have not been investigated to date. Here, we allowed Sb(V)-bearing ferrihydrite (molar ratio of Fe:Sb = 400) to react with varying S(-II) concentrations (Fe(III):S(-II) = 0.2, 0.5, and 1) at pH 6 and 8 over 32 days. Changes in speciation and concentration of Fe, S and Sb in the aqueous, colloidal and solid phase were examined through a combination of aqueous-phase analyses, X-ray diffraction and synchrotron X-ray absorption spectroscopy. Addition of S(-II) caused rapid reduction of Fe(III), thereby producing elemental S and Fe(II). X-ray diffractometry and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that S(-II) addition resulted in the precipitation of Fe(II) sulfides (mackinawite (FeS) and pyrite (FeS2)) and formation of secondary Fe(III) oxides (goethite (FeOOH) and hematite (Fe2O3)). The formation of mackinawite and pyrite was further confirmed by S K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and was found to occur to the greatest extent in the high-sulfide treatments. The initial reductive dissolution of ferrihydrite was paralleled by a fast increase in dissolved Sb concentrations, with ∼25% of total Sb being released in the high-sulfide treatments. The Sb release was followed by Sb immobilization within ∼1–7 days. Since ion-chromatography ICP-MS revealed antimonate (Sb(OH)6-) as the primary Sb aqueous phase species throughout the experiment, with only negligible concentrations of antimonite (Sb(OH)3) and only very minor amounts ( 3 kDa) size fraction at pH 8 under medium and high S(-II) conditions, while no colloidal Sb was found in other treatments. Together, these results show that Fe oxide sulfidization can have opposing effects on Sb mobility. On the one hand, the initial sulfide-promoted Fe oxide dissolution triggers Sb release into the aqueous phase. On the other hand, Sb can subsequently be immobilized via sorption to secondary Fe oxides and newly-formed Fe sulfides during the later stages of sulfidization. Sulfidization reactions, and the complex opposing impacts on Sb mobility, should therefore be considered for the risk assessment and derivation of adequate management strategies at Sb-impacted sites which experience sulfidic conditions.

Fenton reaction is one of most promising approaches for efficient removal of various robust organic pollutants in wastewater, however it faces several intrinsic challenges such as acidic condition, sludge waste and sensitive to sulfide-containing compound. Here we reported a novel FeS1.92 as an efficient and sulfide resistant heterogeneous Fenton catalyst under mild condition. This novel FeS1.92 was facilely prepared through a mechanochemical synthesis of mackinawite (FeS) with sulfur powder (S) by ball milling. The sulfured mackinawite (FeS1.92) exhibits high performance in activating H2O2 to generate hydroxyle radicals for organic waste remediation. Furthermore, this FeS1.92 based heterogeneous Fenton catalyst is highly sulfide resistant and shows improved performance for degrading sulfide-containing organic pollutants. This study provides an effective mechanochemical approach to fabricate heterogeneous Fenton catalysts for sulfide-containing wastewater treatment.

The biogenic mackinawite (FeS) is a promising remover for hexavalent chromium. However, FeS is susceptible to aggregation, affecting the removal efficiency of Cr(VI). To address the aggregation of FeS, kaolinite was selected as the stabilizer to disperse biogenic FeS. Results showed that kaolinite could be used as a supporting material for biogenic FeS during the formation process, which efficiently decreased the aggregation of FeS. FeS-kaolinite enabled to increase the rate and capability of Cr(VI) removal, and the maximum removal capability of FeS-kaolinite reached 399 mg/g at pH 7, which was 2.4 times higher than that of FeS only. The optimal concentration of kaolinite was 3 g/L where the percentage of FeS on FeS-kaolinite was 5% (wt). The removal kinetic was well fitted with the pseudo-second-order model and Cr(VI) could be removed quickly and efficiently in the pH range of 3–8. The efficiency of Cr(VI) removal was not dependent on ionic strength (Cl−, 0.1–1000 mM), HA (5–20 mg/L) and co-existing cations (Ca2+, Zn2+,Cu2+, and Cd2+, 30 mM). Cr(VI) could be rapidly reduced to Cr(III) by FeS-kaolinite on the surface and Cr(III) was coprecipitated into Cr(OH)3 and CrxFe1-x(OH)3. This study suggests biogenic FeS-kaolinite is a good candidate for remediation of Cr(VI) contaminated environment.

Potential acid sulfate soils (PASS) are drained for agriculture, resulting in the formation of active acid sulfate soils (AASS), which gradually evolve into post-active acid sulfate soils (PAASS). Various redox concentrations (precipitates, costings, and mottles) occur in these soils as a result of pedogenic processes including biological activity and effects of land management. Although several studies have determined the mineralogy and geochemistry of ASS, the mineralogy and geochemistry of redox concentrations occurring in a sequence of ASS through PASS to PAASS have not been investigated. This study examined the mineralogy and geochemistry of redox concentrations and matrices within 5 PASS, 8 AASS, and 5 PAASS in Thailand. The labile minerals were predominantly controlled by oxidation status and management inputs. The unoxidized layers of PASS, AASS, and PAASS contained pyrite and mackinawite. The oxidation of Fe sulfides caused acidification and accumulation of yellow redox concentrations of jarosite and Fe (hydr)oxides at shallow depths. As the soils became well developed, they were recognized as PAASS, and the jarosite and goethite transformed to hematite. As ASS were drained, Co, Mn, Ni, and Zn moved downward and were associated with Fe sulfides and Mn oxides in the unoxided layer. Concentrations of As, Cu, Cr, Fe, and V did not change with depth because these elements became associated with jarosite and Fe (hydr)oxides in yellow and red redox concentrations, as well as the root zone, in the partly oxidized layer of AASS and PAASS. Arsenic was associated with pyrite under reducing conditions.

Abiotic iron monosulfide (FeS) has attracted growing interests in dechlorinating trichloroethylene (TCE) in anoxic groundwater, but it is still unclear how biogenic FeS affects the dechlorination and thus the cytotoxity of TCE. In this work, a biogenic FeS was synthesized by Shewanella oneidensis MR-1 with addition of ferrihydrite and S0, and it was used for dechlorination of TCE in alkaline environment and the de-cytotoxicity was evaluated by the growth of Synechocystis sp. PCC6803. The results show that the biogenic FeS was of mackinawite, with a loose flower-like mosaic structure. The dechlorination of TCE by the biogenic FeS was accelerated by 6 times than that by abiotic FeS. TCE was dechlorinated mainly by hydrogenolysis to form dichloroethane (C2H2Cl2), vinyl chloride (C2H3Cl), and finally ethylene, accompanied with transformation of both Fe2+ to Fe3+ and monosulfide to disulfide and polysulfide on the biogenic FeS surface. The concentration for 50% of maximal inhibition effect (EC50) of TCE to Synechocystis was 486 mg/L and the inhibition to Synechocystis under the EC50 was relieved more significantly on addition of the biogenic FeS than that of abiotic FeS. These results indicate that the biogenic FeS promoted the dechlorination and thus de-cytotoxity of TCE.

Naturally occurring minerals, such as the iron sulfide mackinawite, play a key role in the remediation of uranium from groundwater systems. Here, density functional theory (DFT) is used to investigate the interaction of uranium with the most stable surface of stoichiometric mackinawite, {001}-S. The high reactivity of the mineral toward oxygen may affect its ability to sequester uranium; therefore, two models of oxidized mackinawite are also used to study the effect of surface oxidation on adsorption. Weak adsorption of mononuclear uranyl(VI) complexes is found on stoichiometric mackinawite; however, equivalent adsorption modes on the oxidized mackinawite models generally exhibit stronger adsorption. Some of the most energetically stable DFT structures are found to match well with experimental extended X-ray absorption fine structure (EXAFS) data. The implications for the proposed use of mackinawite as a scavenger material for uranium in groundwater systems are discussed.

Arsenic (As) mobilization in rice paddy soils under fluctuating redox conditions is influenced by the biogeochemical cycling of redox sensitive elements such as iron (Fe) and manganese (Mn). Arsenic mobility in paddy soils is highly variable, and the influence of Mn abundances and Mn/Fe ratios on As mobility in these soils have received little attention. In this contribution, we developed a complementary set of field and laboratory experiments designed to evaluate the impact of Mn on interconnected Fe and As solubilization in rice paddy soils experiencing wetting-drying cycles through controlled irrigation. Porewater monitoring and synchrotron-based imaging and spectroscopy of thin sections prepared from an Arkansas paddy soil confirmed that As release was primarily governed by reductive dissolution of Fe (oxy)hydroxide phases. Experiments with laboratory soil microcosms amended with the synthetic nanocrystalline Mn oxide, δ-MnO2, showed that higher initial Mn/Fe inhibited Fe and As mobilization into porewater relative to unamended soil by up to 95% and 45%, respectively. Geochemical modeling suggests that pH increases driven by microbial MnO2 reduction, in conjunction with microbial Fe- and sulfate-reduction in carbonate-rich porewater, enhanced the precipitation of siderite (FeCO3(s)), mackinawite (FeS(s)), and potentially a Mn(II) arsenate phase. These secondary mineral phases likely played a greater role in controlling As solubilization than the role of Mn as a redox buffer regulating the redox conditions in the flooded soils. Field and laboratory experiments showed that alternate wetting and drying approaches with a single dry-down can be effective at reducing dissolved As concentrations in porewater through the oxidation of Fe. Differences in soil Mn/Fe ratios had no clear impact on the effectiveness of dry-downs as a strategy to reduce As mobilization.

Strontium (90Sr) and nickel (59Ni) have been considered as key radionuclides in the safety assessment of radioactive waste disposal. Through various efforts to impede the migration of radioactive nuclides underground, it has been established that some minerals generated from the corrosion of the waste containers have a positive chemical interaction with these radionuclides. Among these minerals we selected mackinawite (FeS), an iron and sulfur compound, and performed a sorption experiment for the Sr and Ni in FeS under anoxic and alkaline conditions by reflecting deep underground environments. The effects of pH on sorption were likewise investigated in the pH range of 8 ~ 12. As a result, it was found that strontium failed to exhibit a good sorption capacity in a weak alkaline range, while nickel showed a noticeably higher sorption affinity over the entire experimental pH range. Moreover, we determined that as the pH increased in the solution, the distribution coefficients (Kd) were increased for both nuclides, which reflects when an alkalinity increses, the surface of the mineral charges much negatively by detaching the hydrogen or cations on the mineral surface. Thus, it can be concluded that the cationic nuclides of Sr and Ni can attach easily to the mineral under strong alkalinity.

Vanadium contamination is a growing environmental hazard worldwide. Aqueous vanadate (HxVVO4(3–x)–(aq)) concentrations are often controlled by surface complexation with metal (oxyhydr)oxides in oxi...

Surface modification of zero-valent iron (nZVI) nanoparticles, which are frequently used in the removal of chlorinated hydrocarbons from contaminated groundwater, can increase their surface stability without significant loss of reactivity. Sulfidation is a process during which thin iron sulfide phases are formed on nZVI particles. In this work, the adsorption capability of two iron sulfide minerals (mackinawite and pyrite) and ZVI with respect to two small polar molecules (H2O and H2S) and trichloroethylene (TCE) was modeled by using the quantum mechanics (QM) approach. High-level QM methods used on cluster models helped in benchmarking and validation of density functional theory methods used on periodic slab models of the (001) surfaces of iron sulfides and the (111) surface of ZVI. This careful computational treatment was necessary for achieving reliable results because modeled iron containing compounds represent computationally demanding systems. The results showed that adsorption was strongly affected by surface topology, accessibility of surface sites, and the shape of adsorbed molecular species. The mackinawite surface is practically hydrophobic having weak interactions with polar molecules (about -5/-6 kcal mol-1), in contrast to the surfaces of pyrite and ZVI (adsorption energies are about three times larger). On the other hand, the adsorption of weakly polar planar TCE molecule is relatively strong and similar for all three surfaces (in the range of -11 to -17 kcal mol-1). Moreover, it was shown that the dominant component of the adsorption energy of TCE had originated from dispersion interactions, which were less important for small polar molecules.

In redox-dynamic environments, sorption to poorly-crystalline, nanometer-sized Fe(III)-(oxyhydr)oxides like ferrihydrite influences the biogeochemical cycling of nutrients and trace elements. Under sulfate-reducing conditions, the reductive dissolution of ferrihydrite leads to the release of associated constituents, which may be re-immobilized via sorption to secondary Fe minerals. To date, studies following the kinetics and transformation pathways of Fe(III)-(oxyhydr)oxides upon exposure to dissolved sulfide (S(−II)) have largely focused on pure Fe minerals. However, in nature, Fe(III)-(oxyhydr)oxides are often found in association with organic matter (OM). Because ferrihydrite–OM associations exhibit characteristics and biogeochemical reactivity differing from those of pure ferrihydrite, in this study, we compared sulfidization kinetics and transformation pathways of a pure ferrihydrite to those of ferrihydrite coprecipitated with contrasting organic ligands; polygalacturonic acid, galacturonic acid, and citric acid (C/Fe molar ratio ∼0.55). Incorporating aqueous- and solid-phase S and Fe speciation analyses (via wet chemistry techniques and S and Fe X-ray absorption spectroscopy) in addition to X-ray diffraction and electron microscopy, we studied both rapid (

Iopromide (IOP), an iodinated X-ray contrast medium (ICM), is identified as a precursor to iodide disinfection byproducts that have high genotoxicity and cytotoxicity to mammals. ICM remains persistent through typical wastewater treatment processes and even through some hydroxyl radical-based advanced oxidation processes. The development of new technologies to remove ICMs is needed. In this work, mackinawite (FeS)-activated sulfite autoxidation was employed for the degradation of IOP-containing water. The experiment was performed in a 500 mL self-made temperature-controlled reactor with online monitoring pH and dissolved oxygen in the laboratory. The effects of various parameters, such as initial pH values, sulfite dosages, FeS dosages, dissolved oxygen, and inorganic anions on the performance of the treatment process have been investigated. Eighty percent of IOP could be degraded in 15 min with 1 g L−1 FeS, 400 μmol L−1 sulfite at pH 8, and high efficiency on the removal of total organic carbon (TOC) was achieved, which is 71.8% via a reaction for 1 h. The generated hydroxyl and oxysulfur radicals, which contributed to the oxidation process, were identified through radical quenching experiments. The dissolved oxygen was essential for the degradation of IOP. The presence of Cl− could facilitate IOP degradation, while NO3− and CO32− could inhibit the degradation process. The reaction pathway involving H-abstraction and oxidative decarboxylation was proposed, based on product identification. The current system shows good applicability for the degradation of IOP and may help in developing a new approach for the treatment of ICM-containing water.

Mackinawite FeS is the most common corrosion product in the early stage of steel in H2S environment and also has an effective catalysis for hydrodesulfurization, hydrogen release reactions and heavy metal ion removal since its high specific surface area and reactive surface like other van der Waals materials. In this paper, ab initio molecular dynamics (AIMD) is used to study the interactions between small molecules (H2S, H2O and H) and FeS at 300 K. The calculation results show that the primary dissociation of H2S only occurs on the FeS(111) surface and H2S is chemically adsorbed on the (011) and (100) surfaces but physically adsorbed on the (001) surface. It will dissociate and generate H atoms when different amounts H2S or H2O molecules appear in the interlayer of FeS, in which H2S is more prone to dissociation. The dissociated H atoms will be “captured” by Fe/S atoms in mackinawite FeS, leading to the shrink of layer. Moreover, H atoms could combine into H2, which suggests that layered FeS has great potential for hydrogen generation. The diffusion coefficient of H atoms in mackinawite FeS layer is estimated about 1.67 × 10−8 m2/s. These findings have significant meaning for application of mackinawite FeS in corrosion science, hydrogen generation, hydrogen storage and other fields.

Methanogens have a high demand for iron (Fe) and sulfur (S); however, little is known of how they acquire, deploy, and store these elements and how this, in turn, affects their physiology. Methanogens were recently shown to reduce pyrite (FeS2), generating aqueous iron sulfide (FeSaq) clusters that are likely assimilated as a source of Fe and S. Here, we compared the phenotypes of Methanococcus voltae grown with FeS2 or ferrous iron [Fe(II)] and sulfide (HS−). FeS2-grown cells are 33% smaller yet have 193% more Fe than Fe(II)/HS−-grown cells. Whole-cell electron paramagnetic resonance revealed similar distributions of paramagnetic Fe, although FeS2-grown cells showed a broad spectral feature attributed to intracellular thioferrate-like nanoparticles. Differential proteomic analyses showed similar expression of core methanogenesis enzymes, indicating that Fe and S source does not substantively alter the energy metabolism of cells. However, a homolog of the Fe(II) transporter FeoB and its putative transcriptional regulator DtxR were up-expressed in FeS2-grown cells, suggesting that cells sense Fe(II) limitation. Two homologs of IssA, a protein putatively involved in coordinating thioferrate nanoparticles, were also up-expressed in FeS2-grown cells. We interpret these data to indicate that, in FeS2-grown cells, DtxR cannot sense Fe(II) and therefore cannot downregulate FeoB. We suggest this is due to the transport of Fe(II) complexed with sulfide (FeSaq), leading to excess Fe that is sequestered by IssA as a thioferrate-like species. This model provides a framework for the design of targeted experiments aimed at further characterizing Fe acquisition and homeostasis in M. voltae and other methanogens. IMPORTANCE FeS2 is the most abundant sulfide mineral in the Earth’s crust and is common in environments inhabited by methanogenic archaea. FeS2 can be reduced by methanogens, yielding aqueous FeSaq clusters that are thought to be a source of Fe and S. Here, we show that growth of Methanococcus voltae on FeS2 results in smaller cell size and higher Fe content per cell, with Fe likely stored intracellularly as thioferrate-like nanoparticles. Fe(II) transporters and storage proteins were upregulated in FeS2-grown cells. These responses are interpreted to result from cells incorrectly sensing Fe(II) limitation due to assimilation of Fe(II) as FeSaq. These findings have implications for our understanding of how Fe/S availability influences methanogen physiology and the biogeochemical cycling of these elements.

The oxygenation of mackinawite (FeS) frequently occurs at anoxic-oxic interfaces in both natural and engineered systems such as intertidal sediment, in activated sludge in water treatment processes, and during sulfidized zero-valent iron particle corrosion. During reoxygenation events, FeS may drive a Fenton-like process leading to the production of strong oxidants though the details of this process are poorly understood. In this study, benzoic acid (BA) has been used to probe both the magnitude and identity of these strong oxidants under circumneutral pH conditions. The major product of BA oxidation during FeS oxygenation was found to be 2,5-dihydroxybenzoic acid (2,5-DHBA) rather than monohydroxybenzoic acids identified to be the major products in a range of hydroxyl radical (HO·)-dominated systems. Based upon relative reactivity with other competitive probes and nature of the hydroxybenzoate product distribution, it is hypothesized that the strong oxidant must be a surface-localized entity such as high-valent iron or surface-associated hydroxyl or sulfur-based radicals with reactivity differing from those formed in free solution. The importance of both the reactivity of the oxidant and adsorption of the substrate to the surface is demonstrated.

Dark formation of hydroxyl radical upon oxidation of reduced iron minerals plays an important role in the degradation and transformation of organic and inorganic pollutants. Herein, we compared the hydroxyl radical formation from various reduced iron minerals at different redox conditions. OH production was generally observed from the oxidation of reduced iron minerals, following the order: mackinawite (FeS) > reduced nontronite (iron-bearing smectite clay) > pyrite (FeS2) > siderite (FeCO3). Structural Fe2+ and dissolved O2 play critical roles in OH production from reduced iron minerals. OH production increases with decreasing pH, and Cl− has little effect on this process. More importantly, dissolved organic matter significantly enhances OH production, especially under O2 purging, highlighting the importance of this process in ambient environments. This sunlight-independent pathway in which OH forms during oxidation of reduced iron minerals is helpful for understanding the degradation and transformation of various inorganic and organic pollutants in the redox-fluctuation environments.

The current study is aimed at proposing a common mechanism of localized corrosion of mild steel in H2S containing aqueous environments, by utilizing experimental findings reported in a number of st...

In terms of long-term safety for radioactive waste disposal, the anionic iodide (I-129) with a long half-life (1.6 × 106 yr) is of a critical importance because this radionuclide migrates in geological media with limited interactions. Various studies have been performed to retard the iodide migration. Recently, some minerals that are likely generated from waste container corrosion, have been suggested to have a considerable chemical interaction with iodide. In this study, chalcocite and mackinawite were selected as candidate minerals for underground corrosion materials, and an iodide sorption experiment were carried out. The experiment was performed under anoxic and alkaline conditions and the pH effects on the iodide sorption were investigated in the range of pH 8 to 12. The results showed that both minerals demonstrated a noticeable sorption capacity on iodide, and the distribution coefficient (Kd) decreased as the pH increased in the experimental condition. In addition, when the alkalinity increased higher than a pH of 12, the sorption capacity of both minerals decreased dramatically, likely due to the competition of hydroxy ions with the iodide. This result confirmed that chalcocite was an especially good sorbing media for iodide under alkaline conditions with a pH value of less than 12. Keywords: Iodide, Sorption, Chalcocite, Mackinawite, pH dependancy. extraction

As iron sulfide mineral phases are important sedimentary sinks for naturally occurring or contaminant metals, it is important to know the fate of metals during the diagenetic transformation of primary sulfide minerals into more stable phases, such as pyrite (FeS2). Furthermore, the trace metal content of pyrite has been proposed as a marine paleoredox proxy. Given the diverse low-temperature diagenetic formation pathways for pyrite, this use of pyrite requires validation. We, therefore, studied nickel (Ni) and cobalt (Co) incorporation into freshly precipitated mackinawite (FeSm), and after experimental diagenesis to pyrite (FeS2) using S0 as an oxidant at 65 °C. Metal incorporation was quantified on bulk digests using ICP-OES or ICP-AES. Bulk mineralogy was characterized with micro-X-ray diffraction (micro-XRD), documenting the transformation of mackinawite to pyrite. Epoxy grain mounts were made anoxically of mackinawite and pyrite grains. We used synchrotron-based micro-X-ray fluorescence (μXRF) to map the distribution of Co and Ni, as well as to collect multiple energy maps throughout the sulfur (S) K-edge. Iron (Fe) and S K-edge micro-X-ray absorption near edge spectroscopy (μXANES) was used to identify the oxidation state and mineralogy within the experimentally synthesized and diagenetically transformed minerals, and map end-member solid phases within the grain mounts using the multiple energy maps. Metal-free FeSm transformed to pyrite, with residual FeSm detectable. Co- and Ni-containing FeSm also transformed to pyrite, but with multiple techniques detecting FeSm as well as S0, implying less complete transformation to pyrite as compared to metal-free FeSm. These results indicate that Co and Ni may inhibit transformation for FeSm to pyrite, or slow it down. Cobalt concentrations in the solid diminished by 30% during pyrite transformation, indicating that pyrite Co may be a conservative tracer of seawater or porewater Co concentrations. Nickel concentrations increased several-fold after pyrite formation, suggesting that pyrite may have scavenged Ni from the dissolution of primary FeSm grains. Nickel in pyrites thus may not be a reliable proxy for seawater or porewater metal concentrations.

Magnetite and maghemite are important components of iron oxides that determine the magnetic properties of rocks, soils, and sediments, and are also materials with broad industrial applications. We investigated the reduction and transformation of both phases with a strain of sulfate-reducing bacteria (SRB). SRB growth resulted in 28.1% and 7.1% sulfate to acid volatile sulfur conversion in magnetite and maghemite, respectively. Transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses indicate that monosulfides (mackinawite and greigite) and polysulfides are the main secondary sulfides in the magnetite experiment, while the maghemite experiment also contained a high proportion of pyrite. XPS analyses indicate the reduction of Fe(III) to Fe(II) on the surface of magnetite and maghemite both by dissolved sulfides and SRB. Mossbauer spectroscopy measurements reveal the formation of superparamagnetic phases in microbial experiments, which indicates the dissolution and particle size decrease of the two minerals both by dissolved sulfides and SRB. X-ray diffraction and Mossbauer spectroscopy analyses suggest a complete transformation of nanomaghemite to nanomagnetite under the mediation of SRB through solid phase Fe(III) reduction. This transformation controls the changing and different patterns of both magnetic susceptibility and magnetic hysteresis for the two minerals. It is suggested that the structural similarity between magnetite and maghemite, and the conductivity of magnetite, constrain the unique solid phase transformation. Our findings indicate that the maghemite–magnetite solid solution is a potential natural battery for the growth of anaerobic microbes in sulfidic environments.

Arsenic (As) release and mobility in groundwater is coupled to the iron (Fe) cycling and the associated transformation of Fe-oxides present in sediments. Recent in situ experiments have provided observations on arsenic mobilization and co-occurring reductive mineral transformation when placing As-loaded ferrihydrite-coated sand for 80 days in wells of an As-contaminated aquifer of Northern China. However, the complex temporal change in solid-associated arsenic and the multiple geochemical processes occurring when the flowing groundwater contacts the As-loaded ferrihydrite-coated sand hamper a detailed evaluation of the experimental data set. In this study, we develop a modeling approach that allows a quantitative interpretation of arsenic release and ferrihydrite transformation observed during the in situ experiments. The model accounts for the interplay of abiotic and biotic geochemical processes (i.e., surface complexation, reductive dissolution, formation of secondary iron minerals, and arsenic sequestration into the newly formed minerals) involved in the transformation of Fe-oxides and controlling arsenic mobility. The results show the capability of the proposed approach to reproduce the temporal trends of solid arsenic and ferrihydrite concentrations, as well as the spatial variability of mineral transformation, observed in different wells using a common set of surface complexation parameters and kinetic rate constants. The simulation outcomes allowed us to disentangle the specific contribution of the different mechanisms controlling the release of arsenic. It was possible to identify an initial rapid but minor release of As (13-23% of the initial surface concentration) due to desorption from ferrihydrite, as well as the reduction of adsorbed As(V) to As(III) upon contact with the flowing anoxic groundwater. Successively, reductive dissolution of ferrihydrite caused the decrease of the amount of the Fe mineral phase and led to a major depletion of solid-associated arsenic. The produced Fe(II) catalyzed the ferrihydrite conversion into more crystalline Fe(III) oxides (i.e., lepidocrocite and goethite) through Ostwald ripening, and resulted in the formation of siderite and mackinawite upon reaction with carbonates and sulfides naturally present in the groundwater. The model results also showed that, whereas the decrease in surface sites during reductive dissolution of ferrihydrite promoted arsenic mobilization, the mineral transformation limited As release through its sequestration into the newly formed secondary mineral phases.

Recently, the new synthesis route to delta-FeOOH nanodiscs based on the γ-irradiation of a deoxygenated iron(III) chloride alkaline aqueous colloidal solution in the presence of diethylaminoethyl-dextran hydrochloride (DEAE-dextran) has been reported by Jurkin et al. [1]. In that work we supposed that γ-irradiation produced reducing conditions and that delta-FeOOH nanoparticles were formed through oxidation of obtained white suspension characteristic of Fe(OH)2. In this work, we studied the impact of dextran sulfate polymer (DEX-sulfate) on the radiolytic synthesis of magnetic iron oxide nanoparticles. The syntheses started with γ-irradiation (130 kGy) of deoxygenated iron(III) chloride alkaline aqueous colloidal solution in the presence of 2-propanol and DEX-sulfate. The radiolytically synthesised samples were isolated by conventional process of sample isolation (centrifugation/washing with water or ethanol) or in the presence of glycerol. The XRD results showed that sample isolated in the presence of glycerol contained Fe(OH)2, hydroxysulfate green rust II (GR SO42-) and goethite (alfa-FeOOH). The Mössbauer results confirmed the presence of Fe(OH)2 and hydroxysulfate green rust II (GR SO42-) in this sample. The radiolytically synthesized samples that were isolated by centrifugation and washing with water or ethanol contained GR SO42- and alfa-Fe2O3. Therefore, the DEX-sulfate favoured the formation of alfa-FeOOH and/or alfa-Fe2O3 through GR-II (SO42-) intermediate product.

Acid sulfate systems commonly contain the metastable ferric oxyhydroxysulfate mineral schwertmannite, as well as phosphate (PO3−4) - a nutrient that causes eutrophication when present in excess. However, acid sulfate systems often experience reducing conditions that destabilize schwertmannite. Under such conditions, the longterm fate of both schwertmannite and PO3−4 may be influenced by interactions during microbially-mediated Fe (III) and SO2-4 reduction. This study investigates the influence of PO3−4 on Fe(III) and SO2-4 reduction and the subsequentmineralogical transformation(s) in schwertmannite-rich systems exposed to reducing conditions. To accomplish this, varied PO3−4 loadings were established in microbially-inoculated schwertmannite suspensions that were incubated under anoxic conditions for 82 days. Increased PO3−4 attenuated the onset of microbial Fe (III) reduction. This delayed consequent pH increases, which in turn had cascading effects on the initiation of SO2-4 reduction and subsequent mineral species formed. Under zero PO3−4 loading, goethite (αFeOOH) formed first, followed by mackinawite (FeS) and siderite (FeCO3). In contrast, in higher PO3−4 treatments, vivianite(Fe3(PO4)2) and/or sulfate green rust (FeII4 FeIII2(OH)12SO4) became increasingly important over time at the expense of goethite and mackinawite compared to PO3−4- free conditions. The findings imply that PO3−4 loading alters the rates and onset of microbial Fe(III)- and SO2-4 - reduction and the subsequent formation of secondary Febearing phases. In addition, schwertmannite reduction and the associated mineralogical evolution under anoxic conditions appears to sequester large quantities of PO3−4 in the form of green rusts and vivianite.

The electrochemical N2 reduction reaction (NRR) in an aqueous medium has recently aroused great attention for the synthesis of NH3 under ambient conditions. However, this process generally suffers from a low NH3 production rate and often requires a noble-metal based electrocatalyst with some sophisticated nanosynthesis method. This work reports a new non-precious, self-supportive iron sulfide (FeSx) NRR electrocatalyst, synthesized by a simple H2S-plasma treatment on low-cost Fe foam. The H2S-plasma treatment sulfurizes the Fe surface to afford a self-supportive FeSx thin layer on the Fe foam (FeSx/Fe). The synthesized FeSx/Fe foam can be directly used as the electrode for the NRR, and it is demonstrated to show a remarkable NH3 production rate of 4.13 × 10−10 mol s−1 cm−2 and a high faradaic efficiency of 17.6%, significantly outperforming many other reported non-precious electrocatalysts. Further material characterization shows that the surface FeSx converts to the mackinawite FeS after the NRR; the mackinawite FeS is possibly the actual high-activity NRR electrocatalyst, and density functional theory calculation is further employed to elucidate the NRR mechanism. Given the high performance and low cost, we envision that the plasma-synthesized FeSx/Fe will be of great promise for the electrochemical NH3 synthesis under ambient conditions.

In some sour reservoirs and tertiary oil recovery blocks, SO42− in the well fluid can cause the corrosion and corrosion fatigue of the sucker rods. In this paper, the corrosion behaviors of super-strength sucker rod FG20 (16Mn2SiCrMoVTiA) steel in the well fluid are investigated by electrochemical measurements, and electron probe micro-analyzer (EPMA) analysis. The results show that FG20 steel has a favorable corrosion resistance in neutral solution. When the hydrogen ions increase, the hydrolysis of SO42− greatly accelerates the corrosion of FG20 steel. The energy dispersive X-ray (EDX) results demonstrate that the corrosion process of FG20 steel in neutral well fluid is an oxygen concentration process, and the protective FeCO3 and Fe2O3 on the surface of the samples can prevent the further corrosion. With the increase of the acidity in the well fluid, the corrosion process converts into a sulphide concentration process, and the sloppy FeS and mackinawite film cannot provide effective protection for the specimens, resulting in the increase of corrosion rate. Keywords: Corrosion behavior, FG20, Electrochemical measurements, EPMA, Corrosion mechanism

We developed a novel solidification and stabilization process using a nanoscale zerovalent iron (NZVI)-cement system for reductive immobilization of hexavalent uranium (U(VI)) in a soil–cement matrix. The NZVI suspension without cement demonstrated high removal efficiency (100% in 2 h) and fast removal kinetics (53.7 Lm−2d−1), which surpassed those of other Fe-containing minerals (i.e., green rust, mackinawite, magnetite, and pyrite). Significant removal of aqueous U(VI) was observed in NZVI-cement slurries and minimal adsorbed U was desorbed by a bicarbonate/carbonate (CARB) solution. Surface analysis using scanning electron microscopy and X-ray photoelectron spectroscopy revealed U distributed homogeneously on the surface of the NZVI-cement and transformed considerably from U(VI) to reduced U species by coupled oxidation of Fe(0)/Fe(II) to Fe(III). Furthermore, the increase in pH and NZVI concentration, and presence of humic acid resulted in the enhanced U(VI) reduction in NZVI-cement slurries. The NZVI-cement system was tested with a soil matrix, resulting in successful immobilization of aqueous U(VI) in both batch and column experiments. Moreover, the U(VI) removed in the NZVI-cement system was not leached out by the CARB solution during long-term experiments. The results suggest an NZVI-cement system could represent a promising remediation alternative for effective and stable immobilization of U(VI) in contaminated sites.

Fe(II)-bearing minerals (magnetite, siderite, green rust, etc.) are common products of microbial Fe(III) reduction, and they provide a reservoir of reducing capacity in many subsurface environments that may contribute to the reduction of redox active elements such as vanadium, which can exist as V(V), V(IV), and V(III) under conditions typical of near-surface aquatic and terrestrial environments. To better understand the redox behavior of V under ferrugenic/sulfidogenic conditions, we examined the interactions of V(V) (1 mM) in aqueous suspensions containing 50 mM Fe(II) as magnetite, siderite, vivianite, green rust, or mackinawite, using X-ray absorption spectroscopy at the V K-edge to determine the valence state of V. Two additional systems of increased complexity were also examined, containing either 60 mM Fe(II) as biogenic green rust (BioGR) or 40 mM Fe(II) as a mixture of biogenic siderite, mackinawite, and magnetite (BioSMM). Within 48 h, total solution-phase V concentrations decreased to &lt, 20 µM in all but the vivianite and the biogenic BiSMM systems, however, &gt, 99.5% of V was removed from solution in the BioSMM and vivianite systems within 7 and 20 months, respectively. The most rapid reduction was observed in the mackinawite system, where V(V) was reduced to V(III) within 48 h. Complete reduction of V(V) to V(III) occurred within 4 months in the green rust system, 7 months in the siderite system, and 20 months in the BioGR system. Vanadium(V) was only partially reduced in the magnetite, vivianite, and BioSMM systems, where within 7 months the average V valence state stabilized at 3.7, 3.7, and 3.4, respectively. The reduction of V(V) in soils and sediments has been largely attributed to microbial activity, presumably involving direct enzymatic reduction of V(V), however the reduction of V(V) by Fe(II)-bearing minerals suggests that abiotic or coupled biotic–abiotic processes may also play a critical role in V redox chemistry, and thus need to be considered in modeling the global biogeochemical cycling of V.

Increasing use and mining of antimony (Sb) has resulted in greater concern involving its fate and transport in the environment. Antimony(V) and (III) are the two most environmentally relevant oxidation states, but little is known about the redox transitions between the two in natural systems. To better understand the behavior of antimony in anoxic environments, the redox transformations of Sb(V) were studied in biotic and abiotic reactors. The biotic reactors contained Sb(V) (2 mM as KSb(OH)6), ferrihydrite (50 mM Fe(III)), sulfate (10 mM), and lactate (10 mM), that were inoculated with sediment from a wetland. In the abiotic reactors, The interaction of Sb(V) with green rust, magnetite, siderite, vivianite or mackinawite was examined under abiotic conditions. Changes in the concentrations of Sb, Fe(II), sulfate, and lactate, as well as the microbial community composition were monitored over time. Lactate was rapidly fermented to acetate and propionate in the bioreactors, with the latter serving as the primary electron donor for dissimilatory sulfate reduction (DSR). The reduction of ferrihydrite was primarily abiotic, being driven by biogenic sulfide. Sb and Fe K-edge X-ray absorption near edge structure (XANES) analysis showed reduction of Sb(V) to Sb(III) within 4 weeks, concurrent with DSR and the formation of FeS. Sb K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy analysis indicated that the reduced phase was a mixture of S- and O-coordinated Sb(III). Reduction of Sb(V) was not observed in the presence of magnetite, siderite, or green rust, and limited reduction occurred with vivianite. However, reduction of Sb(V) to amorphous Sb(III) sulfide occurred with mackinawite. These results are consistent with abiotic reduction of Sb(V) by biogenic sulfide and reveal a substantial influence of Fe oxides on the speciation of Sb(III), which illustrates the tight coupling of Sb speciation with the biogeochemical cycling of S and Fe., Antimony; Biogeochemistry; Dissimilatory sulfate reduction; Microbial reduction; Iron sulfide

International audience; Pyrite formation at low temperature during early diagenesis in (sub-)surface sediments is an essential step of Fe and S biogeochemical cycles and the presence of this ubiquitous mineral of surface environments is often used as an indicator of paleo-redox conditions. Pathways of pyrite formation are usually discussed in environmental settings by involving a variety of nanosized Fe-S mineralogical precursors as a function of the local geochemical conditions. However, the influence of trace element impurities such as Ni and As in the solution at the time of pyrite formation has been poorly studied, whereas specific chemical signatures of trace elements are commonly observed in sedimentary pyrites. A better understanding of the impact of Ni and As incorporation at trace levels on pyrite formation is essential to help refining the use of these elements as paleo-redox indicators and to evaluate the role of pyrite as a sink regulating the biogeochemical cycle of potentially toxic trace elements. In this study, we have performed syntheses of pyrite at low temperature by the polysulfide pathway using aqueous Fe(III) and H2S in the presence of trace amounts of Ni(II) (0.001 mol%Fe) and As(III) (0.001 mol%Fe). Analysis of the solids collected at different time steps over the course of the experiments using X-Ray absorption spectroscopy at both the Fe and S K-edges shows that pyrite starts to precipitate within 5 days in presence of Ni(II) and within 32 days in presence of As(III), while the control experiment showed an intermediate precipitation rate of 14 days. Shell-by-shell analysis of Fe K-edge EXAFS data shows that the initial mineralogical precursors are the same whatever the experimental conditions and correspond to poorly-crystalline FeS (3.0±0.1 Fe-S@2.25 Å; 1.7±0.2 Fe-Fe@2.67 Å). In addition, XANES qualitative analysis suggests the incorporation of small amounts of Fe(III) within these FeS precursors. Synchrotron-based XRD and WAXS-PDF analysis of the starting solids show that in addition to S(0), the FeS precursors correspond to a continuum of FeS particles that ranges from tetragonal nanocrystalline FeS (a = 3.70(2) Å, c = 5.24(7) Å, MCDab = 41±4 Å MCDc = 21±2 Å) to cluster-type FeS (MCDabc < 8.4±4.3 Å). We propose that Ni(II) and As(III) have a different type of interaction with these FeS precursors, resulting respectively in an increase and a decrease in the rate of pyrite nucleation. While Ni(II) would incorporate within the structure of the FeS precursors, As would interact with (poly)sulfides in solution to form thio-As, possibly binding or precipitating onto FeS surfaces and thus slowing FeS transformation to FeS2. Given that both Ni and As were introduced at trace levels in our experiments, these results suggest that the occurrence of trace amounts of impurities could have a strong influence on pyrite precipitation kinetics in natural settings such as pore-scale microenvironments. In addition to emphasizing the importance of trace elements such as Ni or As on the persistence of mobile colloidal FeS species in anoxic conditions, the results of the present study also point to the importance of considering the actual nature of the impurities when using pyrite composition for ancient environments and past climates reconstruction.

Metal sulphides constitute cheap, naturally abundant, and environmentally friendly materials for energy storage applications and chemistry. In particular, iron (II) monosulphide (FeS, mackinawite) is a material of relevance in theories of the origin of life and for heterogenous catalytic applications in the conversion of carbon dioxide (CO2) towards small organic molecules. In natural mackinawite, Fe is often substituted by other metals, however, little is known about how such substitutions alter the chemical activity of the material. Herein, the effect of Ni doping on the structural, electronic, and catalytic properties of FeS surfaces is explored via dispersion-corrected density functional theory simulations. Substitutional Ni dopants, introduced on the Fe site, are readily incorporated into the pristine matrix of FeS, in good agreement with experimental measurements. The CO2 molecule was found to undergo deactivation and partial desorption from the doped surfaces, mainly at the Ni site when compared to undoped FeS surfaces. This behaviour is attributed to the energetically lowered d-band centre position of the doped surface, as a consequence of the increased number of paired electrons originating from the Ni dopant. The reaction and activation energies of CO2 dissociation atop the doped surfaces were found to be increased when compared to pristine surfaces, thus helping to further elucidate the role Ni could have played in the reactivity of FeS. It is expected that Ni doping in other Fe-sulphides may have a similar effect, limiting the catalytic activity of these phases when this dopant is present at their surfaces.

Journal of petroleum exploration and production technologies 11(7), 3129-3143 (2021). doi:10.1007/s13202-021-01230-1, Published by Springer, Berlin ; Heidelberg

The chemical speciation of mercury (Hg), methyl mercury (MeHg), sulfur and iron was investigated in the sediment and porewater of Lake Angessjon, a boreal, shallow (maximum depth 2.5 m), oligo-/dystrophic lake in northern Sweden. The lake receives terrestrial stream runoff from surrounding coniferous forest soils and peatlands having a low pH (4.6) and high concentrations of dissolved organic matter (DOM, annual average: 45 mg L−1), Fe (60 µM), sulfate (105 µM), inorganic Hg (1200 pM) and MeHg (250 pM). Sulfur K-edge XANES and Hg LIII-edge EXAFS spectroscopic measurements were used to characterize and quantify the sulfur speciation in the lake sediment at nine occasions, covering different seasons in the years of 2007 and 2009. In the surface sediment (0–3 cm) sulfate is reduced to zero-valent S and inorganic sulfide, that in turn reacts with Fe to form FeSm (mackinawite) and FeS2 (framboidal pyrite). The latter mineral becomes increasingly dominant by depth in the sediment. Thermodynamic modeling successfully predicted measured porewater concentrations of Hg in the sediment. Metacinnabar (β-HgS) and Hg(NOM-RS)2 complexes (the latter formed as a reaction between Hg(II) and thiol groups associated with natural organic matter, NOM-RSH) were the dominant forms of Hg(II) in the solid phase of sediments and Hg(II)-polysulfides (aq) dominated in the porewater. We argue that FeSm is a key component that indirectly controlled the Hg(II) speciation in the sediment by keeping the aqueous phase concentration of inorganic sulfide in the 0.5–2 µM range throughout the year. Besides providing a pool of readily soluble inorganic sulfide for formation of β-HgS(s), as demonstrated by previously reported EXAFS experiments, we further suggest FeSm may serve as a precursor for the formation of a more crystalline (less soluble) β-HgS(s) phase than present in environments devoid of FeSm. Support for this was provided by comparing our results with previously reported thermodynamic modelling results of Hg(II) and MeHg solubility in organic soils devoid of FeSm. In more general terms, we suggest the presence or absence of FeSm, through its influence on the chemical speciation of Hg and MeHg, may be a key factor behind the variability in rates of Hg(II) and MeHg transformation processes, such as methylation, reduction and demethylation, reported for different environmental settings.

Arsenic incorporation into newly formed As sulfides has recently been identified as an important As sequestration pathway in both laboratory experiments and natural As-wetlands. Here, we used an in situ experimental technique with double nylon experimental bags (10-μm mesh) to study the effect of low-cost organic materials (sawdust, wood cubes and hemp shives) on As sulfidation in three naturally As-enriched wetland soils under water-saturated (~1 m depth) and neutral pH conditions. After 15 months of in situ incubation, all of the organic materials and their corresponding inner bags were covered by yellow-black mineral accumulations, dominantly composed of crystalline As4S4 polymorphs (realgar and bonazziite) and reactive Fe(II) sulfides (probably mackinawite); while the major fraction of As (~80%) was sequestered as AsS minerals. The amount of As accumulation in the experimental bags varied significantly (0.03–4.24 g As kg−1) and corresponded with different levels of As (0.23–9.4 mg As L−1) in the groundwater. Our findings suggest an authigenic formation of AsS minerals in strongly reducing conditions of experimental bags by a combination of reduced exchange of solutes through the pores of the bag and comparatively fast microbial production of dissolved sulfide. Arsenic sulfide formation, as an effective treatment mechanism for natural and human-constructed wetlands, appears to be favored for As(III)-rich waters with a low Fe(II)/As(III) molar ratio. These conditions prevent the consumption of dissolved As and sulfide by their preferential incorporation into natural organic matter, and newly-formed Fe(II) sulfides, respectively.

Iron-based heterogeneous Fenton systems have been widely proposed for recalcitrant contaminants degradation. However, low efficiency of H2O2 decomposition and Fe(II)/Fe(III) recycling quite limited their applications. In this work, Co-doped iron sulfide (FeS) was successfully prepared through a modified hydrothermal method, and characterized by XRD, FESEM, HRTEM, XPS and BET. With Co(II) substitution, FeS structure transformed from pyrrhotite to mackinawite. The 10% Co-FeS was highly effective in H2O2 activation toward Rhodamine B (RhB) degradation. The pseudo first-order kinetic constant of 10% Co-FeS was 0.323 min−1, which was 31.4 and 85 times higher than that of CoS2 and FeS, respectively. Quenching experiments and EPR analysis illustrated that •OH was the dominant radicals for RhB degradation and the role of Co(II) in H2O2 direct decomposition was negligible. Batch experiment suggested that the excellent catalytic performance of 10% Co-FeS were ascribed to: (i) Co incorporation into FeS structure facilitated electron transfer between S species and Fe3+, thus accelerating Fe(II)/Fe(III) conversion on the surface, and (ii) more active sites were exposed. The Co-doped FeS exhibited high stability with low Fe/Co leaching and great recyclability. This novel strategy brought potential insights to develop highly efficient catalyst like metal sulfides for wastewater treatment.