FeS2 Research Articles

Tracing the evolution of the world's first mined bauxite from palaeotopography to pyritization: Insights from Minjera deposits, Istria, Croatia

The Minjera bauxites are the first analysed and mined bauxites in the world. They are a group of pyritised bauxites situated in northern Istria, developed during the subaerial exposure phase which marked a major part of the Late Cretaceous and Palaeocene in northern Istria. In this study, the morphology, petrography, mineralogy, geochemistry as well as stable sulphur isotopes of the D-1 and D-15 deposits from Minjera were studied, as well as the evolution of their bedrock and cover. This study found that those two deposits differ in morphology, mineralogy and geochemistry as a consequence of their different palaeotopographical positions, with the D-1 deposit located at a higher position at the time of its formation compared to D-15, which led to the higher degree of leaching and desilicification in the D-1 deposit. The pyritisation in the studied deposits was a multi-phase process, which began with the deposition of framboidal pyrite and micrometre-sized anhedral pyrite, over which colloform pyrite was precipitated. This indicates that the solutions were initially supersaturated with iron sulphide, saturation of which subsequently changed, as finally euhedral, dendritic and acicular pyrite were deposited, indicating undersaturated conditions. The final stage was marked by deposition of pyrite veins. This formational sequence of pyrites is also supported by stable sulphur isotopes, as the δ34S values exhibit a wide range from -40.86 to 2.32 ‰, where lower values indicate an open system with an unrestricted sulphate supply in which supersaturated conditions could have been achieved, while the higher values indicate a change towards a closed system with limited sulphate supply. The organic matter necessary for microbial sulphate reduction was derived from the marshy environment established atop of the bauxite. The initial flooding started in the Palaeocene, with the first part of the sequence being deposited under lacustrine conditions, which changed towards fully marine with the deposition of Foraminiferal limestones.

Synthesis of biocompatible hydrogel of alginate-chitosan enriched with iron sulfide nanocrystals

This work aimed to synthesize and characterize a biocompatible hydrogel of alginate and chitosan enriched with iron sulfide nanocrystals. Three concentrations of iron sulfide nanocrystals (FeS2NCs) 0.03905, 0.0781, and 0.2343 mg/ml were used. Gel swelling was determined using phosphate-buffered saline solution at 1, 2, 4, 6, 24, 48, and 72 h. The microstructure, the morphology, and the elastic strength were determined by optical microscopy, scanning electron microscopy, and rheological studies, respectively. The functional groups were identified through Fourier Transform Infrared spectroscopy. Biocompatibility was determined in a murine model; after seven days of subdermal inoculation, histological sections stained with H&E were analyzed, and then histopathological features were evaluated. All the compounds obtained showed a loss modulus lower than the storage modulus. The 0.2343 mg/ml FeS2NCs hydrogel showed higher swelling than the control. In the in vivo evaluation, no adverse effects were found. The presence of FeS2NCs was well tolerated in the subcutaneous tissue of mice, according to histopathological analysis. The hydrogels synthesized with added FeS2NCs demonstrate a swelling ratio of 150 %, rheologically exhibiting gel-like behavior rather than viscous liquids. Furthermore, they did not present any adverse effects on the subcutaneous tissue.

PEGylated Opto-Magnetic Gold and Silver Sulfide Iron Oxide Nanoprobes for Synergistic Photothermal Therapy

PEGylated Opto-Magnetic Gold and Silver Sulfide Iron Oxide Nanoprobes for Synergistic Photothermal Therapy

Shape-controlled electro-synthesis of pyrrhotite

Recently, iron sulfide nanomaterials have drawn increased interest, due to their novel properties and extensive applications depending on their structure. To date, various methods have been employed for the synthesis of iron sulfide nanostructures with different shapes and morphologies. The synthesis method of iron sulfide nanomaterial is a challenge, as a small variation in sulfur content can lead to formation of different phases of iron sulfide. In this study, iron sulfide nanostructures were synthesized using our fast, simple, efficient, economical and environmentally friendly method in an electrochemical cell containing two iron sheets as electrodes in an aqueous solution of sodium sulfide. This method, with many advantages such as low-toxicity, low cost and easy handling, helps to control the properties of the products through the synthesis by tuning the growth conditions. Here, the influence of applied voltage ranging from 5 V to 25 V and annealing temperatures of 200 °C and 800 °C on the structure and magnetic properties of the products were studied. The samples were analyzed by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD patterns confirmed the formation of monoclinic and hexagonal pyrrhotite at 200 °C and 800 °C, respectively. Based on SEM images, pyrrhotite in different shapes, such as quasi-spherical, feathers, sheets and flower-like structures, are formed depending on the applied voltage and annealing temperature. According to VSM results, all samples annealed at 200 °C are magnetically soft with only a little hysteresis, but the magnetization increases from 2.3 emu/g to 10.1 emu/g when applied voltage varies from 5 V to 25 V. All samples annealed at 800 °C exhibit an antiferromagnetic behavior. With increasing the applied voltage, the value of remanence magnetization and coercivity increases up to ∼2000 Oe and ∼0.14 emu/g, respectively.

Green remediation of mercury-contaminated soil using iron sulfide nanoparticles: Immobilization performance and mechanisms, effects on soil properties, and life cycle assessment

Mercury (Hg) pollution in soil has grown into a severe environmental issue. Effective in situ immobilization techniques are crucially demanded. In this study, we explored the application of carboxymethyl cellulose stabilized iron sulfide nanoparticles (CMC-FeS) for in situ immobilization of Hg in soil. CMC-FeS (a CMC-to-FeS molar ratio of 0.0004) was prepared via the reaction between FeSO4 and Na2S using CMC as a stabilizer. Remedying the Hg-polluted soil using 0.03 % CMC-FeS via batch experiments effectively reduced the acid leachable Hg by 97.5 % upon equilibrium after 71 days. Column elution tests demonstrated that the addition of CMC-FeS decreased the peak Hg concentration by 89.9 % and the total Hg mass eluted by 94.9 % after 523 pore volumes. CMC-FeS immobilized Hg in soil via chemical precipitation, ion exchange, and surface complexation. After the CMC-FeS treatment, Hg was transformed from more available exchangeable, carbonate-bound, and organic material-bound forms into the less available residual fraction, reducing the environmental risk of soil Hg from medium to low. The application of CMC-FeS boosted the soil enzyme activities and enhanced the soil bacterial diversity whereas decreased the production of methylmercury. CMC-FeS also facilitated long-term immobilization of Hg in soil. The acid leachable Hg and relative Hg bioaccessibility was decreased. Lift cycle assessment indicated that the preparation and application of CMC-FeS for in situ Hg remediation in soil met green chemistry principles. The present study confirms that CMC-FeS can be applied as an efficient and “green” amending agent for long-term Hg immobilization in soil/sediment.

Application of pyrite trace-metal and S and Ni isotope signatures to distinguish sulfate- versus iron-driven anaerobic oxidation of methane

The formation of authigenic pyrite in marine sediments involves multiple reactions between ferrous iron (Fe2+) and hydrogen sulfide (H2S). Ferrous iron is commonly provided through the reductive dissolution of Fe-(oxyhydr)oxides by organic matter (i.e., dissimilatory Fe reduction), dissolved sulfide (i.e., abiotic Fe reduction) or methane (i.e., Fe-AOM), whereas sulfide is supplied by organoclastic sulfate reduction (OSR) or sulfate-driven anaerobic oxidation of methane (SD-AOM). Since Rayleigh-type distillation operates widely in sediments of gas-hydrate-bearing zones, sulfur and nickel isotope compositions (i.e., δ34S and δ60Ni) cannot readily distinguish OSR- from SD-AOM-associated pyrite. However, these microbial pathways may yield different patterns of trace-element enrichment in pyrite. To better understand the linkage of trace-element patterns to specific microbial pathways (i.e., Fe reduction, Fe-AOM, OSR and SD-AOM), and to evaluate the use of S and Ni isotopic signatures as tracers for pyrite formation pathways in methane-rich sediments, we report pyrite-associated trace element and δ34S and δ60Ni isotope analyses of sediments from a gas hydrate borehole (Site GMGS4-SC-03) from the Shenhu area, Pearl River Mouth Basin, South China Sea. Pyrite formed in conjunction with Fe- and/or SD-AOM exhibits abundant framboidal overgrowths and extremely high δ34S (up to +142.8‰) and δ60Ni (up to +2.72‰), representing the highest stable S and Ni isotopic compositions of pyrite reported to date. These pyrite morphologies are enriched in Co and Ni, which may be a diagnostic signature of an SD-AOM pathway. By contrast, OSR-associated pyrite is enriched in Cu and Zn due to OSR-induced release of trace elements from decaying organic matter. In addition, the relationship of As to Cu and/or Zn can distinguish microbial Fe/Mn reduction from Fe/Mn-AOM, because microbial Fe/Mn reduction releases trace elements from both Fe/Mn-(oxyhydr)oxides (i.e., As) and organic matter (i.e., Cu and Zn), whereas Fe/Mn-AOM only releases trace elements from Fe/Mn-(oxyhydr)oxides. Furthermore, an observed covariation between As and either Co or Ni in most pyrite with high δ34S, indicates that this pyrite captured both As released during Fe/Mn-AOM and Co and Ni from SD-AOM. Thus, the high nickel isotope values measured in this study likely dominantly reflect release of isotopically heavy Ni from Fe- and Mn-(oxyhydr)oxides. Our results demonstrate that the trace-element composition of pyrite in gas-hydrate-bearing sediments can record the geochemical signature of the dominant microbial processes.

Inhibition of acid rock drainage with iron-silicate or phosphate film: in rainy and submerged environments.

Iron phosphate-based coating and iron silicate-based coating were used to inhibit the oxidation of sulfide minerals in rainy and submerged environments. The inhibiting effectiveness of coating agents on the oxidation of iron sulfide minerals was investigated using pyrite and rock samples resulting from acid drainage. The film formed with both surface-coating agents was identified by pyrite surface analysis. It was also confirmed that the formation of coatings varies depending on the crystallographic orientation. The inhibitory effects under rainy and submerged conditions were investigated using column experiments. Submerged conditions accelerated deterioration compared to that under rainy conditions. Iron phosphate coating had a significantly better oxidation-inhibitory effect (84.86-98.70%) than iron silicate coating (56.80-92.36%), and at a concentration of 300mM, H+ elution was inhibited by more than 90% throughout the experiment. Furthermore, methods for effective film formation were investigated in terms of producing Fe3+; (1) application of coating agents mixed with oxidant (H2O2), (2) application of coating agent after the use of the oxidant. In a rainy environment, applying iron phosphate-based coating using the sequential method showed oxidation inhibition effects for cycles 1-9, whereas applying the mixed material showed effects for cycles 9-13. The use of a surface-coating agent after applying an oxidant did not inhibit oxidation. The surface coating agent and the oxidizing agent should be applied as a mixture to form a film.

Iron Sulfide Microspheres Supported on Cellulose-Carbon Nanotube Conductive Flexible Film as an Electrode Material for Aqueous-Based Symmetric Supercapacitors with High Voltage.

Nanostructured iron disulfide (FeS2) was uniformly deposited on regenerated cellulose (RC) and oxidized carbon nanotube (CNT)-based composite films using a simple chemical bath deposition method to form RC/CNT/FeS2 composite films. The RC/CNT composite film served as an ideal substrate for the homogeneous deposition of FeS2 microspheres due to its unique porous architecture, large specific surface area, and high conductivity. Polypyrrole (PPy), a conductive polymer, was coated on the RC/CNT/FeS2 composite to improve its conductivity and cycling stability. Due to the synergistic effect of FeS2 with high redox activity and PPy with high stability and conductivity, the RC/CNT/FeS2/PPy composite electrode exhibited excellent electrochemical performance. The RC/CNT/0.3FeS2/PPy-60 composite electrode tested with Na2SO4 aqueous electrolyte could achieve an excellent areal capacitance of 6543.8 mF cm-2 at a current density of 1 mA cm-2. The electrode retained 91.1% of its original capacitance after 10,000 charge/discharge cycles. Scanning electron microscopy (SEM) images showed that the ion transfer channels with a pore diameter of 5-30 μm were formed in the RC/CNT/0.3FeS2/PPy-60 film after a 10,000 cycle test. A symmetrical supercapacitor device composed of two identical pieces of RC/CNT/0.3FeS2/PPy-60 composite electrodes provided a high areal capacitance of 1280 mF cm-2, a maximum energy density of 329 μWh cm-2, a maximum power density of 24.9 mW cm-2, and 86.2% of capacitance retention after 10,000 cycles at 40 mA cm-2 when tested at a wide voltage window of 1.4 V. These results demonstrate the greatest potential of RC/CNT/FeS2/PPy composite electrodes for the fabrication of high-performance symmetric supercapacitors with high operating voltages.

Deciphering the Catalytic Mechanism of Peroxidase-like Activity of Iron Sulfide Nanozymes.

Iron sulfide nanomaterials represented by FeS2 and Fe3S4 nanozymes have attracted increasing attention due to their biocompatibility and peroxidase-like (POD-like) catalytic activity in disease diagnosis and treatments. However, the mechanism responsible for their POD-like activities remains unclear. Herein, taking the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2 on FeS2(100) and Fe3S4(001) surfaces, the catalytic mechanism was investigated in detail using density functional theory (DFT) calculations and experimental characterizations. Our experimental results showed that the catalytic activity of FeS2 nanozymes was significantly higher than that of Fe3S4 nanozymes. Our DFT calculations indicated that the surface iron ions of iron sulfide nanozymes could effectively catalyze the production of HO• radicals via the interactions between Fe 3d electrons and the frontier orbitals of H2O2 in the range of -10 to 5 eV. However, FeS2 nanozymes exhibited higher POD-like activity due to the surface Fe(II) binding to H2O2, forming inner-orbital complexes, which results in a larger binding energy and a smaller energy barrier for the base-like decomposition of H2O2. In contrast, the surface iron ions of Fe3S4 nanozymes bind to H2O2, forming outer-orbital complexes, which results in a smaller binding energy and a larger energy barrier for the base-like decomposition of H2O2. The charge transfer analysis showed that FeS2 nanozymes transferred 0.12 e and Fe3S4 nanozymes transferred 0.05 e from their surface iron ions to H2O2, respectively. The simulations were consistent with the experimental observations that the FeS2 nanozymes had a greater affinity for H2O2 compared to that of Fe3S4 nanozymes. This work provides a theoretical foundation for the rational design and accurate preparation of iron sulfide functional nanozymes.

Iron sulfide mineral/polylactic acid mixotrophic biofilter for simultaneous nitrate and phosphate removal

Heterotrophic denitrification based on polylactic acid (PLAHD) can remove nitrate effectively, but it is expensive and can't remove phosphate. Autotrophic denitrification based on iron sulfide (ISAD) can simultaneously remove nitrate and phosphate cost-effectively, but its nitrate rate is slow. So, iron sulfide mineral/polylactic acid mixotrophic biofilter (ISPLAB) was constructed to combine advantages of ISAD and PLAHD. ISPLAB achieved nitrogen and phosphorus removal rates of 98.04 % and 94.12 %, respectively, at a hydraulic retention time (HRT) of 24 h. The study also revealed that controlling molecular weight (Mw) of PLA improved the release of soluble organic matter; adding iron sulfide enhanced the hydrolysis of PLA and precipitated PO43− of Fe2+/Fe3+, thereby facilitated simultaneous nitrogen and phosphorus removal. Microbial community analysis resulted that denitrifying bacterias (Phaeodactylibacter and Methylotenera), sulfur-reducing bacterias (Hyphomicrobium), sulfur-oxidizing bacteria (Denitratisoma), iron-reducing bacteria (Romboutsia) and hydrolyzed bacterias (norank_f_norank_o_1–20 and norank_f_Caldilineaceae) coexisted in the ISPLAB system. Organics and iron sulfide drived the denitrification process in ISPLAB.

Continuous-flow columns packed with zero-valent iron and iron sulfide as a feasible strategy to remediate the persistent contaminant nitroguanidine

The insensitive munitions compound nitroguanidine (NQ) is used by the U.S. Army to avoid unintended explosions. However, NQ also represents an emerging contaminant whose environmental emissions can cause toxicity toward aquatic organisms, indicating the need for effective remediation strategies. Thus, we investigated the feasibility of treating water contaminated with NQ in continuous-flow columns packed with zero-valent iron (ZVI) or iron sulfide (FeS). Initially, the impact of pH on NQ transformation by ZVI or FeS was evaluated in batch experiments. The pseudo first-order rate constant for NQ transformation (k1, NQ) by ZVI was 8–10 times higher at pH 3.0 compared to pH 5.5 and 7.0, whereas similar k1, NQ values were obtained for FeS at pH 5.5–10.0. Based on these findings, the influent pH fed to the ZVI- and FeS-packed columns was adjusted to 3.0 and 5.5, respectively. Both reactors transformed NQ into nitrosoguanidine (NsoQ). Further transformation of NsoQ by ZVI produced aminoguanidine, guanidine, and cyanamide, whereas NsoQ transformation by FeS produced guanidine, ammonium, and traces of urea. ZVI outperformed FeS as a reactive material to remove NQ. The ZVI-packed column effectively removed NQ below detection even after 45 d of operation (490 pore volumes, PV). In contrast, NQ breakthrough (removal efficiency <85%) was observed after 18 d (180 PV) in the FeS-packed column. The high NQ removal efficiency and long service life of the ZVI-packed column (>490 PV) suggest that the technology is a promising approach for NQ treatment in packed-bed reactors and in situ remediation.

Effect of sulfidation on ethaline-assisted electrodeposited iron sulfide-based electrocatalyst for efficient saline water splitting

This study investigated the synthesis of ethaline-assisted iron sulfide on nickel foam (NF) using the electrodeposition method to facilitate saline water splitting. The oxidization of iron and the formation of Fe(OH)3 on the cathode surface pose challenges for the electrodeposition of iron sulfide from aqueous solutions. To tackle these issues, deep eutectic solvent-assisted electrodeposition and ethaline-assisted sulfidation methods have been investigated for synthesizing FeS2. These approaches aim to enhance the efficiency of the iron sulfide electrode by preventing unwanted oxidation and ensuring the formation of high-quality coatings. Sulfidation in non-aqueous media was performed at varying durations, revealing that sulfur content significantly impacts the morphology of the prepared electrode. The optimum FeS2/NF catalyst offers the lowest overpotential of 194 mV at 10 mA cm−2 for oxygen evolution reaction (OER) and 176 mV at 10 mA cm−2 for hydrogen evolution reaction (HER) in saline water splitting. The enhanced catalytic activity is attributed to the formation of multiphasic components in the catalyst. The electrodes exhibited stability in saline water conditions for approximately 10 h for both OER and HER. Moreover, FeS2/NF exhibited stability for 50 h in OER and 20 h in HER when applied to pure water splitting. The investigation explores the unique synthesis of FeS2 in non-aqueous media and examines its catalytic activity in saline water electrolysis.

Sulfidation of Iron - Based Nanomaterial as Catalyst for Water Splitting Using Hydrothermal

Consumption of fossil fuels causes greenhouse effect and global warming, hence the need for renewable energy sources that are environmentally friendly. Hydrogen is one of the abundant elements on earth. Hydrogen refers to a clean and renewable energy source, hydrogen can be a good choice to reduce greenhouse gas emissions. One way to produce hydrogen is by electrochemical water splitting. This study aims to determine the characterization of iron-based nanomaterials (iron sulfide - iron hydroxide) as a water splitting catalyst in general. Iron sulfide synthesis was carried out using hydrothermal sulfidation method for 6 hours at 80 oC with nickel foam as substrate. Synthesis of iron sulfide varying the concentration of sodium sulfide nonahydrate (0.0125 M, 0.025 M, 0.05 M and 0.1 M) produced brownish yellow to blackish grey colored samples. Characterization results using XRD showed that iron sulfide peaks were detected at higher concentrations of sodium sulfide nonahydrate. Based on the results of analyzing iron hydroxide using SEM, it is known that the sample is in the form of nano walls and on iron sulfide, it is known that the sample is in the form of nanoscale particles. Based on electrochemical measurement results, iron hydroxide can be a good catalyst for hydrogen evolution reaction (HER) compared with commercial Pt/C. The overpotential of iron hydroxide is smaller than Pt/C, which is only 15 mV at a current density 10 mA/cm2 and iron sulfide can be a good catalyst for oxygen evolution reaction (OER) with electrocatalytic measurement results close to commercial RuO2. This is indicated by the small overpotential (260 mV at current densisty 10 mA/cm2 and small tafel slope (51 mV/dec).

Nitrate Chemodenitrification by Iron Sulfides to Ammonium under Mild Conditions and Transformation Mechanism.

Autotrophic denitrification utilizing iron sulfides as electron donors has been well studied, but the occurrence and mechanism of abiotic nitrate (NO3-) chemodenitrification by iron sulfides have not yet been thoroughly investigated. In this study, NO3- chemodenitrification by three types of iron sulfides (FeS, FeS2, and pyrrhotite) at pH 6.37 and ambient temperature of 30 °C was investigated. FeS chemically reduced NO3- to ammonium (NH4+), with a high reduction efficiency of 97.5% and NH4+ formation selectivity of 82.6%, but FeS2 and pyrrhotite did not reduce NO3- abiotically. Electrochemical Tafel characterization confirmed that the electron release rate from FeS was higher than that from FeS2 and pyrrhotite. Quenching experiments and density functional theory calculations further elucidated the heterogeneous chemodenitrification mechanism of NO3- by FeS. Fe(II) on the FeS surface was the primary site for NO3- reduction. FeS possessing sulfur vacancies can selectively adsorb oxygen atoms from NO3- and water molecules and promote water dissociation to form adsorbed hydrogen, thereby forming NH4+. Collectively, these findings suggest that the NO3- chemodenitrification by iron sulfides cannot be ignored, which has great implications for the nitrogen, sulfur, and iron cycles in soil and water ecosystems.

Antioxidant activity and cytotoxicity of greigite nanoparticles synthesized by hydrothermal technique.

The effects of 180, 210, and 230°C reaction temperatures on the structural and magnetic properties of synthesized iron sulfide nanoparticles were studied. The Rietveld refinement analysis result of the X-ray diffraction data indicated that greigite was the dominant phase in all samples. The sample was prepared at 210°C for 18h and had a greater wt% ratio of the greigite phase. The crystallite and particle sizes increased with increasing reaction temperatures. Scanning electron microscope images confirmed the presence of aggregation of synthesized rod-shaped nanoparticles. The magnetic hysteresis curves of all samples showed ferromagnetic behavior at room temperature. The magnetic saturation of three samples increases with increased reaction temperature, but the coercive force has the opposite behavior. Antioxidant activity and cytotoxicity of the sample synthesized at 210°C were investigated. This sample killed cancer cells at relatively moderate and high concentrations with high viability of normal cells, demonstrating the sample's suitability for use in killing cancer cells while avoiding normal cells.

The behavior of pyrite during in-situ leaching of uranium by CO2 + O2: A case study of the Qianjiadian uranium deposit in the Songliao Basin, northeastern China

Oxidative weathering of pyrite, a widespread iron sulfide mineral, is crucial for the uranium mineralization in sandstone-hosted uranium deposits and the ore utilization leaching under manual intervention. To understand the behavior of pyrite under CO2 + O2 leaching conditions in sandstone-hosted uranium deposits, samples of uranium ore from the mineralized zone of the Qianjiadian IV uranium deposit located in the lower section of the Yaojia Formation were collected for this study. The stirring leaching experiment was carried out through the processes of the pyrite-bearing uranium ore samples thinned before and after the reaction, followed by an optical microscopic study and the TESCAN Integrated Mineral Analyzer analysis, and finally, the thermodynamic simulation by making use of PHREEQC3.0.The results revealed the following: (1) The dissolution particles of pyrite become smaller, which may increase the porosity of the ore layer and the exposure ratio of uranium minerals. And more soluble pyrite with a high free surface will be more competitive with uranium minerals for the consumption of O2. (2) The ion (Fe2+) produced by the dissolution of pyrite will be oxidized to Fe3+ by excess O2 (4 mol), which provides an oxidant for the oxidation of uranium minerals, and the generated SO42- will combine with the Ca2+ released from calcite to form a permanent precipitate of gypsum, which may block pores and cover the uranium ore. (3) Pyrite and calcite will consume O2 and CO2 in the injection system, thus jointly inhibiting the leaching of uranium minerals. After the injection of excessive CO2 and O2, the concentration of Ca2+, SO42-, Fe3+, UO22+, and HCO3– in the system will continue to accumulate, resulting in the secondary precipitation of calcite, co-precipitation of gypsum, iron minerals, colloids, and hexavalent uranium minerals, resulting in plugging pores and seriously affecting the effective leaching of uranium.This study contributes to the understanding of the behavior of pyrite during uranium recovery through CO2 + O2 leaching. It also contributes to the understanding of quantitative uranium mineralization in sandstone-hosted uranium deposits and process parameters in in-situ leaching (ISL) of uranium.

Cr(VI) removal during cotransport of nano-iron-particles combined with iron sulfides in groundwater: Effects of D. vulgaris and S. putrefaciens

Iron-based materials such as nanoscale zerovalent iron (nZVI) are effective candidates to in situ remediate hexachromium (Cr(VI))-contaminated groundwater. The anaerobic bacteria could influence the remediation efficiency of Cr(VI) during its cotransport with nZVI in porous media. To address this issue, the present study investigated the adsorption and reduction of Cr(VI) during its cotransport with green tea (GT) modified nZVI (nZVI@GT) and iron sulfides (FeS and FeS2) in the presence of D. vulgaris or S. putrefaciens in water-saturated sand columns. Experimental results showed that the nZVI@GT preferred to heteroaggregate with FeS2 rather than FeS, forming nZVI@GT-FeS2 heteroaggregates. Although the presence of D. vulgaris further induced nZVI@GT-FeS2 heteroaggregates to form larger clusters, it pronouncedly improved the dissolution of FeS and FeS2 for more Cr(VI) reduction associated with lower Cr(VI) flux through sand. In contrast, S. putrefaciens could promote the dispersion of the heteroaggregates of nZVI@GT-FeS2 and the homoaggregates of nZVI@GT or FeS by adsorption on the extracellular polymeric substances, leading to the improved transport of Fe-based materials for a much higher Cr(VI) immobilization in sand media. Overall, our study provides the essential perspectives into a chem-biological remediation technique through the synergistic removal of Cr(VI) by nZVI@GT and FeS in contaminated groundwater. Environmental implicationThe green-synthesized nano-zero-valent iron particles (nZVI@GT) using plant extracts (or iron sulfides) have been used for in situ remediation of Cr(VI) contaminated groundwater. Nevertheless, the removal of Cr(VI) (including Cr(VI) adsorption and Cr(III) generation) could be influenced by the anaerobic bacteria governing the transport of engineered nanoparticles in groundwater. This study aims to reveal the inherent mechanisms of D. vulgaris and S. putrefaciens governing the cotransport of nZVI@GT combined with FeS (or FeS2) to further influence the Cr(VI) removal in simulated complex groundwater media. Our findings provides a chemical and biological synergistic remediation strategy for nZVI@GT application in Cr(VI)-contaminated groundwater.

Cosmic dust impacts on the Hubble Space Telescope.

Exposure of the Hubble Space Telescope to space in low Earth orbit resulted in numerous hypervelocity impacts by cosmic dust (micrometeoroids) and anthropogenic particles (orbital debris) on the solar arrays and the radiator shield of the Wide Field and Planetary Camera 2, both subsequently returned to Earth. Solar cells preserve residues from smaller cosmic dust (and orbital debris) but give less reliable information from larger particles. Here, we present images and analyses from electron, ion and X-ray fluorescence microscopes for larger impact features (millimetre- to centimetre-scale) on the radiator shield. Validated by laboratory experiments, these allow interpretation of composition, probable origin and likely dimensions of the larger impactors. The majority (~90%) of impacts by grains greater than 50 μm in size were made by micrometeoroids, dominated by magnesium- and iron-rich silicates and iron sulfides, metallic iron-nickel and chromium-rich spinel similar to that in ordinary chondrite meteorites of asteroid origin. Our re-evaluation of the largest impact features shows substantially fewer large orbital debris impacts than reported by earlier authors. Mismatch to the NASA ORDEM and ESA MASTER models of particle populations in orbit may be partly due to model overestimation of orbital debris flux and underestimation of larger micrometeoroid numbers. This article is part of the theme issue 'Dust in the Solar System and beyond'.

Sulfide mediated zero valent iron for enhanced nickel removal under neutral condition: Reaction kinetic, mechanism, and stability

The application of sodium sulfide (Na2S) as sulfidation reagent of zero valent iron (ZVI) has been well studied, however, the effect of Na2S existence on ZVI reactivity remains obscure. In this study, Ni(II) removal performance, mechanism, and stability by ZVI with Na2S were investigated at neutral condition. The results showed that Ni(II) removal sharply increased from < 5–100% by ZVI within 60 min with the increase of Na2S concentration, but the subsequent Ni(II) release occurred. In addition to the slight Ni(II) removal by Na2S in aqueous phase, Ni(II) was mainly removed by the adsorption and reduction by Na2S mediated ZVI system. Characterization analysis indicated that Na2S could lead to the severe Fe0 corrosion and the main corrosion product on ZVI was lepidocrocite, which played the dominant role for Ni(II) immobilization. Meanwhile, the formation of iron sulfides on ZVI surface would enhance Ni(II) reduction and partially transform the adsorbed Ni(II) to NiS. Moreover, the higher ionic strength could further enhance the initial Ni(II) removal rate but the stability became poor. Regardless of the additive methods, the Ni(II) removal significantly enhanced in the system of ZVI and Na2S combination. Overall, this work reveals the sulfide mediated Fe0 corrosion and provides a potential method for enhancing the reactivity of ZVI in the treatment of Ni(II) pollution.

Sulfur cycling likely obscures dynamic biologically-driven iron redox cycling in contemporary methane seep environments.

Deep-sea methane seeps are amongst the most biologically productive environments on Earth and are often characterised by stable, low oxygen concentrations and microbial communities that couple the anaerobic oxidation of methane to sulfate reduction or iron reduction in the underlying sediment. At these sites, ferrous iron (Fe2+) can be produced by organoclastic iron reduction, methanotrophic-coupled iron reduction, or through the abiotic reduction by sulfide produced by the abundant sulfate-reducing bacteria at these sites. The prevalence of Fe2+in the anoxic sediments, as well as the availability of oxygen in the overlying water, suggests that seeps could also harbour communities of iron-oxidising microbes. However, it is unclear to what extent Fe2+ remains bioavailable and in solution given that the abiotic reaction between sulfide and ferrous iron is often assumed to scavenge all ferrous iron as insoluble iron sulfides and pyrite. Accordingly, we searched the sea floor at methane seeps along the Cascadia Margin for microaerobic, neutrophilic iron-oxidising bacteria, operating under the reasoning that if iron-oxidising bacteria could be isolated from these environments, it could indicate that porewater Fe2+ can persist is long enough for biology to outcompete pyritisation. We found that the presence of sulfate in our enrichment media muted any obvious microbially-driven iron oxidation with most iron being precipitated as iron sulfides. Transfer of enrichment cultures to sulfate-depleted media led to dynamic iron redox cycling relative to abiotic controls and sulfate-containing cultures, and demonstrated the capacity for biogenic iron (oxyhydr)oxides from a methane seep-derived community. 16S rRNA analyses revealed that removing sulfate drastically reduced the diversity of enrichment cultures and caused a general shift from a Gammaproteobacteria-domainated ecosystem to one dominated by Rhodobacteraceae (Alphaproteobacteria). Our data suggest that, in most cases, sulfur cycling may restrict the biological "ferrous wheel" in contemporary environments through a combination of the sulfur-adapted sediment-dwelling ecosystems and the abiotic reactions they influence.