Insight into the crystal facet-dependent Cr(VI) reduction: A comparative study of pyrite {100} and {111} facets.

The migration and transformation of hexavalent chromium (Cr(VI)) in the environment are regulated by pyrite (FeS2). However, variations in pyrite crystal facets influence the adsorption behavior and electron transfer between pyrite and Cr(VI), thereby impacting the Cr(VI) reduction performance. Herein, two naturally common facets of pyrite were synthesized hydrothermally to investigate the facet-dependent mechanisms of Cr(VI) reduction. The experimental results revealed that the {111} facet exhibited approximately 1.30-1.50 times higher efficiency in Cr(VI) reduction compared to the {100} facet. Surface analyses and electrochemical results indicated that {111} facet displayed a higher iron-sulfur oxidation level, which was affected by its superior electrochemical properties during the reaction with Cr(VI). Density functional theory (DFT) calculations demonstrated that the narrower band gap and lower work function on {111} facet were more favorable for the electron transfer between Fe(II) and Cr(VI). Furthermore, different adsorption configurations were observed on {100} and {111} surfaces due to the unique arrangements of Fe and S atoms. Specifically, O atoms in Cr2O72- directly bound with the S sites on {100} but the Fe sites on {111}. According to the density of states (DOS), the Fe site had better reactivity than the S site in the reaction, which appeared to be related to the fracture of S-S bonds. Additionally, the adsorption configuration of Cr2O72- on {111} surface showed a stronger adsorption energy and a more stable coordination mode, favoring subsequent Cr(VI) reduction process. These findings provide an in-depth analysis of facet-dependent mechanisms underlying Cr(VI) reduction behavior, offering new insights into studying environmental interactions between heavy metals and natural minerals.

Synergistic promotion of antimony transformation in the interaction of Acidithiobacillus ferrooxidans and pyrite by driving the formation of reactive oxygen species and secondary minerals.

As one of the important microorganisms in the mining area, the role of iron-sulfur oxidizing microorganisms in antimony (element symbolized as Sb) migration and transformation in mining environments has been largely neglected for a long time. Therefore, the processes of the typical iron-sulfur oxidizing bacterium Acidithiobacillus ferrooxidans (A. ferrooxidans) and pyrite interaction coupled with the migration and transformation of Sb were investigated in this paper. The bio-oxidation process of pyrite by A. ferrooxidans not only accelerates the oxidation rate of Sb(III) to Sb(V) (62.93% of 10 mg L-1 within 4 h), but also promotes the adsorption and precipitation of Sb (32.89 % of 10 mg L-1 within 96 h), and changes in the dosage of minerals, Sb concentration, and pH value affect the conversion of Sb. The characterization results show that the interaction between A. ferrooxidans and pyrite produces a variety of reactive species, such as H2O2 and •OH, resulting in the oxidation of Sb(III). In addition, A. ferrooxidans mediates the formation of stereotyped iron-sulfur secondary minerals that can act as a major driver of Sb (especially Sb(V)) adsorption or co-precipitation. This study contributes to the further understanding of the diversified biogeochemical processes of iron-sulfur oxidizing bacteria-iron-sulfur minerals-toxic metals in mining environments and provides ideas for the development of in-situ treatment technologies for Sb.

Geochip 5.0 insights into the association between bioleaching of heavy metals from contaminated sediment and functional genes expressed in consortiums.

The heavy metal contamination in river and lake sediments endangers aquatic ecosystems. Herein, the feasibility of applying different exogenous mesophile consortiums in bioleaching multiple heavy metal-contaminated sediments from Xiangjiang River was investigated, and a comprehensive functional gene array (GeoChip 5.0) was used to analyze the functional gene expression to reveal the intrinsic association between metal solubilization efficiency and consortium structure. Among four consortiums, the Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans consortium had the highest solubilization efficiencies of Cu, Pb, Zn, and Cd after 15 days, reaching 50.33, 29.93, 47.49, and 79.65%, while Cu, Pb, and Hg had the highest solubilization efficiencies after 30 days, reaching 63.67, 45.33, and 52.07%. Geochip analysis revealed that 31,346 genes involved in different biogeochemical processes had been detected, and the systems of 15 days had lower proportions of unique genes than those of 30 days. Samples from the same stage had more genes overlapping with each other than those from different stages. Plentiful metal-resistant and organic remediation genes were also detected, which means the metal detoxification and organic pollutant degradation had happened with the bioleaching process. The Mantel test revealed that Pb, Zn, As, Cd, and Hg solubilized from sediment influenced the structure of expressed microbial functional genes during bioleaching. This work employed GeoChip to demonstrate the intrinsic association between functional gene expression of mesophile consortiums and the bioleaching efficiency of heavy metal-contaminated sediment, and it provides a good reference for future microbial consortium design and remediation of river and lake sediments.

Bioinspired axial S-coordinated single-atom cobalt catalyst to efficient activate peroxymonosulfate for selective high-valent Co-Oxo species generation.

The efficient activation and selective high-valent metal-oxo (HVMO) species generation remain challenging for peroxymonosulfate (PMS)-based advanced oxidation processes (PMS-AOPs) in water purification. The underlying mechanism of the activation pathway is ambiguous, leading to a massive dilemma in the control and regulation of HVMO species generation. Herein, bioinspired by the bio-oxidase structure of cytochrome P450, the axial coordination strategy was adopted to tailor a single-atom cobalt catalyst (CoN4S-CB) with an axial S coordination. CoN4S-CB high-selectively generated high-valent Co-Oxo species (Co(IV)=O) via PMS activation. Co(IV)=O demonstrated an ingenious oxygen atom transfer (OAT) reaction to achieve the efficient degradation of sulfamethoxazole (SMX), and this allowed robust operation in various complex environments. The axial S coordination modulated the 3d orbital electron distribution of the Co atom. Density functional theory (DFT) calculation revealed that the axial S coordination decreased the energy barrier for PMS desorption and lowered the free energy change (ΔG) for Co(IV)=O generation. CoN4S-PMS* had a narrow d-band close to the Fermi level, which enhanced charge transfer to accelerate the cleavage of O-O and O-H bonds in PMS. This work provides a broader perspective on the activator design with natural enzyme structure-like active sites to efficient activate PMS for selective HVMO species generation.

Biogenic carbon encapsulated iron oxides mediated oxalic acid for Cr(VI) reduction in aqueous: Efficient performance, electron transfer and radical mechanisms.

Carbonaceous materials have a potential to mediated oxalic acid (OA) for Cr(VI) reduction, but the rational modification is needed for boosting the mediation of electron transfer. Herein, we utilized polyvinyl alcohol to envelop schwertmannite synthesized by Acidithiobacillus ferrooxidans biomineralization, and pyrolyzed them to obtain the carbon encapsulated iron oxides (C-2.0-Sch-PVA). SEM and TEM results demonstrated that a moderate calcination temperature would yield a neural network-like carbon encapsulated structure. C-2.0-Sch-PVA efficiently mediated OA to reduce Cr(VI), 98.4% of Cr(VI) (40 mg L-1) was reduced with 0.75 g L-1 C-2.0-Sch-PVA and 4 mM OA in 60 min. It still performed excellent results in a wide pH range, multiple anions and different water matrixes. The carbon encapsulated structure as electron shuttle mediated the electron transfer, and the O-moieties on its surface were a premise for initiating the Cr(VI) reduction process. The electron transfer from the inner iron oxides to the conjugated structure of the outer carbon shells facilitated Cr(VI) reduction as well. Moreover, OA raised the persistent free radicals' level in C-2.0-Sch-PVA as another important pathway for Cr(VI) reduction. Overall, C-2.0-Sch-PVA provides an excellent demonstration in the carbonaceous materials modification for mediating OA to reduce Cr(VI) in aqueous.

Enhancing Cr(VI) bio-reduction by conductive materials and enrichment of functional microbes under anaerobic conditions.

A few studies reported the impact of mineral conductivity properties on contaminant-mineral-microbe interactions and microbial community structure changes in the interaction process. To fill the gap, conductive minerals (magnetite/hematite) and an insulative mineral (quartz) were introduced into Cr(VI) reduction systems to investigate the effect of mineral conductivity properties on Cr(VI) removal. Results showed that conductive minerals enhanced Cr(VI) reduction rate as compared to insulative minerals. Higher reduction percentage (>86%) was observed when both ERB (extracellular respiratory bacteria) and conductive minerals were presence than those with only minerals (<10%) or ERB (<55%), indicating a synergistic effect existed in this bio-remediation system. Moreover, surface elements detection manifested higher Fe-containing groups and Fe(III)-Cr(III) complexes covered on conductive minerals surface when ERB was present. Electrochemical data suggested that ERB facilitated the activity of electron transference on the surface of conductive minerals. Our results indicated that conductive minerals did act as an "electron shuttle" while insulative minerals increased adsorption sites to accelerate Cr(VI) reduction. 16S rRNA sequences results demonstrated that conductive minerals changed the microbial community structure and increased the diversity of the functional microbes including Pseudomonas spp. and Exiguobacterium spp. This work is of deep significance for better understanding the process of elements biogeochemical and elimination of pollutants.

An efficient, economical, and easy mass production biochar supported zero-valent iron composite derived from direct-reduction natural goethite for Cu(II) and Cr(VI) remove.

In this study, a novel biochar-supported zero-valent iron (ZVI) composite was synthesised by a one-pot co-pyrolysis reduction method, and was used to remove Cu(II) and Cr(VI). The raw materials for the composite were derived from natural bagasse/straw and goethite. Scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, Fourier-transform infrared (FTIR) spectroscopy, thermogravimetry (TG), and Brunauer-Emmett-Teller (BET) analysis were used to characterise the biochar and biochar-supported ZVI composites. Batch removal experiments on the effects of the initial pH and citric acid concentrations were performed as well as kinetic studies and isotherm experiments. The composite materials showed better Cu(II) and Cr(VI) removal performance than single biochar and mineral. The removal of Cu(II) and Cr(VI) is pH-dependent, and proceeds via heterogeneous multilayer chemisorption. Electrochemical analysis revealed that straw biochar-supported ZVI composite exhibited greater electrical conductivity and electron transfer rate than pure biochar and ZVI. FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS) elucidated the uptake mechanism, showing that Cu(II) and Cr(VI) were easily adsorbed onto the biochar surface and were then reduced by ZVI. These results indicate that biochar-supported ZVI composite is effective for heavy metal remediation, which is economical, environment-friendly, and suitable for mass production.

Development of a hydroxyl group-mediated biosynthetic schwertmannite as a persulfate activator for efficient degradation of RhB and Cr(VI) removal.

Recently, sulfate radical-based advanced oxidation processes (SR-AOPs) have shown broad potential for restoring the water environment. However, the application of SR-AOPs to simultaneously remove organic pollutants and Cr(VI) has rarely been reported. Herein, we developed a modified schwertmannite (Sch-PVA) synthesized via the mediation of Acidithiobacillus ferrooxidans in the introduction of polyvinyl alcohol (PVA). This modification significantly changed the morphology and structure of the schwertmannite (Sch). The specific surface area and the density of functional sites also increased. Sch-PVA significantly increased the persulfate (PDS) activation efficiency. Even in 100 mg L-1 rhodamine B (RhB) conditions, 96.3% of RhB was eliminated by 0.5 g L-1Sch-PVA and 6 mM PDS in 120 min. Moreover, excellent performance was exhibited over a wide pH range. The dissolution of the passivation layer facilitated the exposure of new adsorption and reduction sites, thereby enhancing the simultaneous removal of RhB and Cr(VI). Quenching experiments and electron spin resonance (ESR) measurements verified that sulfate and hydroxyl radicals were generated. The hydroxyl groups on the Sch-PVA surface played a key role in the bonding with and the activation of PDS. In conclusion, Sch-PVA provides new insights into the catalyst application for simultaneous removal of organic pollutants and Cr(VI).

Hexavalent chromium remediation based on the synergistic effect between chemoautotrophic bacteria and sulfide minerals.

Hexavalent chromium (Cr(VI)) is an environmental concern due to the carcinogenic and mutagenic effect on living organisms. Sulfide minerals based Cr(VI) reduction is an economical and efficient strategy for Cr(VI) remediation. In this study, Cr(VI) reduction through the synergistic effect between chemoautotrophic bacteria and sulfide mineral is systematically investigated. Sulfide minerals dissolution and Cr(VI) reduction performance highly depends on mineral acid soluble property. Cr(VI) reduction capacity of pyrrhotite, pyrite, marcasite and sphalerite was 50, 104, 104 and 44 mg/g (Cr(VI)/mineral) respectively in the biotic system. Acidithiobacillus ferrooxidans (A. ferrooxidans) significantly enhanced pyrite and marcasite based Cr(VI) reduction kinetic and capacity. Proton consumption, iron coprecipitation and the biological activity deficiency in the abiotic system significantly inhibited Cr(VI) reduction. Elemental sulfur and secondary iron mineral as the main composition of the passivation layer inhibited sustainable Cr(VI) reduction. A. ferrooxidans facilitated acid nonsoluble mineral dissolution and surface passivation layer removal, and promoted Cr(VI) reduction. Acid nonsoluble sulfide mineral disulfide bond rapture, S°/Sn2- oxidization, and Fe(III)/Cr(III) dissolution were accelerated by A. ferrooxidans, which facilitated Cr(VI) reduction reactive sites regeneration. Our study demonstrated that chemoautotrophic bacterial accelerated Cr(VI) reduction reaction through promoting acid nonsoluble sulfide mineral dissolution. This research is of environmental and practical significance to remediate redox sensitive contaminant based on the synergistic effect between sulfide minerals and chemoautotrophic A. ferrooxidans.