Au nanoparticles decorated graphitic carbon nitride nanosheets as a sensitive and selective fluorescence probe for Fe3+ and dichromate ions in aqueous medium.

Graphitic carbon nitride mutated with metal nanoparticles has captivated great interest as an effective fluorescent sensor for the detection of harmful ions present in water. In the present work, bulk-gCN was synthesized using melamine as precursor, and further Au-gCN nanocomposite were fabricated via in-situ direct reduction deposition method. The structural, morphological, compositional, stability and optical properties of bulk gCN and Au-gCN nanocomposite were examined using various scattering and spectroscopic techniques such as HRTEM, XPS, XRD and SEM. The synthesized bulk gCN straggles during selectivity studies with different cations and anions because of its uneven surface morphology, however in Au-gCN gold nanoparticles are uniformly distributed on the gCN sheets which results in its enhanced selectivity over bulk gCN. This leads to the fabrication of an optical sensor for Fe3+ and Cr2O72- ions with limit of detection of 4.62 and 2.77 µM, respectively. The sensing of Fe3+ ions corresponds to the photoinduced electron transfer (PET) mechanism, while the detection of chromate species is associated with an inner filter effect (IFE). The practical applicability of the sensor was also evaluated for different environmental water samples. The high stability, sensitivity, and specificity of Au-gCN nanocomposite make it a potential fluorescent probe for Fe3+ and Cr2O72- ions in water samples.

Influence of tartaric acid on the electron transfer between oxyanions and lepidocrocite.

Iron oxide minerals control the environmental behavior of trace elements. However, the potential effects of electron transfer directions by iron oxides between organic acids and trace elements remain unclear. This study investigates the redox capacity of tartaric acid (TA) with chromate (Cr(Ⅵ)) or arsenate (As(V)) on lepidocrocite (Lep) from the perspective of electron transfer. The results demonstrated the configurations of TA (bidentate binuclear (BB)), As(V) (BB), and Cr(Ⅵ) (BB and protonated monodentate binuclear (HMB)) on Lep. Frontier molecular orbital calculations and X-ray photoelectron spectroscopy (XPS) binding energy shifts further indicated different electron transfer directions between TA and the oxyanions on Lep. The iron of Lep might act as electron acceptors when TA is adsorbed, whereas the iron and oxygen of Lep act as electron donors when As(V) is adsorbed. The iron of Lep might accept electrons from its oxygen and subsequently transfer these electrons to Cr(Ⅵ). Macroscopic validation experiments showed the reduction of Cr(VI), whereas no reduction of As(V). The XPS analysis showed a peak shift, with the possible formation of As-Fe-TA ternary complexes and electron transfer on Lep. These findings indicate that mineral interfacial electron transfer considerably influences the transport and transformation of oxyanions.

Metal-Site Dispersed Zinc-Chromium Oxide Derived from Chromate-Intercalated Layered Hydroxide for Highly Selective Propane Dehydrogenation.

Propane dehydrogenation (PDH) is a crucial approach for propylene production. However, commonly used CrOx-based catalysts have issues including easy sintering at elevated reaction temperatures and relying on high acidity supports. In this work, we develop a strategy, to strongly anchor and isolate active sites against their commonly observed aggregation during reactions, by taking advantage of the net trap effect in chromate intercalated Zn-Cr layered hydroxides as precursors. Furthermore, the intercalated chromate overcomes the collapse of traditional layered hydroxides during their transformation to metal oxide, thus exposing more available active sites. A joint fine modulation including crystal structure, surface acidity, specific surface area, and active sites dispersion is performed on the final mixed metal oxides for propane dehydrogenation. As a result, Zn1Cr2-CrO42--MMO delivers attractive propane conversion (~27%) and propylene selectivity (>90%) as compared to other non-noble-metal-based catalysts.

Evidence of turmeric adulteration with lead chromate across South Asia.

Food adulteration with toxic chemicals is a global public health threat. Lead chromate adulterated spices have been linked with lead poisoning in many countries, from Bangladesh to the United States. This study systematically assessed lead chromate adulteration in turmeric, a spice that is consumed daily across South Asia. Our study focused on four understudied countries that produce >80 % of the world's turmeric and collectively include 1.7 billion people, 22 % of the world's population. Turmeric samples were collected from wholesale and retail bazaars from 23 major cities across India, Pakistan, Sri Lanka, and Nepal between December 2020 and March 2021. Turmeric samples were analyzed for lead and chromium concentrations and maximum child blood lead levels were modeled in regions where samples had detectable lead. A total of 356 turmeric samples were collected, including 180 samples of dried turmeric roots and 176 samples of turmeric powder. In total, 14 % of the samples (n = 51) had detectable lead above 2 µg/g. Turmeric samples with lead levels greater than or equal to 18 µg/g had molar ratios of lead to chromium near 1:1, suggestive of lead chromate adulteration. Turmeric lead levels exceeded 1000 µg/g in Patna (Bihar, India) as well as Karachi and Peshawar (Pakistan), resulting in projected child blood lead levels up to 10 times higher than the CDC's threshold of concern. Given the overwhelmingly elevated lead levels in turmeric from these locations, urgent action is needed to halt the practice of lead chromate addition in the turmeric supply chain.

Sphingobium sp. SJ10-10 encodes a not-yet-reported chromate reductase and the classical Rieske dioxygenases to simultaneously degrade PAH and reduce chromate.

Both polycyclic aromatic hydrocarbons (PAHs) and heavy metals persist in the environment and are toxic to organisms. Their co-occurrence makes any of them difficult to remove during bioremediation and poses challenges to environmental management and public health. Microorganisms capable of effectively degrading PAHs and detoxifying heavy metals concurrently are required to improve the bioremediation process. In this study, we isolated a new strain, Sphingobium sp. SJ10-10, from an abandoned coking plant and demonstrated its capability to simultaneously degrade 92.6 % of 75 mg/L phenanthrene and reduce 90 % of 3.5 mg/L hexavalent chromium [Cr(VI)] within 1.5 days. Strain SJ10-10 encodes Rieske non-heme iron ring-hydroxylating oxygenases (RHOs) to initiate PAH degradation. Additionally, a not-yet-reported protein referred to as Sphingobium chromate reductase (SchR), with low sequence identity to known chromate reductases, was identified to reduce Cr(VI). SchR is distributed across different genera and can be classified into two classes: one from Sphingobium members and the other from non-Sphingobium species. The widespread presence of SchR in those RHO-containing Sphingobium members suggests that they are excellent candidates for bioremediation. In summary, our study demonstrates the simultaneous removal of PAHs and Cr(VI) by strain SJ10-10 and provides valuable insights into microbial strategies for managing complex pollutant mixtures.

A PadR family transcriptional repressor regulates the transcription of chromate efflux transporter in Enterobacter sp. Z1.

Chromium is a prevalent toxic heavy metal, and chromate [Cr(VI)] exhibits high mutagenicity and carcinogenicity. The presence of the Cr(VI) efflux protein ChrA has been identified in strains exhibiting resistance to Cr(VI). Nevertheless, certain strains of bacteria that are resistant to Cr(VI) lack the presence of ChrB, a known regulatory factor. Here, a PadR family transcriptional repressor, ChrN, has been identified as a regulator in the response of Enterobacter sp. Z1(CCTCC NO: M 2019147) to Cr(VI). The chrN gene is cotranscribed with the chrA gene, and the transcriptional expression of this operon is induced by Cr(VI). The binding capacity of the ChrN protein to Cr(VI) was demonstrated by both the tryptophan fluorescence assay and Ni-NTA purification assay. The interaction between ChrN and the chrAN operon promoter was validated by reporter gene assay and electrophoretic mobility shift assay. Mutation of the conserved histidine residues His14 and His50 resulted in loss of ChrN binding with the promoter of the chrAN operon. This observation implies that these residues are crucial for establishing a DNA-binding site. These findings demonstrate that ChrN functions as a transcriptional repressor, modulating the cellular response of strain Z1 to Cr(VI) exposure.

Relationships between blood chromium exposure and liver injury: Exploring the mediating role of systemic inflammation in a chromate-exposed population.

Hexavalent chromium and its compounds are prevalent pollutants, especially in the work environment, pose a significant risk for multisystem toxicity and cancers. While it is known that chromium accumulation in the liver can cause damage, the dose-response relationship between blood chromium (Cr) and liver injury, as well as the possible potential toxic mechanisms involved, remains poorly understood. To address this, we conducted a follow-up study of 590 visits from 305 participants to investigate the associations of blood Cr with biomarkers for liver injury, including serum alanine aminotransferase (ALT), aspartate aminotransferase (AST), total bilirubin (TBIL), and direct bilirubin (DBIL), and to evaluate the mediating effects of systemic inflammation. Platelet (PLT) and the platelet-to-lymphocyte ratio (PLR) were utilized as biomarkers of systemic inflammation. In the linear mixed-effects analyses, each 1-unit increase in blood Cr level was associated with estimated effect percentage increases of 0.82% (0.11%, 1.53%) in TBIL, 1.67% (0.06%, 3.28%) in DBIL, 0.73% (0.04%, 1.43%) in ALT and 2.08% (0.29%, 3.87%) in AST, respectively. Furthermore, PLT mediated 10.04%, 11.35%, and 10.77% increases in TBIL, DBIL, and ALT levels induced by chromate, respectively. In addition, PLR mediated 8.26% and 15.58% of the association between blood Cr and TBIL or ALT. These findings shed light on the mechanisms underlying blood Cr-induced liver injury, which is partly due to worsening systemic inflammation.

Bioreduction of chromate in a syngas-based membrane biofilm reactor.

This study leveraged synthesis gas (syngas), a renewable resource attainable through the gasification of biowaste, to achieve efficient chromate removal from water. To enhance syngas transfer efficiency, a membrane biofilm reactor (MBfR) was employed. Long-term reactor operation showed a stable and high-level chromate removal efficiency > 95%, yielding harmless Cr(III) precipitates, as visualised by scanning electron microscopy and energy dispersive X-ray analysis. Corresponding to the short hydraulic retention time of 0.25 days, a high chromate removal rate of 80 µmol/L/d was attained. In addition to chromate reduction, in situ production of volatile fatty acids (VFAs) by gas fermentation was observed. Three sets of in situ batch tests and two groups of ex situ batch tests jointly unravelled the mechanisms, showing that biological chromate reduction was primarily driven by VFAs produced from in situ syngas fermentation, whereas hydrogen originally present in the syngas played a minor role. 16 S rRNA gene amplicon sequencing has confirmed the enrichment of syngas-fermenting bacteria (such as Sporomusa), who performed in situ gas fermentation leading to the synthesis of VFAs, and organics-utilising bacteria (such as Aquitalea), who utilised VFAs to drive chromate reduction. These findings, combined with batch assays, elucidate the pathways orchestrating synergistic interactions between fermentative microbial cohorts and chromate-reducing microorganisms. The findings facilitate the development of cost-effective strategies for groundwater and drinking water remediation and present an alternative application scenario for syngas.

Growth-dependent cr(VI) reduction by Alteromonas sp. ORB2 under haloalkaline conditions: toxicity, removal mechanism and effect of heavy metals.

Bacterial reduction of hexavalent chromium (VI) to chromium (III) is a sustainable bioremediation approach. However, the Cr(VI) containing wastewaters are often characterized with complex conditions such as high salt, alkaline pH and heavy metals which severely impact the growth and Cr(VI) reduction potential of microorganisms. This study investigated Cr(VI) reduction under complex haloalkaline conditions by an Alteromonas sp. ORB2 isolated from aerobic granular sludge cultivated from the seawater-microbiome. Optimum growth of Alteromonas sp. ORB2 was observed under haloalkaline conditions at 3.5-9.5% NaCl and pH 7-11. The bacterial growth in normal culture conditions (3.5% NaCl; pH 7.6) was not inhibited by 100 mg/l Cr(VI)/ As(V)/ Pb(II), 50 mg/l Cu(II) or 5 mg/l Cd(II). Near complete reduction of 100 mg/l Cr(VI) was achieved within 24 h at 3.5-7.5% NaCl and pH 8-11. Cr(VI) reduction by Alteromonas sp. ORB2 was not inhibited by 100 mg/L As(V), 100 mg/L Pb(II), 50 mg/L Cu(II) or 5 mg/L Cd(II). The bacterial cells grew in the medium with 100 mg/l Cr(VI) contained lower esterase activity and higher reactive oxygen species levels indicating toxicity and oxidative stress. In-spite of toxicity, the cells grew and reduced 100 mg/l Cr(VI) completely within 24 h. Cr(VI) removal from the medium was driven by bacterial reduction to Cr(III) which remained in the complex medium. Cr(VI) reduction was strongly linked to aerobic growth of Alteromonas sp. The Cr(VI) reductase activity of cytosolic protein fraction was pronounced by supplementing with NADPH in vitro assays. This study demonstrated a growth-dependent aerobic Cr(VI) reduction by Alteromonas sp. ORB2 under complex haloalkaline conditions akin to wastewaters.

Prediction of Cr(VI) and As(V) adsorption on goethite using hybrid surface complexation-machine learning model.

This study aimed to develop surface complexation modeling-machine learning (SCM-ML) hybrid model for chromate and arsenate adsorption on goethite. The feasibility of two SCM-ML hybrid modeling approaches was investigated. Firstly, we attempted to utilize ML algorithms and establish the parameter model, to link factors influencing the adsorption amount of oxyanions with optimized surface complexation constants. However, the results revealed the optimized chromate or arsenate surface complexation constants might fall into local extrema, making it unable to establish a reasonable mapping relationship between adsorption conditions and surface complexation constants by ML algorithms. In contrast, species-informed models were successfully obtained, by incorporating the surface species information calculated from the unoptimized SCM with the adsorption condition as input features. Compared with the optimized SCM, the species-informed model could make more accurate predictions on pH edges, isotherms, and kinetic data for various input conditions (for chromate: root mean square error (RMSE) on test set = 5.90 %; for arsenate: RMSE on test set = 4.84 %). Furthermore, the utilization of the interpretable formula based on Local Interpretable Model-Agnostic Explanations (LIME) enabled the species-informed model to provide surface species information like SCM. The species-informed SCM-ML hybrid modeling method proposed in this study has great practicality and application potential, and is expected to become a new paradigm in surface adsorption model.

Unraveling the crucial contribution of additive chromate to efficient and stable alkaline seawater oxidation on Ni-based layered double hydroxides.

Seawater electrolysis to generate hydrogen offers a clean, green, and sustainable solution for new energy. However, the catalytic activity and durability of anodic catalysts are plagued by the corrosion and competitive oxidation reactions of chloride in high concentrations. In this study, we find that the additive CrO42- anions in the electrolyte can not only promote the formation and stabilization of the metal oxyhydroxide active phase but also greatly mitigate the adverse effect of Cl- on the anode. Linear sweep voltammetry, accelerated corrosion experiments, corrosion polarization curves, and charge transfer resistance results indicate that the addition of CrO42- distinctly improves oxygen evolution reaction (OER) kinetics and corrosion resistance in alkaline seawater electrolytes. Especially, the introduction of CrO42- even in the highly concentrated NaCl (2.5 M) electrolyte prolongs the durability of NiFe-LDH to almost five times the case without CrO42-. Density functional theory calculations also reveal that the adsorption of CrO42- can tune the electronic configuration of active sites of metal oxyhydroxides, enhance conductivity, and optimize the intermediate adsorption energies. This anionic additive strategy can give a better enlightenment for the development of efficient and stable oxygen evolution reactions for seawater electrolysis.

Efficient nitrate and Cr(VI) removal by denitrifier: The mechanism of S. oneidensis MR-1 promoting electron production, transportation and consumption.

When Cr(VI) and nitrate coexist, the efficiency of both bio-denitrification and Cr(VI) bio-reduction is poor because chromate hinders bacterial normal functions (i.e., electron production, transportation and consumption). Moreover, under anaerobic condition, the method about efficient nitrate and Cr(VI) removal remained unclear. In this paper, the addition of Shewanella oneidensis MR-1 to promote the electron production, transportation and consumption of denitrifier and cause an increase in the removal of nitrate and Cr(VI). The efficiency of nitrate and Cr(VI) removal accomplished by P. denitrificans as a used model denitrifier increased respectively from 51.3% to 96.1% and 34.3% to 99.8% after S. oneidensis MR-1 addition. The mechanism investigations revealed that P. denitrificans provided S. oneidensis MR-1 with lactate, which was utilized to secreted riboflavin and phenazine by S. oneidensis MR-1. The riboflavin served as coenzymes of cellular reductants (i.e., thioredoxin and glutathione) in P. denitrificans, which created favorable intracellular microenvironment conditions for electron generation. Meanwhile, phenazine promoted biofilm formation, which increased the adsorption of Cr(VI) on the cell surface and accelerated the Cr(VI) reduction by membrane bound chromate reductases thereby reducing damage to other enzymes respectively. Overall, this strategy reduced the negative effect of chromate, thus improved the generation, transportation, and consumption of electrons. SYNOPSIS: The presence of S. oneidensis MR-1 facilitated nitrate and Cr(VI) removal by P. denitrificans through decreasing the negative effect of chromate due to the metabolites' secretion.

Microbial innovations in chromium remediation: mechanistic insights and diverse applications.

The ubiquity of hexavalent chromium (Cr(VI)) from industrial activities poses a critical environmental threat due to its persistence, toxicity and mutagenic potential. Traditional physico-chemical methods for its removal often entail significant environmental drawbacks. Recent advancements in remediation strategies have emphasized nano and bioremediation techniques as promising avenues for cost-effective and efficient Cr(VI) mitigation. Bioremediation harnesses the capabilities of biological agents like microorganisms, and algae to mitigate heavy metal contamination, while nano-remediation employs nanoparticles for adsorption purposes. Various microorganisms, including E. coli, Byssochlamys sp., Pannonibacter phragmitetus, Bacillus, Aspergillus, Trichoderma, Fusarium, and Chlorella utilize bioreduction, biotransformation, biosorption and bioaccumulation mechanisms to convert Cr(VI) to Cr(III). Their adaptability to different environments and integration with nanomaterials enhance microbial activity, offering eco-friendly solutions. The study provides a brief overview of metabolic pathways involved in Cr(VI) bioreduction facilitated by diverse microbial species. Nitroreductase and chromate reductase enzymes play key roles in nitrogen and chromium removal, with nitroreductase requiring nitrate and NADPH/NADH, while the chromium reductase pathway relies solely on NADPH/NADH. This review investigates the various anthropogenic activities contributing to Cr(VI) emissions and evaluates the efficacy of conventional, nano-remediation, and bioremediation approaches in curbing Cr(VI) concentrations. Additionally, it scrutinizes the mechanisms underlying nano-remediation techniques for a deeper understanding of the remediation process. It identifies research gaps and offers insights into future directions aimed at enhancing the real-time applicability of bioremediation methods for mitigating with Cr(VI) pollution and pave the way for sustainable remediation solutions.

Simultaneous adsorption of chromate and arsenate onto ferrihydrite/alginate composite beads: Competition and mechanism.

Ferrihydrite is an effective adsorbent of chromate and arsenate. In order to gain insight into the application of ferrihydrite in water treatment, macroporous alginate/ferrihydrite beads, synthesized using two different methods (internal and encapsulation processes), were used in this work. The properties of the ferrihydrite were assessed using various techniques, including X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) theory, and zetametry. The results showed that the specific surface area of the ferrihydrite was 242 m2/g, and the PZC was pH8. The kinetic and isotherm adsorption properties of the ferrihydrite were evaluated in this study. The results indicate that the pseudo second-order and Freundlich models accurately describe the kinetic and isotherm adsorption properties of chromates and arsenates. For chromate removal, ferrihydrite exhibited a relatively high adsorption capacity (40.7 mgCr/g) compared to other adsorbents. However, the arsenate adsorption capacity of MFHB-SI (140.8 mgAs/g) was shown to be the most optimal. The internal synthesis process was suitable for arsenate retention due to the resulting arsenate precipitation. The competitive adsorption analyses indicated that the presence of chromate does not limit the adsorption of arsenate. However, the presence of arsenate almost completely inhibits the adsorption of chromate when the arsenate concentration is above 50 mg/L, due to the precipitation reaction of arsenate.

Reductions in spice lead levels in the republic of Georgia: 2020-2022.

Spice adulteration using yellow lead chromate-based pigments has been documented as a growing global health concern. Spices from the Republic of Georgia with extremely high levels of lead, up to an order of magnitude higher than any other spices worldwide, have been implicated as sources of child lead poisoning. The objectives of this study were to 1) evaluate lead concentrations in spices sampled across the country of Georgia between 2020 and 2022, and 2) assess factors associated with spice adulteration, specifically the role of spice quality and regulatory enforcement. Spice samples were collected from 29 cities nationwide. The most populous cities were selected in each administrative region as well as those of importance to the spice supply chain. Sampling was carried out at the largest spice bazaars in each city. The regions of Adjara and Imereti were the focus of qualitative interviews conducted in 2021 with key businesspeople selling spices with very high and low levels of lead. The same cities and bazaars were visited at each of three sampling periods between 2020 and 2022. In total, 765 spice samples were collected. Lead concentrations in spices decreased over time, with a maximum of 14,233 µg/g in 2020 down to 36 µg/g in the final sampling round of 2022. A logistic regression determined that sampling round, region and spice type were associated with elevated lead in samples. Samples from Adjara and those containing marigold had the highest lead levels. Interviews with eighteen prominent spice vendors revealed difficulties sourcing sufficient quantities of high quality, brightly colored marigold, and concerns about adulteration. Interviews with two authorities from the National Food Authority highlighted the increased attention on regulating lead in spices since 2018. Continued monitoring and periodic regulatory enforcement may adequately disincentivize further adulteration with lead chromate in the spice industry in Georgia.

In-situ reactivation and reuse of micronsized sulfidated zero-valent iron using SRB-enriched culture: A sustainable PRB technology.

Sulfidated zero-valent iron (S-ZVI) is an attractive material of permeable reactive barriers (PRBs) for the remediation of contaminated groundwater. However, S-ZVI is prone to be passivated due to the oxidation of reactive and conductive iron sulfide (FeSx) shell and the formation of inactive and non-conductive ferric (hydr)oxides, which serve as electron transfer barriers to hinder the electron flow from Fe° core to contaminants. This study thus proposed a novel approach for in-situ reactivation and reuse of micronsized S-ZVI (S-mZVI) in PRB using sulfate-reducing bacteria (SRB) enriched culture to realize long-lasting remediation of Cr(VI)-contaminated groundwater. S-mZVI were passivated after reactions with Cr(VI) due to the formation of electron transfer barriers (mainly inactive and non-conductive Fe(III) (hyd)oxides, which increased the polarization resistance from 16.38 to 27.38 kΩ cm2 and hindered the electron transfer from the Fe° core. Interestingly, the passivated S-mZVI was efficiently reactivated by providing the SRB-enriched culture and organic carbon within 12 h, and the Cr(VI) removal capacity of S-mZVI in the three use cycles increased to 37.4 mg Cr/g, which was 2.1 times higher than that of the virgin S-mZVI. After biological reactivation, the Rp of reactivated S-mZVI decreased to 12.30 kΩ cm2. SRB-mediated reactivation removed the electron transfer barriers via biotic and abiotic reduction of Fe(III) (hyd)oxides. Especially, the microbial Fe(III) reduction mediated by FmnA-dmkA-fmnB-pplA-ndh2-eetAB-dmkB protein family enhanced the Fe2+ release from the surface and the subsequent re-formation of reactive and conductive FeSx shell. A long-term PRB column test further demonstrated the feasibility of in-situ biological reactivation and reuse of S-mZVI for enhanced Cr(VI)-contaminated groundwater remediation. Within 64 days, the Cr(VI) removal capacity of S-mZVI in the four use cycles increased by 3.2 times, compared to the virgin one. The bio-reactivation using the SRB-enriched culture and sulfate locally-available in groundwater will reduce the chemical and maintenance costs associated with the frequent replacement of reactive ZVI-based materials. The PRB technology based on the bio-renewable S-mZVI can be a sustainable alternative to the conventional PRBs for the long-lasting and low-cost remediation of groundwater contaminated by oxidative pollutants.

Unveiling the inhibitory mechanisms of chromium exposure on microbial reductive dechlorination: Kinetics and microbial responses.

Chromium and organochlorine solvents, particularly trichloroethene (TCE), are pervasive co-existing contaminants in subsurface aquifers due to their extensive industrial use and improper disposal practices. In this study, we investigated the microbial dechlorination kinetics under different TCE-Cr(Ⅲ/VI) composite pollution conditions and elucidated microbial response mechanisms based on community shift patterns and metagenomic analysis. Our results revealed that the reductive dechlorinating consortium had high resistance to Cr(III) but extreme sensitivity to Cr(VI) disturbance, resulting in a persistent inhibitory effect on subsequent dechlorination. Interestingly, the vinyl chloride-respiring organohalide-respiring bacteria (OHRB) was notably more susceptible to Cr(III/VI) exposure than the trichloroethene-respiring one, possibly due to inferior competition for growth substrates, such as electron donors. In terms of synergistic non-OHRB populations, Cr(III/VI) exposure had limited impacts on lactate fermentation but significantly interfered with H2-producing acetogenesis, leading to inhibited microbial dechlorination due to electron donor deficiencies. However, this inhibition can be effectively mitigated by the amendment of exogenous H2 supply. Furthermore, being the predominant OHRB, Dehalococcoides have inherent Cr(VI) resistance defects and collaborate with synergistic non-OHRB populations to achieve concurrent bio-detoxication of Cr(VI) and TCE. Our findings expand the understanding of the response patterns of different functional populations towards Cr(III/VI) stress, and provide valuable insights for the development of in situ bioremediation strategies for sites co-contaminated with chloroethene and chromium.

Forming a chromium-based interstrand DNA crosslink: Implications for carcinogenicity.

The reduction of the carcinogen chromate has been proposed to lead to three Cr(III)-containing DNA lesions: binary adducts (Cr(III) and DNA), interstrand crosslinks, and ternary adducts (Cr(III) linking DNA to a small molecule or protein). Although the structures of binary adducts have recently been elucidated, the structures of interstrand crosslinks and ternary adducts are not known. Analysis of Cr(III) binding to an oligonucleotide duplex containing a 5'-CG site allows elucidation of the structure of an oxide- or hydroxide-bridged binuclear Cr(III) assembly bridging the two strands of DNA. One Cr(III) is directly coordinated by the N-7 atom of a guanine residue, and the complex straddles the helix to form a hydrogen bond between another guanine residue and a Cr(III)-bound aquo ligand. No involvement of the phosphate backbone was observed. The properties and stability of this Cr-O(H)-Cr-bridged complex differ significantly from those reported for Cr-induced interstrand crosslinks, suggesting that interstrand crosslinks resulting from chromate reduction may be organic in nature.

Docking assisted mechanistic elucidation of bio conversion of hexavalent chromium by Serratia marcescens AJRR-22 that is effective yet long term sustainable in bio-geosphere.

Environmental accumulation of hexavalent chromium [Cr(VI)] in the food chain can induce detrimental effects on plants and animals, which calls for effective remediation strategies using biological entities. The bacterium isolated from an iron mine in Odisha, India, is identified asSerratia marcescensAJRR-22. This multi-metal tolerant strain is capable of bio-converting up to 350 mg/L Cr(VI) within 72 h of incubation. Observable electron dense precipitates in transmission electron microscopic images, data patterns in fluorescence microscopy and flow cytometry clearly reveal the chromate reduction ability of the strain. The molecular study is depicted by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopic analyses. Furthermore, a simulation study to estimate the interactions of chromium bound flavin reductasewith predicted docked complexes suggests significant negative Gibbs free energy and a low inhibition constant (Ki), signifying strong spontaneous binding of Cr(VI) to the enzyme, which makes the strain an efficient candidate for chromium bioremediation.

Reduction and precipitation of chromium(VI) using a palladized membrane biofilm reactor.

H2-driven reduction of hexavalent chromium (Cr(VI)) using precious-metal catalysts is promising, but its implementation in water treatment has been restricted by poor H2-transfer efficiency and high catalyst loss. We investigated the reduction of Cr(VI) through hydrogenation catalyzed by elemental-palladium nanoparticles (PdNPs) generated in-situ within biofilm of a membrane biofilm reactor (MBfR), creating a Pd-MBfR. Experiments were conducted using a Pd-MBfR and a non-Pd MBfR. The Pd-MBfR achieved Cr(VI) (1000 µg L-1) reduction of >99 % and reduced the concentration of total Cr to below 50 µg L-1, much lower than the total Cr concentration in the non-Pd MBfR effluent (290 µg L-1). The Pd-MBfR also had a lower concentration of dissolved organic compounds compared to the non-Pd MBfR, which minimized the formation of soluble organo-Cr(III) complexes and promoted precipitation of Cr(OH)3. Solid-state characterizations documented deposition of Cr(OH)3 as the product of Cr(VI) reduction in the Pd-MBfR. Metagenomic analyses revealed that the addition and reduction of Cr(VI) had minimal impact on the microbial community (dominated by Dechloromonas) and functional genes in the biofilm of the Pd-MBfR, since the PdNP-catalyzed reduction process was rapid. This study documented efficient Cr(VI) reduction and precipitation of Cr(OH)3 by the Pd-MBfR technology.