Speciation-specific chromium bioaccumulation and detoxification in fish using hydrogel microencapsulated biogenic nanosilver and zeolite synergizing with biomarkers.

Grass carp intestinal waste-mediated biosynthesized nanosilver (AgNPs) was valorized using guaran and zeolite matrices, resulting in AgNPs-guaran, AgNPs-zeolite, and AgNPs-guaran -zeolite composites. The valorized products were examined using Environmental Scanning Electron Microscopy, Energy Dispersive X-ray analysis and X-ray Diffraction analysis to confirm uniform dispersion and entrapment of AgNPs within the matrixes. These valorized products were evaluated for their efficacy in detoxifying the ubiquitous and toxic hexavalent chromium (Cr6+) in aquatic environments, with Anabas testudineus exposed to 2 mg l-1 of Cr6+ for 60 days. Remarkable reduction of Cr6+ concentration to 0.86 ± 0.007 mg l-1 was achieved with AgNPs-guaran-zeolite composite, indicating successful reclamation of contaminated water and food safety assurance. Consistency in results was further corroborated by minimal stress-related alterations in fish physiological parameters and integrated biomarker response within the experimental group treated with the AgNPs-guaran-zeolite composite. Despite observed chromium accumulation in fish tissues, evidence of physiological stability was apparent, potentially attributable to trivalent chromium accumulation, serving as an essential nutrient for the fish. Additionally, the challenge study involving Anabas testudineus exposed to Aeromonas hydrophila exhibited the lowest cumulative mortality (11.11%) and highest survival rate (87.5%) within the same experimental group. The current study presents a novel approach encompassing the valorization of AgNPs for Cr6+ detoxification under neutral to alkaline pH conditions, offering a comprehensive framework for environmental remediation.

A critical review of MXene-based composites in the adsorptive and photocatalysis of hexavalent chromium removal from industrial wastewater.

The growing concern of water pollution is a critical issue stemming from industrialization and urbanization. One of the specific concerns within this broader problem is the toxicity associated with chromium (Cr), especially in its Cr (VI) form. Transition metal carbides/nitrides (MXenes) are attractive materials for the treatment of water due to their unique properties such as layered structure, high surface area, conductivity, flexibility, scalable manufacture, and surface functions. Adsorption and photocatalysis reactions are the two promising methods for the removal of Cr (VI) by using MXenes. Still, most of the previous reviews were limited to the single application area. Hence, this review covers recent developments in MXene-based composites, highlighting their dual role as both adsorbents and photocatalysts in the removal of Cr (VI). MXene-based composites are found to be effective in both adsorption and photodegradation of Cr (VI). Most MXene-based composites have demonstrated exceptional removal efficiency for Cr (VI), achieving impressive adsorption capacities ranging from 100 to 1500 mg/g and degradation percentages between 80% and 100% in a relatively short period. The active functional groups present on the surface of MXene have a viable impact on the adsorption and photodegradation performance. The mechanism of Cr (VI) removal is explained, with MXenes playing a key role in electrostatic attraction for adsorption and as co-catalysts in photocatalysis. However, MXene-based composites have limitations such as instability, competition with co-existing ions, and regeneration challenges. Further research is needed to address these limitations. Additionally, MXene-based composites hold promise for addressing water contamination, heavy metal removal, hydrogen production, energy storage, gas sensing, and biomedical applications.

A novel HMGA2/MPC-1/mTOR signaling pathway promotes cell growth via facilitating Cr (VI)-induced glycolysis.

Mitochondrial Pyruvate Carrier 1 (MPC1) is localized on mitochondrial outer membrane to mediate the transport of pyruvate from cytosol to mitochondria. It is also well known to act as a tumor suppressor. Hexavalent chromium (Cr (VI)) contamination poses a global challenge due to its high toxicity and carcinogenesis. This research was intended to probe the potential mechanism of MPC1 in the effect of Cr (VI)-induced carcinogenesis. First, Cr (VI)-treatments decreased the expression of MPC1 in vitro and in vivo. Overexpression of MPC1 inhibited Cr (VI)-induced glycolysis and migration in A549 cells. Then, high mobility group A2 (HMGA2) protein strongly suppressed the transcription of MPC1 by binding to its promoter, and HMGA2/MPC1 axis played an important role in oxidative phosphorylation (OXPHOS), glycolysis and cell migration. Furthermore, endoplasmic reticulum (ER) stress made a great effect on the interaction between HMGA2 and MPC1. Finally, the mammalian target of the rapamycin (mTOR) was determined to mediate MPC1-regulated OXPHOS, aerobic glycolysis and cell migration. Collectively, our data revealed a novel HMGA2/MPC-1/mTOR signaling pathway to promote cell growth via facilitating the metabolism reprogramming from OXPHOS to aerobic glycolysis, which might be a potential therapy for cancers.

Cr (VI)-induced ribosomal DNA copy number variation is associated with semen quality impairment: Evidence from human to animal study.

OBJECTIVES: This study aimed to analyze the possible role of rDNA copy number variation in the association between hexavalent chromium [Cr (VI)] exposure and semen quality in semen donors and further confirm this association in mice. METHODS: In this cross-sectional study, whole blood and semen samples were collected from 155 semen donors in the Zhejiang Human Sperm Bank from January 1st to April 31st, 2021. Adult C57BL/6 J male mice were treated with different doses of Cr (VI) (0, 10, or 15 mg/kg b.w./day). Semen quality, including semen volume, total spermatozoa count, sperm concentration, progressive motility, and total motility, were analyzed according to the WHO laboratory manual. Cr concentration was detected using inductively coupled plasma mass spectrometry. The rDNA copy number was measured using qPCR. RESULTS: In semen donors, whole blood Cr concentration was negatively associated with semen concentration and total sperm counts. Semen 5 S and 45 S rDNA copy numbers were negatively associated with whole blood Cr concentration and whole blood 5.8 S rDNA copy number was negatively associated with semen Cr concentration. In mice, Cr (VI) damaged testicular tissue, decreased semen quality, and caused rDNA copy number variation. Semen quality was related to the rDNA copy number in whole blood, testicular tissue, and semen samples in mice. CONCLUSION: Cr (VI) was associated with decreased semen quality in semen donors and mice. Our findings suggest an in-depth analysis of the role of the rDNA copy number variation in the Cr (VI)-induced impairment of semen quality.

Microbial electrochemical Cr(VI) reduction in a soil continuous flow system.

Microbial electrochemical technologies represent innovative approaches to contaminated soil and groundwater remediation and provide a flexible framework for removing organic and inorganic contaminants by integrating electrochemical and biological techniques. To simulate in situ microbial electrochemical treatment of groundwater plumes, this study investigates Cr(VI) reduction within a bioelectrochemical continuous flow (BECF) system equipped with soil-buried electrodes, comparing it to abiotic and open-circuit controls. Continuous-flow systems were tested with two chromium-contaminated solutions (20-50 mg Cr(VI)/L). Additional nutrients, buffers, or organic substrates were introduced during the tests in the systems. With an initial Cr(VI) concentration of 20 mg/L, 1.00 mg Cr(VI)/(L day) bioelectrochemical removal rate in the BECF system was observed, corresponding to 99.5% removal within nine days. At the end of the test with 50 mg Cr(VI)/L (156 days), the residual Cr(VI) dissolved concentration was two orders of magnitude lower than that in the open circuit control, achieving 99.9% bioelectrochemical removal in the BECF. Bacteria belonging to the orders Solirubrobacteriales, Gaiellales, Bacillales, Gemmatimonadales, and Propionibacteriales characterized the bacterial communities identified in soil samples; differently, Burkholderiales, Mycobacteriales, Cytophagales, Rhizobiales, and Caulobacterales characterized the planktonic bacterial communities. The complexity of the microbial community structure suggests the involvement of different microorganisms and strategies in the bioelectrochemical removal of chromium. In the absence of organic carbon, microbial electrochemical removal of hexavalent chromium was found to be the most efficient way to remove Cr(VI), and it may represent an innovative and sustainable approach for soil and groundwater remediation. Integr Environ Assess Manag 2024;00:1-17. © 2024 The Author(s). Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Circulating lung-cancer-related non-coding RNAs are associated with occupational exposure to hexavalent chromium - A cross-sectional study within the SafeChrom project.

BACKGROUND: Hexavalent chromium (Cr(Ⅵ)) is classified as a group 1 human carcinogen and increases the risk of lung cancer. Non-coding RNAs (ncRNAs) have key regulatory roles in lung cancer, but less is known about their relation to Cr(Ⅵ) exposure. OBJECTIVES: We aimed to 1) measure the expression of lung cancer-related circulating ncRNAs in exposed workers and controls; 2) assess associations between ncRNAs expression and Cr concentrations in red blood cells (RBC) and urine; and 3) evaluate correlations between the ncRNAs. METHODS: The study included 111 Cr(VI) exposed workers and 72 controls recruited from the SafeChrom project. Cr concentrations were measured in RBC (biomarker of long-term exposure) and urine (biomarker of short-term exposure) samples. Long ncRNA (lncRNA) and microRNA (miRNA) were extracted from plasma followed by deoxyribonuclease treatment, complementary DNA synthesis, and quantitative real-time polymerase chain reaction using target-specific assays for three lncRNAs (H19, MALAT1, NORAD), and four miRNAs (miR-142-3p, miR-15b-5p, miR-3940-5p, miR-451a). RESULTS: Expression levels of lncRNAs MALAT1 and NORAD, and all four miRNAs, were significantly lower in Cr(VI) exposed workers compared with controls, and correlated significantly with RBC-Cr concentrations (rS = -0.16 to -0.38). H19 was non-significantly increased in exposed workers but significantly correlated with miR-142-3p (rS = -0.33) and miR-15b-5p (rS = -0.30), and NORAD was significantly positively correlated with all four miRNAs (rS = 0.17 to 0.46). In multivariate regression models adjusting for confounders, expressions of lncRNAs MALAT1 and NORAD and all miRNAs were still significantly lower in the exposed group compared with controls, and the expression decreased with increasing RBC-Cr concentrations. CONCLUSIONS: Cr(VI) exposure was inversely and in a dose-response manner associated with the expression of circulating non-coding RNA, which suggests ncRNAs as potential biomarkers for Cr(VI)-induced toxicity. Correlations between miRNAs and lncRNAs suggest that they participate in the same lncRNA-miRNA-messenger RNA regulatory axes, which may play important roles in Cr(VI) carcinogenesis.

Acute particulate hexavalent chromium exposure induces DNA double strand breaks and activates homologous recombination repair in rat lung tissue.

Hexavalent chromium [Cr(VI)] is an established human lung carcinogen, but the carcinogenesis mechanism is poorly understood. Chromosome instability, a hallmark of lung cancer, is considered a major driver of Cr(VI)-induced lung cancer. Unrepaired DNA double strand breaks are the underlying cause, and homologous recombination repair is the primary mechanism preventing Cr(VI)-induced DNA breaks from causing chromosome instability. Cell culture studies show acute Cr(VI) exposure causes DNA double strand breaks and increases homologous recombination repair activity. However, the ability of Cr(VI)-induced DNA breaks and repair impact has only been reported in cell culture studies. Therefore, we investigated whether acute Cr(VI) exposure could induce breaks and homologous recombination repair in rat lungs. Male and female Wistar rats were acutely exposed to either zinc chromate particles in a saline solution or saline alone by oropharyngeal aspiration. This exposure route resulted in increased Cr levels in each lobe of the lung. We found Cr(VI) induced DNA double-strand breaks in a concentration-dependent manner, with females being more susceptible than males, and induced homologous recombination repair at similar levels in both sexes. Thus, these data show this driving mechanism discovered in cell culture indeed translates to lung tissue in vivo.

Implementing magnetically-active Sn-based nanocomposites in hexavalent chromium removal from drinking water.

A novel nanocomposite consisting of Fe3O4-loaded tin oxyhydroxy-chloride is demonstrated as an efficient adsorbent for the removal of hexavalent chromium in compliance to the new drinking water regulation. This study introduces a continuous-flow production of the nanocomposite through the separate synthesis of (i) 40 nm Fe3O4 nanoparticles and (ii) multilayered spherical arrangements of a tin hydroxy-chloride identified as abhurite, before the application of a wet-blending process. The homogeneous distribution of Fe3O4 nanoparticles on the abhurite's morphology, features nanocomposite with magnetic response whereas the 10 % loaded nanocomposite preserves a Cr(VI) uptake capacity of 7.2 mg/g for residual concentrations below 25 µg/L. Kinetic and thermodynamic examination of the uptake evolution indicates a relative rapid Cr(VI) capture dominated by interparticle diffusion and a spontaneous endothermic process mediated by reduction to Cr(III). The efficiency of the optimized nanocomposite was validated in a pilot unit operating in a sequence of a stirring reactor and a rotary magnetic separator showing an alternative and competitive application path than typical fixed-bed filtration, which is supported by the absence of any acute cellular toxicity according to human kidney cell viability tests.

Unveiling the Roles of Alloyed Boron in Hexavalent Chromium Removal Using Borohydride-Synthesized Nanoscale Zerovalent Iron: Electron Donor and Antipassivator.

Nanoscale zerovalent iron synthesized using borohydride (B-NZVI) has been widely applied in environmental remediation in recent decades. However, the contribution of boron in enhancing the inherent reactivity of B-NZVI and its effectiveness in removing hexavalent chromium [Cr(VI)] have not been well recognized and quantified. To the best of our knowledge, herein, a core-shell structure of B-NZVI featuring an Fe-B alloy shell beneath the iron oxide shell is demonstrated for the first time. Alloyed boron can reduce H+, contributing to more than 35.6% of H2 generation during acid digestion of B-NZVIs. In addition, alloyed B provides electrons for Fe3+ reduction during Cr(VI) removal, preventing in situ passivation of the reactive particle surface. Meanwhile, the amorphous oxide shell of B-NZVI exhibits an increased defect density, promoting the release of Fe2+ outside the shell to reduce Cr(VI), forming layer-structured precipitates and intense Fe-O bonds. Consequently, the surface-area-normalized capacity and surface reaction rate of B-NZVI are 6.5 and 6.9 times higher than those of crystalline NZVI, respectively. This study reveals the importance of alloyed B in Cr(VI) removal using B-NZVI and presents a comprehensive approach for investigating electron pathways and mechanisms involved in B-NZVIs for contaminant removal.

Modified Ordered Mesoporous Carbons for Cr(VI) Removal from Wastewater.

The pristine CMK-3 carbon was ozonized and then chemically modified by the Zr and Fe compounds. The synthesized carbonaceous materials were characterized with physicochemical methods. The obtained carbons had a high specific surface area (ca. 800 m2 g-1) and an acidic surface. The Cr(VI) adsorption properties of the oxidized and Zr/Fe-modified carbon were studied. The highest static adsorption capacity towards Cr(VI) ions was evaluated for Zr/Fe-modified carbon (50.1 mg g-1) at pHeq = 5.8 after 240 min. The Elovich and Freundlich theoretical models were well fitted to the Cr(VI) adsorption kinetic and isotherm data on the Zr/Fe-modified CMK-3-type carbon. The leading Cr(VI) adsorption mechanism acting on the Zr/Fe-modified carbon was probably based on the redox reactions between Cr(VI) and the carbonaceous surface. Electrostatic attraction and surface complexation processes could also occur during Cr(VI) adsorption in the studied system. The effect of the competitive anions on the concentration level, such as in the galvanic wastewater for Cr(VI) adsorption onto chemically modified carbon, was negligible. The HCl and HNO3 media were insufficient for the Zr/Fe-modified carbon regeneration after Cr(VI) adsorption. The Zr/Fe-modified carbon was successfully applied for the efficient (>90%) Cr(VI) removal from the model galvanic wastewater.

Employing a Toxic Aging Coin approach to assess hexavalent chromium (Cr[VI])-induced neurotoxic effects on behavior: Heads for age differences.

We are facing a rapidly growing geriatric population (65+) that will live for multiple decades and are challenged with environmental pollution far exceeding that of previous generations. Consequently, we currently have a poor understanding of how environmental pollution will impact geriatric health distinctly from younger populations. Few toxicology studies have considered age differences with geriatric individuals. Critically, all top ten most prevalent age-related diseases are linked to metal exposures. Hexavalent chromium [Cr(VI)] is a metal of major environmental health concern that can induce aging phenotypes and neurotoxicity. However, there are many knowledge gaps for Cr(VI) neurotoxicity, including how Cr(VI) impacts behavior. To address this, we exposed male rats across three ages (3-, 7-, and 18-months old) to Cr(VI) in drinking water (0, 0.05, 0.1 mg/L) for 90 days. These levels reflect the maximum contaminant levels determined by the World Health Organization (WHO) and the U.S. Environmental Protection Agency (US EPA). Here, we report how these Cr(VI) drinking water levels impacted rat behaviors using a battery of behavior tests, including grip strength, open field assay, elevated plus maze, Y-maze, and 3-chamber assay. We observed adult rats were the most affected age group and memory assays (spatial and social) exhibited the most significant effects. Critically, the significant effects were surprising as rats should be particularly resistant to these Cr(VI) drinking water levels due to the adjustments applied in risk assessment from rodent studies to human safety, and because rats endogenously synthesize vitamin C in their livers (vitamin C is a primary reducer of Cr[VI] to Cr[III]). Our results emphasize the need to broaden the scope of toxicology research to consider multiple life stages and suggest the current regulations for Cr(VI) in drinking water need to be revisited.

Groundwater Cr(VI) contamination and remediation: A review from 1999 to 2022.

Hexavalent chromium (Cr(VI)) contamination of groundwater has traditionally been an environmental issue of great concern due to its bioaccumulative and highly toxic nature. This paper presents a review and bibliometric analysis of the literature on the interest area "Cr(VI) in groundwater" published in the Web of Science Core Collection from 1999 to 2022. First, information on 203 actual Cr(VI)-contaminated groundwater sites around the world was summarized, and the basic characteristics of the sources and concentrations of contamination were derived. 68.95% of the sites were due to human causes and 56.43% of these sites had Cr(VI) concentrations in the range of 0-10 mg/L. At groundwater sites with high Cr(VI) contamination due to natural causes, 75.00% of the sites had Cr(VI) concentrations less than 0.2 mg/L. A total of 936 papers on "Cr(VI) in groundwater" were retrieved for bibliometric analysis: interest in research on Cr(VI) in groundwater has grown rapidly in recent years; 59.4% of the papers were published in the field of environmental sciences. A systematic review of the progress of studies on the Cr(VI) removal/remediation based on reduction, adsorption and biological processes is presented. Out of 666 papers on Cr(VI) removal/remediation, 512, 274, and 75 papers dealt with the topics of reduction, adsorption, and bioremediation, respectively. In addition, several studies have demonstrated the potential applicability of natural attenuation in the remediation of Cr(VI)-contaminated groundwater. This paper will help researchers to understand and investigate methodological strategies to remove Cr(VI) from groundwater in a more targeted and effective manner.

Mixed N,O-donor Directed Blue Emissive Nano-dispersed Mesoporous Mn(II)-MOF: Dual Sensing Probe for Recyclable and Ultrasensitive ppb-Level Recognition of TNP and Cr(VI)-Oxoanions.

A new mesoporous Mn(II)-MOF [Mn2(phen)2(nia)2]∞ with 4-c uninodal net topology and reiterating rectangular channels in its cargo-net like extension was synthesized using π-conjugated phenanthroline (phen) and syn-syn bridging 5-nitroisopthalic acid (nia) linkers. The MOF (1) exhibited phase purity, uniform morphology, photo and thermal stability, and robustness; duly triggered by the exceptional framework rigidity via intermolecular H-bonding and interlayer π-π stacking interactions. The bright-blue luminescence of the MOF nano-dispersion was explored for sensitive, specific and ultrafast detection of trinitrophenol (TNP) with extremely low LOD (90.62 nM), high KSV (18.27×104 M-1) and Kq (4×1014 M-1s-1). The vapor-phase TNP sensing was also accomplished. Additionally, 1 served towards discriminatory, aqueous-phase monitoring of Cr(VI)-oxoanions, depicting LODs: 36.08 and 35.70 ppb; KSV: 3.46×104 and 4.87×104 M-1; Kq: 3.26×1013 M-1s-1 and 4.31×1013 M-1s-1; and response time: 32 and 40s for CrO4 2- and Cr2O7 2- respectively. The quenching mechanisms (i. e., RET, PET, IFE, weak interactions, collisional quenching and π⋅⋅⋅π stacking) was explained from several experimental investigations and theoretical DFT calculations. The recyclable sensing events and quantification from complex environmental matrices with admirable recovery rates and high KSV (13.02-22.44×104; ~6.31-10.98×104 and ~6.60-11.42×104 M-1 for TNP, CrO4 2- and Cr2O7 2-) undoubtedly advocated the consistency of the probe.

Pharmacodynamic Evaluation and Mechanism of Ginseng Polysaccharide against Nephrotoxicity Induced by Hexavalent Chromium.

Hexavalent chromium is a common pollutant in the environment. Long-term exposure to hexavalent chromium can cause damage to multiple organs. The kidney is one of the main organs that metabolizes heavy metal toxicity, and the accumulation of Cr (VI) in the body can lead to serious damage to kidney function. Studies have shown that ginseng polysaccharides have the function of preventing cisplatin-induced endoplasmic reticulum stress, inflammatory response, and apoptosis in renal cells, but their efficacy and mechanisms against hexavalent chromium-induced nephrotoxicity need to be explored. The aim of this study was to explore the efficacy and mechanism of ginseng polysaccharide against hexavalent chromium-induced nephrotoxicity. The results of pharmacodynamic experiments showed that ginseng polysaccharide could significantly reduce the kidney index, urea nitrogen (BUN), and serum creatinine (Cre) values of K2Cr2O7-treated mice. The results of mechanistic experiments showed that ginseng polysaccharides could alleviate oxidative stress, apoptosis, and biofilm damage in renal tissues caused by Cr (VI). Lipidomic correlation analysis showed that ginseng polysaccharides could protect the organism by regulating the expression of differential lipids. This study opens new avenues for the development of alternative strategies for the prevention of kidney injury caused by hexavalent chromium.

Response patterns of the microbiome during hexavalent chromium remediation by Tagetes erecta L.

Chromium pollution, particularly hexavalent chromium [Cr(VI)], may threaten the environment and human health. This study investigated the potential of Tagetes erecta L. (Aztec marigold) for phytoremediation of soil contaminated with Cr(VI), and focused on the effects of varying concentrations of Cr(VI) on both the physicochemical properties of soil and microbiome of Tagetes erecta L. We observed that Tagetes erecta L. showed tolerance to Cr(VI) stress and maintained normal growth under these conditions, as indicated by bioconcentration factors of 0.33-0.53 in shoots and 0.39-0.70 in roots. Meanwhile, the structure and diversity of bacterial communities were significantly affected by Cr(VI) pollution. Specifically, Cr(VI) had a more significant effect on the microbial community structure in the endophytic of Tagetes erecta L. than in the rhizosphere (p < 0.05). The genera Devosia and Methylobacillus were positively correlated with Cr(VI) concentrations. Biomarkers such as Bacilli and Pseudonocardia were identified under the different Cr(VI)-contaminated treatments using LEfSe. In addition, the interaction and stability of the endophytic microbiome were enhanced under Cr(VI) stress. This study explored the interactions between heavy metals, microorganisms, and plants, providing valuable insights for developing in situ bioremediation of Cr(VI)-contaminated soils.

Green synthesis of nZVI-modified biochar significantly enhanced the removal of Cr(VI) from aqueous solution.

Water contamination by hexavalent chromium (Cr(VI)) seriously jeopardizes human health, which is a pressing environmental concern. Biochar-loaded green-synthesized nZVI, as a green and environmentally friendly material, can efficiently reduce Cr(VI) to Cr(III) while removing Cr(VI) from water. Therefore, in this study, an efficient green-modified biochar material (TP-nZVI/BC) was successfully prepared using tea polyphenol (TP) and sludge biochar (BC) using a low-cost and environmentally friendly green synthesis method. The preparation conditions of TP-nZVI/BC were optimized using response surface methodology (RSM), revealing that the dosage of tea polyphenols plays a crucial role in the removal performance (R2 = 1271.09), followed by reaction time and temperature. The quadratic regression model proved accurate. The optimal preparation conditions are as follows: tea polyphenols (TP) dosage at 48 g/L, reaction temperature at 75 ℃, and a reaction time of 3 h. TP-nZVI/BC removed Cr(VI) from water at a rate 7.6 times greater than BC. The pseudo-second-order kinetic model (R2 = 0.987) accurately describes the adsorption process, suggesting that chemical adsorption predominantly controls the removal process. The adsorption of Cr(VI) by TP-nZVI/BC can be well described by the Langmuir model, and the maximum adsorption capacity reached 105.65 mg/g. FTIR and XPS analyses before and after adsorption demonstrate that nZVI plays a crucial role in the reduction process of Cr(VI), and the synergistic effects of surface adsorption, reduction, and co-precipitation enhance Cr(VI) removal. In summary, using green-modified biochar for Cr(VI) removal is a feasible and promising method with significant potential.

Thiol-functionalized black carbon as effective and economical materials for Cr(VI) removal: Simultaneous sorption and reduction.

Hazardous Cr(VI) continues to pose critical concerns for environmental and public health, demanding the development of effective remediation methods. In this study, thiol-functionalized black carbon (S-BC) was proposed for Cr(VI) removal by mixing thioglycolic acid (TGA) with black carbon (BC) derived from rice straw residue at 80 °C for 8 h. Using a 1:40 (g mL-1) BC-to-TGA ratio, the resulting S-BC40 sample demonstrated significantly enhanced Cr(VI) sorption capacities of 201.23, 145.78, and 106.60 mg g-1 at pH 3.5, 5.5, and 7.5, surpassing its BC counterpart by 2.0, 2.3, and 2.2 times. Additionally, S-BC40 converted all sorbed Cr into Cr(III) species at pH ≥ 5.5, resulting in an equal distribution of Cr(OH)3 and organic Cr(III) complexes. However, approximately 13% of Cr sorbed on BC remained as Cr(VI) at pH 3.5 and 7.5. Both C-centered and S-centered thiyl radicals might contribute to Cr(VI) reduction; however, sufficient C-S groups replenished via thiol-functionalization was the key for the complete Cr(VI) reduction on S-BC samples as pH ≥ 5.5. Thanks to the exceptional Cr(VI) sorption capacity, affordability, and accessibility, thiol-functionalization stands out as a promising modification method for BC. It presents a distinct opportunity to concurrently achieve the objectives of efficient Cr(VI) remediation and waste recycling.

Inhibitory mechanism of Cr(VI) on sulfur-based denitrification: Bio-toxicity, bio-electron characteristics, and microbial evolution.

Sulfur-based denitrification is a promising technology for efficient nitrogen removal in low-carbon wastewater, while it is easily affected by toxic substances. This study revealed the inhibitory mechanism of Cr(VI) on thiosulfate-based denitrification, including bio-toxicity and bio-electron characteristics response. The activity of nitrite reductase (NIR) was more sensitive to Cr(VI) than that of nitrate reductase (NAR), and NIR was inhibited by 21.32 % and 19.86 % under 5 and 10 mg/L Cr(VI), resulting in 10.12 and 15.62 mg/L of NO2--N accumulation. The biofilm intercepted 36.57 % of chromium extracellularly by increasing 25.78 % of extracellular polymeric substances, thereby protecting microbes from bio-toxicity under 5 mg/L Cr(VI). However, it was unable to resist 20-30 mg/L of Cr(VI) bio-toxicity as 19.95 and 14.29 mg Cr/(g volatile suspended solids) invaded intracellularly, inducing the accumulation of reactive oxygen species by 165.98 % and 169.12 %, which triggered microbial oxidative-stress and damaged the cells. In terms of electron transfer, S2O32- oxidation was inhibited, and parts of electrons were redirected intracellularly to maintain microbial activity, resulting in insufficient electron donors. Meanwhile, the contents of flavin adenine dinucleotide and cytochrome c decreased under 5-30 mg/L Cr(VI), reducing the electron acquisition rate of denitrification. Thermomonas (the dominant genus) possessed denitrification and Cr(VI) resistance abilities, playing an important role in antioxidant stress and biofilm formation. ENVIRONMENTAL IMPLICATION: Sulfur-based denitrification (SBD) is a promising method for nitrate removal in low-carbon wastewater, while toxic heavy metals such as Cr(VI) negatively impair denitrification. This study elucidated Cr(VI) inhibitory mechanisms on SBD, including bio-toxicity response, bio-electron characteristics, and microbial community structure. Higher concentrations Cr(VI) led to intracellular invasion and oxidative stress, evidenced by ROS accumulation. Moreover, Cr(VI) disrupted electron flow by inhibiting thiosulfate oxidation and affecting electron acquisition by denitrifying enzymes. This study provided valuable insights into Cr(VI) toxicity, which is of great significance for improving wastewater treatment technologies and maintaining efficient and stable operation of SBD in the face of complex environmental challenges.

Human Health Effects of Oral Exposure to Chromium: A Systematic Review of the Epidemiological Evidence.

The toxicity and carcinogenicity of hexavalent chromium via the inhalation route is well established. However, a scientific debate has arisen about the potential effects of oral exposure to chromium on human health. Epidemiological studies evaluating the connection between ingested chromium and adverse health effects on the general population are limited. In recent years, a wealth of biomonitoring studies has emerged evaluating the associations between chromium levels in body fluids and tissues and health outcomes. This systematic review brings together epidemiological and biomonitoring evidence published over the past decade on the health effects of the general population related to oral exposure to chromium. In total, 65 studies were reviewed. There appears to be an inverse association between prenatal chromium exposure and normal fetal development. In adults, parameters of oxidative stress and biochemical alterations increase in response to chromium exposure, while effects on normal renal function are conflicting. Risks of urothelial carcinomas cannot be overlooked. However, findings regarding internal chromium concentrations and abnormalities in various tissues and systems are, in most cases, controversial. Environmental monitoring together with large cohort studies and biomonitoring with multiple biomarkers could fill the scientific gap.

The influence of Mn(II) on transformation of Cr-absorbed Schwertmannite: Mineral phase transition and elemental fate.

Schwertmannite (Sch) is considered as an effective remover of Chromium (Cr) due to its strong affinity for toxic Cr species. Since the instability of Sch, the environmental fate of Cr deserves attention during the transformation of Sch into a more stable crystalline phase. The ubiquitous manganese(II) (Mn(II)) probably affects the transformation of Sch and thus the environmental fate of Cr. Therefore, this study investigated the impact of Mn(II) on the transformation of Cr-absorbed Sch (Cr-Sch) and the associated behavior of SO42- and Cr. We revealed that the transformation products of Cr-Sch at pH 3.0 and 7.0 were goethite and Sch, respectively. The presence of Mn(II) weakened the crystallinity of the transformation products, and the trend was positively correlated with the concentration of Mn(II). However, Mn(II) changed the transformation products of Cr-Sch from hematite to goethite at pH 10.0. Mn(II) replaced Fe(III) in the mineral structures or formed Mn-O complexes with surface hydroxyl groups (-OH), thereby affecting the transformation pathways of Sch. The presence of Mn(II) enhanced the immobilization of Cr on minerals at pH 3.0 and 7.0. Sch is likely to provide an channel for electron transfer between Mn(II) and Cr(VI), which promotes the reduction of Cr(VI). Meanwhile, Mn(Ⅱ) induced more -OH production on the surface of secondary minerals, which played an important role in increasing the Cr fixation. In addition, part of the Mn(Ⅱ) was oxidized to Mn(Ⅲ)/Mn(Ⅳ) at pH 3.0 and pH 7.0. This study helps to predict the role of Mn(II) in the transformations of Cr-Sch in environments and design remediation strategies for Cr contamination.