BACKGROUND: In response to growing concerns regarding heavy metal contamination in food, particularly chromium (Cr)(VI) contamination, this study presented a simple, sensitive and practical method for Cr(VI) detection.
RESULTS: A magnetic separation-based capture-exponential enrichment ligand system evolution (SELEX) method was used to identify and characterize DNA aptamers with a high affinity for Cr(VI). An aptamer, Cr-15, with a dissociation constant (Kd) of 4.42 ± 0.44 μmol L-1 was obtained after only eight rounds of selection. Further innovative methods combining molecular docking, dynamic simulation and thermodynamic analysis revealed that CrO4 2- could bind to the 19th and 20th guanine bases of Cr-15 via hydrogen bonds. Crucially, a label-free fluorometric aptasensor based on SYBR Green I was successfully constructed to detect CrO4 2-, achieving a linear detection range of 60-300 nmol L-1 with a lower limit of detection of 44.31 nmol L-1. Additionally, this aptasensor was able to quantitatively detect CrO4 2- in grapes and broccoli within 40 min, with spike recovery rates ranging from 89.22% to 108.05%. The designed fluorometric aptasensor exhibited high selectivity and could detect CrO4 2- in real samples without sample processing or target pre-enrichment.
CONCLUSIONS: The aptasensor demonstrated its potential as a reliable tool for monitoring Cr(VI) contamination in fruit and vegetable products. © 2024 Society of Chemical Industry.

A new type of polyethyleneimine-protected copper nanoclusters (PEI-CuNCs) is favorably developed by a one-pot method under mild conditions. The obtained PEI-CuNCs is characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, Fourier-transform infrared (FTIR) spectroscopy and other techniques. It is worth noting that the proposed PEI-CuNCs demonstrate a selective response to chromium(VI) over other competitive species. Fluorescence quenching of PEI-CuNCs is determined to be chromium(VI) concentrations dependence with a low limit of detection of 8.9 nM. What is more, the as-developed PEI-CuNCs is further employed in building a detection platform for portable recognition of chromium(VI) in real samples with good accuracy. These findings may offer a distinctive strategy for the development of methods for analyzing and monitoring chromium(VI) and expand their application in real sample monitoring.

The toxicity and carcinogenicity of Cr(VI) makes it a major threat to the health of animals and people. However, how to efficiently remove Cr(VI) still faces important challenges. In this study, a new metal-free polypyrrole-red phosphorus (PPy-RP) composite is successfully synthesized by in-situ oxidation polymerization for Cr(VI) removal from wastewater. The maximum adsorption capacity (qm) of Cr(VI) on PPy-RP-1 is 513.2 mg/g when the pH value is 2, which is far superior to RP nanosheets (207.8 mg/g) and PPy (294.9 mg/g). The improved qm can be ascribe to the good dispersion and increased specific surface area of PPy-RP adsorbent. Encouragingly, PPy-RP adsorbent still exhibits excellent stability after 7 cycles tests without a significant decline in removal efficiency, and remain above 81.4%. Based on the fittings of adsorption isotherms and kinetics, the process conforms to the pseudo-first-order kinetic model and the single-layer adsorption of the Langmuir model with an R2 value of 0.98533. The adsorption process is chemical and monolayer. The experimental result demonstrates that the PPy-RP can efficient removal Cr(VI) by electrostatic attraction and complexation reaction (formation of N-Cr(VI) bond) through the PPy on the surface. The results of this study indicate that PPy-RP is a promising adsorbent to remove the Cr(IV).

Iron minerals, which exert excellent biocompatibility and reactivity with redox-active microorganisms, have attracted attention as a precursor to synthesizing composite materials with higher catalytic efficiency in driving redox-active microorganisms to reduce Cr(VI). However, researches on the effective preparation method of composites, the interaction between bacteria and composite materials and the mechanism of electron transfer are still scarce. In this work, Fe-complex@BC prepared by a one-step method using goethite was used for chromium treatment together with soil microorganisms. The composite was the best-performing in promoting Cr(VI) bioreduction (up to 3.48 mg (L·h)-1) than Fe-complex (2.26 mg (L·h)-1) and biochar (0.5 mg (L·h)-1), even about 19 times higher than that of bioreduction without materials. Specifically, Fe-complex@BC shortened the electron transfer distance due to its excellent adsorption properties for bacteria and Cr(VI). Its high redox activity also promoted Cr(VI) bioreduction by directly enhancing electron transfer. In addition, the presence of the Fe(III)/Fe(II) cycle proved that the active sites of composite could be regenerated to reduce Cr(VI) persistently by receiving extracellular electrons from bacteria. High-throughput 16 S rDNA gene sequencing indicated the composite could promote the proliferation of electrochemically active bacteria, which directly enhanced bioreduction. This study developed the low-cost Fe@BC material prepared by a one-step co-pyrolysis method, which exerts a synergistic effect with soil microorganisms and presents a promising potential for chromium pollution treatment.

Pyrite was applied to Cr(VI) bioremediation as an inorganic electron donor due to the ability to provide electrons, while the role of pyrite in Cr(VI) bioremediation where organics as electron donors remains unknown. Herein a pyrite-based Cr(VI) bioreduction process in the sediment system containing lactate was demonstrated to be effective to detoxify Cr(VI): over 2200 mg L-1 Cr(VI) was continuously removed within 210 h with high reactivity (10.5 mg/(L·h)) all along. High-throughput 16S rDNA gene sequencing indicated that the pyrite could shape a functioning community that electrochemically active bacteria dominated (such as Fusibacter sp. and Rhodobacteraceae) instead of iron-oxidizing bacteria and sulfur-oxidizing bacteria. Mineralogy analysis results indicated that Fe(III), S22- and S0 formed on the pyrite surface after the oxidation of Cr(VI) might serve as the electron acceptor of microflora, then the S2- and Fe(II) with strong Cr(VI) reduction ability were formed by microbial reduction to enhance the removal of Cr(VI). This study provides new insights into thoroughly understanding the role of pyrite in the practical application of Cr(VI) bioreduction.

The cycling of Fe/S is often related to the formation and fate of schwertmannite which is particularly suitable as a scavenger for heavy metals and metalloids in acid mine drainage (AMD). However, the interactions between reactivity of S(-II) and schwertmannite with structurally incorporated Cr(VI) remain elusive. This work evaluated dissolution experiments in combination with XRD, SEM, FTIR, TEM, and XPS characterization to provide detailed information regarding the transformation of schwertmannite induced by S(-II) following changes in pH, Cr loading, and S(-II) concentration. Our results found that the presence of sulfide significantly decreased the stabilization of schwertmannite under acidic conditions. The reactivity of the three schwertmannite samples depended on the contents of Cr(VI) that were structurally incorporated and followed the order Sch > 0.13Cr-Sch > 0.17Cr-Sch. High S(-II) concentrations and low Cr doping favored the release of Fe and SO42- from schwertmannite. Attenuation of Cr mobility occurred via elevating the S(-II) concentrations and pH values resulting in Cr concentrations spanning ∼1.39 to ∼0.10 mg L-1 and ∼1.58 to ∼0.12 mg L-1 for 0.13Cr-Sch and 0.17Cr-Sch, respectively. Combining the results of characterization, goethite was the dominant end product constituted secondary phase together with sulfide minerals (FeS, FeS2), iron oxides (Fe3O4, Fe2O3), and CrFe minerals on the bulk mineral surface. The substituted Cr significantly inhibited the reductive transformation of schwertmannite by sulfide and led to the formation of lepidocrocite. Thus, we concluded that a three-stage transformation mechanistic pathway governed partial conversion of schwertmannite to goethite. This finding provides new understanding of the biogeochemical processes of iron minerals affected by reducing substances that control the transport and fate of immobilizing contaminants in an AMD-polluted area.

A novel collaborative strategy for enhanced removal of Cr(VI) using nano zero valent iron (nZVI) assisted by schwertmannite (Sch) with two synthesis methods was designed. Batch experiments demonstrated that nZVI/Sch-AP (synthesized by abiotic precipitation of Fe3+ species) exhibited excellent removal performance for Cr(VI) than nZVI/Sch-CO (synthesized by chemical oxidation of Fe2+ species). The results indicated that the removal efficiencies of Cr(VI) by nZVI/Sch-AP and nZVI/Sch-CO were highly pH-dependent and achieved to be 99.99% and 98.01% under the optimal conditions of 10 mg L-1 Cr(VI) concentration, a pH of 6.3 and a Fe(0)/Cr(VI) molar ratio of 12. But nZVI/Sch-AP emerged greater k of 0.1097 min-1 than that of nZVI/Sch-CO (0.0485 min-1). Humic acid exhibited promotion effect on the Cr(VI) removal in low concentration of 1 mg L-1. Results of XRD and XPS demonstrated that α-FeOOH was the dominant products in both incubations of nZVI/Sch-AP and nZVI/Sch-CO, accompanied with FeCr2O4 and CrFe mixed (oxy)hydroxides, and γ-FeOOH was found alone in the incubations of nZVI/Sch-CO. We proposed a consecutive and simultaneous process involving surface absorption-reduction and co-precipitation/immobilization for the removal. This study provides new insights into the elimination of Cr(VI) from wastewater by nZVI/Sch, especially in acid mine drainage.

Related studies have shown that chromium (Cr) is toxic to cells, and hydrogen can protect cells by regulating endoplasmic reticulum (ER) stress and autophagy. However, there are few reports on the protective effects of hydrogen on heavy metal-induced cell damage. The objective of this study was to investigate the protection of hydrogen-rich medium (HRM) on Cr(VI)-induced ER stress and autophagy in DF-1 cells. Therefore, HRM were pretreated for 30 min before Cr(VI) treatment, and detected the autophagy and ER stress-related indicators to determine the role of HRM. The results showed that HRM could reduce the cell damage caused by Cr(VI), and 3-methyladenine (3-MA) could protect cells by inhibiting over autophagy. HRM can reverse the changes of ER stress- and autophagy-related indexes caused by Cr(VI), and inhibit the excessive autophagy caused by Cr(VI). In conclusion, HRM can protect cells from damage induced by Cr(VI), and play a role by inhibiting ER stress-mediated autophagy.

Chromium(VI) (Cr(VI)) is an environmental priority pollutant, and its mobility in natural environment is strongly controlled by ferrihydrite. Ferrihydrite always contains various ions, which may change the properties of ferrihydrite, thereby affecting the behavior of pollutants. This study aims to investigate the adsorption of Cr(VI) by Mn-incorporated ferrihydrite and the mobility behavior of Cr(VI) during aging. Results showed that the incorporation of Mn enhanced the adsorption of Cr(VI) on ferrihydrite, and the adsorption performance increased with the increase of Mn content. The maximum adsorption capacity for Cr(VI) reached to 48.5 mg/g with molar ratio of Mn/Fe 5%, while it was 36.1 mg/g for pure ferrihydrite. After aging for 7 days, ferrihydrite transformed into goethite and hematite. The adsorbed Cr(VI) on the surface of ferrihydrite was released into the solution during aging. The incorporation of Mn retarded the transformation of ferrihydrite, which inhibited the migration of adsorbed Cr(VI). Nevertheless, the incorporation of Mn resulted in the transformation of adsorbed Cr(VI) to non-desorbed Cr(VI), thereby enhancing the retention of Cr(VI). Our results suggest that the incorporation of Mn into ferrihydrite has an important role on the mobility of Cr(VI), which enhances our understanding of the behavior of Cr(VI) in the environment.

A novel citrate-crosslinked Zn-MOF/chitosan (ZnBDC/CSC) composite was successfully prepared by immobilizing Zn-MOF (ZnBDC) on citrate-crosslinked chitosan (CSC) using citric acid as a chemical bridge. ZnBDC/CSC was characterized by XRD, FT-IR, solid-state 13C NMR, BET and SEM. The adsorption of ZnBDC/CSC for Cr(VI) and MO from aqueous solutions were studied at pH 5.0. The adsorption conditions, such as adsorption time and initial concentration of Cr(VI) and MO solutions were investigated. The results indicated that ZnBDC/CSC showed high adsorption capacity for both Cr(VI) (225 ± 4 mg g-1) and MO (202 ± 3 mg g-1), respectively. The adsorption of Cr(VI) on ZnBDC/CSC could be well described by Langmuir isotherm model, while MO followed Freundlich model. The adsorption kinetic of Cr(VI) and MO demonstrated a better fitness to the pseudo-second order kinetic model. Thermodynamic parameters (enthalpy (ΔH), entropy (ΔS) and Gibbs free energy (ΔG)) demonstrated that the adsorption processes of Cr(VI) and MO on ZnBDC/CSC were exothermic, disordered and spontaneous at 298-318 K. The adsorption mechanism of ZnBDC/CSC for Cr(VI) could be mainly explained by electrostatic attraction and cation-π interaction, while for MO, it could be assigned to n-π and π-π interactions, electrostatic attraction and hydrogen bonding. ZnBDC/CSC could be recycled and reused for the removal of Cr(VI) and MO.