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Microbial treatment of Cr(VI) is an environmentally friendly and low-cost approach. However, the mechanism of mutualism and the role of interspecies electron transfer in Cr(VI) reducing microflora are unclear. Herein, we constructed an intersymbiotic microbial association flora to augment interspecies electron transfer via functionalizing electroactive Shewanella oneidensis MR-1 with metal-reducing microflora, and thus the efficiency of Cr(VI) reduction. The findings suggest that the metal-reducing active microflora could converts glucose into lactic acid and riboflavin for S. oneidensis MR-1 to act as a carbon source and electron mediator. Thus, when adding initial 25 mg/L Cr (VI), this microflora exhibited an outstanding Cr (VI) removal efficiency (100%) at 12 h and elevated Cr (III) immobilization efficiency (80%) at 60 h with the assistance of 25 mg/L Cu(II). A series of electrochemical experiments proved this remarkable removal efficiency were ascribed to the improved interspecies electron transfer efficiency through direct interspecies electron transfer and riboflavin through mediated interspecies electron transfer. Furthermore, the metagenomic analysis revealed the expression level of the electron transport pathway was promoted. Intriguing high abundance of genes participating in the bio-reduction and biotransformation of Cr(VI) was also observed in functional microflora. These outcomes give a novel strategy for enhancing the reduction and fixation of harmful heavy metals by coculturing function microflora with electrogenic microorganisms., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microbial reduction of hexavalent chromium (Cr (VI)) shows better efficiency and cost-effectiveness. However, immobilization of Cr (III) remains a challenge as there is a limited supply of electron donors. A greener and cleaner option for donating external electrons was using bioelectrochemical systems to perform the microbial reduction of Cr(VI). In this system, we constructed a polydopamine (PDA) decorated Shewanella oneidensis MR-1 (S. oneidensis MR-1) bioelectrode with bidirectional electron transport, abbreviated as PDA@S. oneidensis MR-1. The conjugated PDA distributed on the intracellular and extracellular of individual S. oneidensis MR-1 has been shown to accelerate electron transfer by outer membrane C-type cytochromes and flavin-bound MtrC/OmcA pathway by various electrochemical analyses. As expected, the PDA@S. oneidensis MR-1 biofilm achieved 88.1% Cr (VI) removal efficiency (RE) and 58.1% Cr (III) immobilization efficiency (IE) within 24 h under the autotrophic conditions at the optimal voltage (-150 mV) compared with the control potential (0 mV). The PDA@S. oneidensis MR-1 biofilm showed increased RE activity was attributed to the shortening of the distance between individual bacteria by PDA. This research provides a viable strategy for in situ bioremediation of Cr(VI) polluted aquatic environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Inc.)

The recovery of heavy metals from electroplating sludge is important for alleviating heavy metal pollution and recycling metal resources. However, the selective recovery of metal resources is limited by the complexity of electroplating sludge. Herein, CuFe bimetallic Fenton-like catalysts were successfully prepared from electroplating sludge by a facile room-temperature ultrasonic-assisted co-precipitation method. The prepared CuFe-S mainly consisted of nanorods with diameters of 20-30 nm and lengths of 100-200 nm and a small number of irregular particles. Subsequently, we performed tetracycline (TC) degradation experiments, and the results showed that the product CuFe-S had very good performance over a wide pH range (2-11). At an initial pH = 2, CuFe-S could degrade 91.9% of 50 mg L -1 TC aqueous solution within 30 min, which is better than that of a single metal catalyst. Free radical scavenging experiments and electron paramagnetic resonance (EPR) tests revealed that ·OH was the main active species for the degradation of TC by CuFe-S. In conclusion, a CuFe bimetallic Fenton-like catalyst was developed for the catalytic degradation of antibiotics, which provides a novel technical route for the resource utilization of electroplating sludge and shows an important practical application prospect., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Chromium ore processing residue (COPR) is a hazardous waste generated during the production of chromate. Currently, approximately 10% of Cr 2 O 3 cannot be extracted after chromite sodium roasting and remains in COPR, wasting valuable Cr resources. In this study, Mg was selectively removed by using (NH 4 ) 2 SO 4 roasting in combination with H 2 SO 4 leaching. The results showed that the selective removal of 79.55% Mg from COPR could be achieved under the optimum (NH 4 ) 2 SO 4 roasting conditions (80 mmol (NH 4 ) 2 SO 4 , 800 °C, 2 h). During the subsequent sodium roasting and acid leaching stages, the Cr extraction rate was 84.63% for the COPR direct roasting and 95.39% for the Mg removal residue roasting. The increased Cr extraction efficiency is attributed to the transformation of Mg-rich spinel and diopside (the Mg & Cr coexisting phases) in COPR converted into easily extractable (Fe,Cr) 2 O 3 and Cr 2 O 3 after the Mg treatment. This study investigated that the phase transformation of the Cr host phases is crucial for the sufficient extraction of Cr and provides inspiration for the development of efficient and practical Cr extraction techniques. Moreover, the method can be extended to the effective extraction of Cr from other Cr-containing wastes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Low concentrations of antibiotics can regulate the formation of electroactive biofilms, however, the underlying mechanisms, especially the composition and spatial distribution of extracellular polymeric substances (EPS) and their effects on extracellular electron transfer (EET) process, have not been fully deciphered. Here, the response of EPS of Geobacter sulfurreducens biofilm to low concentrations of tetracycline (μg L -1 to mg L -1 ) was explored, and the impact of such EPS variations on EET efficiency was further elucidated by transcriptomic analysis. Results showed that 0.05 mg L -1 of tetracycline achieved both beneficial quantitative and spatial regulation of redox-active proteins and non-conducting exopolysaccharides in EPS, while higher concentrations induced negative effects. Moreover, 1 mg L -1 of tetracycline upregulated multiple exopolysaccharide biosynthesis-related genes, indicating a stress response for cell-protection, while 0.05 mg L -1 of tetracycline upregulated most direct EET-related gene expressions, resulting in the promoted EET efficiency. Furthermore, 0.05 mg L -1 of tetracycline selectively enriched Geobacter (45.55% vs 19.55% in control, respectively) from mixed inoculum. This research provides a new insight of how antibiotics at low concentrations regulated EET process through modulation of EPS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The synergistic effect of heteroatoms is a viable method to enhance the adsorption performance of heavy metal onto carbon-based materials. However, the high cost, complex operation and a lot of pollution from the synthesis process have limited its development. Herein, a facile two-step pyrolysis method is used to prepare in situ N and S doped porous biochar from paper mill sludge for the removal of Cr(VI) from aqueous environment. The NSC-450 sample prepared under the optimum conditions has a large specific surface area of 3336.7 m 2 g -1 , an average pore size of 2.56 nm and a total pore volume of 2.10 cm 3 g -1 , manifesting the excellent adsorption capacity of 356.25 mg g -1 for Cr(VI). The adsorption of Cr(VI) by NSC-450 is consistent with the Langmuir isotherm and pseudo-second-order model, suggesting a spontaneous and endothermic chemisorption process. The analysis results show that the NH, graphitic nitrogen and thiophene structures have a positive effect on converting a large amount of Cr(VI) to Cr(III) by synergistic reduction, indicating obviously facilitating Cr(VI) removal compared to other sites. Therefore, in this material, the strong adsorption mechanism is mainly reductive complexation. Moreover, the effects of real water quality, anions, cations and fulvic acid on the adsorption behavior of Cr(VI) onto the NSC-450 were further investigated. The results demonstrate that the chromium removal rate remains above 82% even in actual electroplating wastewater, suggesting NSC-450 has great practical application prospect. This work offered a feasible method for high-value utilization of sludge, but also provided a novel perspective for the future design of heteroatom-doped carbon materials for promoting to eliminate hexavalent chromium from water environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Chromite ore processing residue (COPR) has been a severe environmental contaminant which is worthy of attention. In this study, we developed an eco-friendly and practical technology for effectively stabilizing and recovering Cr(VI) in COPR via combining FeSO 4 reducing agent and the hydrothermal treatment. A stable spinel phase product was formed during detoxification. In addition, the ferrochrome resources in the treated COPR can be obtained by magnetic separation. As we studied, the hydrothermal environment promoted the release of unstable Na 2 CrO 4 from COPR into the solution, and the released CrO 4 2- was reduced to Cr(III) by FeSO 4 . Subsequently, Cr(III), Fe(II) and Fe(III) were hydrothermally mineralized to form the magnetic spinel phase Fe 2+ (Cr 3+ X , Fe 3+ 2-x )O 4 (FeCr spinel substance), which was conducive to the magnetic separation of ferrochrome resources. Under the optimal hydrothermal conditions (0.15 g FeSO 4 /2 g COPR, treatment at 180 °C for 8 h), the total Cr leaching concentration of treated COPR (COPR-HT) was decreased from 120.51 mg L -1 to 0.23 mg L -1 , well below the regulatory limit of 1.5 mg L -1 (HJ/T 301-2007, China EPA). After 300 days aging under atmospheric conditions, the total Cr leaching concentration of COPR-HT was still below 1.5 mg L -1 . Besides, the COPR-HT after magnetic separation contained 11.52 wt% Cr 2 O 3 and 53.44 wt% Fe 2 O 3 , which can be used as the raw material for steel industry. The underlying mechanism of COPR stabilization was explained by XRD, XPS and SEM-EDS analysis. This work converted the toxic and unstable Cr(VI) in COPR into the long-term stable FeCr spinel substance that is easy to magnetically separate. It has important reference for the harmless disposal and resource utilization of other chromium-containing hazardous wastes including chromium slag and electroplating sludge., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Sulfidated nanoscale zero-valent iron (S-nZVI) has shown excellent removal capacity for the removal of cadmium (Cd) in aqueous phase. Herein, the effectiveness and the mechanism of S-nZVI for the remediation of Cd contaminated soil were investigated for the first time. The results of sequential extraction procedures (SEP) showed that the exchangeable (EX) Cd was decreased by over 97.6% at the optimal dosage of 5 g kg -1 S-nZVI during 30 d incubation and converted to less available Cd such as iron-manganese oxides-bound (OX) and organic matter-bound (OM) fractions. pH has negligible effect on the immobilization of Cd in soil, since OX fraction was stabilized in the range of 72-92% at initial soil pH range from 5.3 to 7.5. SEM-EDS analysis of the separated magnetic particles implied that Cd was successfully enriched on S-nZVI and the distribution of Cd was closely related to Fe, S, and O. CdO and CdS was confirmed as the key products for Cd immobilization in soil. Meanwhile, the S-nZVI was oxided to α-FeOOH, γ-FeOOH, and γ-Fe 2 O 3 . The existence of CdO was visibly related to the iron oxides, suggesting the synergetic immobilization effect by iron oxides. Overall, S-nZVI was promising for the remediation of Cd-contaminated soil., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This work demonstrated that electroplating sludges (EPS) of specific composition may be used for the synthesis of layered double hydroxide (LDH) materials for energy applications after appropriate treatment. The unique composition and structure of EPS render it with good electrochemical energy storage performance. The EPS containing Ni, Fe, and Al was dissolved by acid and added with urea precipitator. The LDH material was prepared by a facile hydrothermal method. The increase of urea in a certain range is conducive to the formation of intact LDH. However excessive urea levels promoted the transformation from LDH to Ni(HCO 3 ) 2 . Various active Ni bridged by N in ‒O‒CN promoted electron transfer, ‒O‒CN content in LDHs was proportional to the urea amount. The prepared LDHs exhibited a specific capacitance of 1652.20 F g -1 at 0.5 A g -1 , and the value remained at 766.69 F g -1 after 1000 cycles. The prepared LDH has excellent supercapacitor performance, which is closely related to its structure. Therefore, the proposed recycling strategy of EPS resources can be used to prepare LDH supercapacitors, paving the way for new applications of EPS in the field of energy storage., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study, the reaction between sulfidated nanoscale zero-valent iron (S-nZVI) and heavy metal cations as well as the role of sulfur were investigated. The results showed the corrosion products of S-nZVI were lepidocrocite (γ-FeOOH) or/and magnetite (Fe 3 O 4 ), depending on heavy metal species. While the removal of Hg(II), Ag(I), Cu(II), and Pb(II) by S-nZVI was rapid and could achieve over 99% within 5 mins, the removal of Ni(II) and Zn(II) was low in efficiency and unstable. Sulfur was existed as iron sulfides at fresh S-nZVI, but was displaced by the heavy metals and formed the related sulfide compound, or oxidized to S 0 and SO 4 2- . The removal mechanisms are strongly dependent on the solubility product constant (K sp ) of metal sulfides. For Hg(II) and Ag(I), with K sp of corresponding metal sulfides much lower than that of iron sulfide, the removal mechanism is the displacement reaction. For Cu(II) and Pb(II), with K sp of corresponding metal sulfides moderately lower than that of iron sulfide, the removal mechanisms are the displacement reaction and complexation with surface groups of S-nZVI. For Zn(II) and Ni(II), whose K sp of corresponding metal sulfides slightly lower than that of iron sulfide, are mainly removed by complexation with surface groups of S-nZVI., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Nanosized clay minerals have been widely used as efficient supports to immobilize catalyst nanoparticles. However, clay support-induced interactions and their influences on the catalyst structure and performance currently have not been fully understood. Here, Co 3 O 4 nanoparticles supported on halloysite nanotubes (HNTs) were synthesized by a facile deposition-precipitation approach followed by thermal treatment. A series of characterization methods were employed for the Co 3 O 4 /HNTs hybrid nanostructure to identify its crystal phase, chemical composition, morphology, specific surface area, surface chemical states, and redox property. Characterization results showed that HNTs not only impacted the particle size of Co 3 O 4 nanoparticles, but also modified surface chemical surface states of the later, which ultimately promoted the effective catalytic reduction of 4-nitrophenol (4-NP) and azo dyes with sodium borohydride. The interaction between HNTs and Co 3 O 4 nanoparticles was found to shorten the induction period of the 4-NP reduction. Meanwhile, the Co 3 O 4 /HNTs catalyst for the 4-NP reduction achieved an apparent rate constant of 0.265 min -1 and an activity parameter of 1.63 × 10 4 min -1 g -1 as well as a turnover frequency of 4.37 min -1 . In addition, Co 3 O 4 /HNTs showed an improvement in reduction efficiency of the azo dyes when compared to bare Co 3 O 4 nanoparticles., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Here, hierarchical nanostructures of clay-based hybrids were synthesized via a space-confined growth of layered basic zinc acetate (LBZA) nanosheets standing upright on both sides of bentonite clay platelets. These thermally instable LBZA nanosheets were thermally decomposed and fragmented into ZnO nanoparticles well-dispersed on bentonite platelets. The morphology and structure of LBZA/bentonite and ZnO/bentonite was characterized by SEM, TEM, XRD, TG-DSC, and FTIR. Surface density of LBZA nanosheets on bentonite platelets was simply controlled by tuning the amount of zinc acetate. LBZA/bentonite and ZnO/bentonite was used for the adsorption of Congo red (CR) and photodegradation of methyl orange (MO), respectively. Results showed that LBZA/bentonite exhibited higher adsorption capacity for Congo red (CR) than original bentonite. In addition, bentonite-supported ZnO nanoparticles efficiently promoted the photodegradation of MO under UV light irradiation., (Copyright © 2019 Elsevier B.V. All rights reserved.)