To enhance the stability and adsorption performance of chitosan in Cr(VI)-contaminated acidic wastewater, a novel EDAC-modified-EDTA-crosslinked chitosan derivative (CSEC) was synthesized via a one-pot method with chitosan, 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC), and Na2EDTA as raw materials. To further improve the mechanical strength and separation performance of CSEC, a novel composite bead (CSEP) of CSEC and imidazolium-functionalized polysulfone (IMPSF) was prepared through a phase inversion method. The chemical composition and microstructure of CSEC and CSEP were characterized by FESEM, FTIR, NMR and XPS techniques. The maximum adsorption capacities of CSEC and CSEP for Cr(VI) were 145.96 and 135.82 mg g-1 at pH 3, respectively, and the equilibrium time for Cr(VI) adsorption by CSEC and CSEP was 5 min and 8 h, respectively. The adsorption process of Cr(VI) by both CSEC and CSEP was exothermic and spontaneous. Compared to CSEC, CSEP has significantly enhanced resistance to interference from coexisting anions. The removal mechanism of Cr(VI) by CSEP might involve redox reaction as well as electrostatic attraction between Cr(VI) oxyanions and various nitrogen cations, including protonated amino groups, guanidinium groups, protonated tertiary amine groups, and imidazolium cations. The CSEP beads have potential application value in the treatment of acidic wastewater containing Cr(VI).

The reactivity and stability of zero-valent iron (ZVI) and sulfidated zero-valent iron (S-ZVI) are inherently contradictory. Iron sulfides (FeSX) on the S-ZVI surface play multiple roles, including electrostatic adsorption and catalyzing reduction. We proposed to balance the reactivity and air stability of S-ZVI by regulating FeSX. Benefiting from the superior coordination and accelerate electron transport capabilities of phosphate, herein, eco-friendly ammonium dihydrogen phosphate (ADP) was employed to synthesize N, P, and S-incorporated ZVI (NPS-ZVI) and regulate the FeSX. Raman, FTIR, XPS, and density functional theory (DFT) calculations were combined to reveal that HPO42- acts as the main P species on the Fe surface. The superior reactivity of NPS-ZVI was quantified by kobs, kSA, and kM of Cr(VI), which were 210.77, 27.44, and 211.17-fold than ZVI, respectively. NPS-ZVI demonstrated excellent reusability, with no risk of secondary pollution. Critically, NPS-ZVI could effectively maintain FeSX stability under the combination of diffusion limitation and surface protection mechanisms of ADP. The superior reactivity of NPS-ZVI was attributed to the fact that ADP maintains FeSX stability and accelerates electron transport. This study provides a novel strategy in balancing the reactivity and air stability of S-ZVI and offers theoretical support for material modification.

Biosynthetic metal sulfides showed great application prospects in the environmental treatment against high-valence metal pollutants. However, the efficiency of biosynthesis, agglomeration during the reaction process, and the formation of the passivation layer during the reduction process were always the important factors restricting its development. This study explored the composition of the culture medium to promote the growth of highly corrosive sulfate-reducing bacteria (SRB) and its metabolism to produce FeS nanoparticles (NPs). The results showed that reducing the carbon source (CS) and adding electron carriers in the culture medium effectively promoted the production of small, dispersed, and loose FeS NPs in cells. At pH = 7, 24 °C and 10 min reaction time, 0.1 g/L FeS NPs produced by SRB under the conditions of 10 % CS with 10 ppm cytochrome c medium could achieve 100 % removal efficiency of 1 mM hexavalent chromium (Cr(VI)). Under this condition, FeS NPs could be produced by intracellular metabolism in SRB cells, and environmental factors such as pH, metal cations, and Cl- had little effect on the removal of Cr(VI) by this FeS NPs. The surface proteins of FeS NPs significantly enhanced their antioxidant properties. After 7 days of natural environment exposure, the Cr(VI) removal efficiency of FeS NPs was only reduced by 16 % compared with the initial sample. This work provided an in-depth understanding of Cr(VI) removal by SRB biosynthesis of FeS and contributes to the widespread application of FeS in the future.

Micron-scale zero-valent iron (ZVI)-based material has been applied for hexavalent chromium (Cr(VI)) decontamination in wastewater treatment and groundwater remediation, but the passivation problem has limited its field application. In this study, we combined aluminum chloride solution with ZVI (pcZVI-AlCl3) to enhance Cr(VI) removal behavior under aerobic conditions. The optimal pre-corrosion conditions were found to be 2.5 g/L ZVI, 0.5 mM AlCl3, and a 4 h preconditioning period. Different kinds of techniques were applied to detect the properties of preconditioned ZVI and corrosion products. The 57Fe Mössbauer spectra showed that proportions of ZVI, Fe3O4, and FeOOH in pcZVI-AlCl3 were 49.22%, 34.03%, and 16.76%, respectively. The formation of Al(OH)3 in the corrosion products improved its pHpzc (point of zero charge) for Cr(VI) adsorption. Continuous-flow experiments showed its great potential for Cr(VI) removal in field applications. The ZVI and corrosion products showed a synergistic effect in enhancing electron transfer for Cr(VI) removal. The mechanisms underlying Cr(VI) removal by pcZVI-AlCl3 included adsorption, reduction, and precipitation, and the contribution of adsorption was less. This work provides a new strategy for ZVI pre-corrosion to improve its longevity and enhance Cr(VI) removal.

Tea saponins (TS), a natural biosurfactant extracted from tea trees, were co-ball milled with commercial micro zero-valent iron (mZVI) to produce TS modified mZVI (TS-BZVI) for efficient hexavalent chromium (Cr(VI)) removal. The findings demonstrated that TS-BZVI could nearly remove 100% of Cr(VI) within 2 h, which was 1.43 times higher than that by ball milled mZVI (BZVI) (70%). Kinetics analysis demonstrated a high degree of compatibility with the pseudo-second-order (PSO), revealing that TS-BZVI exhibited a 2.83 times faster Cr(VI) removal rate involved primarily chemisorption. Further, X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) measurements indicated that the TS co-ball milling process improved the exposure of Fe(II) and Fe(0) on mZVI, which further promoted the Cr(VI) reduction process. Impressively, the introduction of TS increased the hydrophobicity of ZVI, effectively inhibiting the H2 evolution by 95%, thus improved electron selectivity for efficient Cr(VI) removal. Ultimately, after operating for 10 days, a simulated permeable reactive barrier (PRB) column experiment revealed that TS-BZVI had a higher Cr(VI) elimination efficiency than BZVI, indicating that TS-BZVI was promising for practical environment remediation.

The present research study combines chitin from shrimp waste with the oxide-rich metakaolin. Metakaolin is a blend of mixed oxides rich in silica and alumina with good adsorbent properties. The chitin@metakaolin (CHt@M.K.) composite was synthesized and characterized using FTIR, SEM, TGA, XRD and XPS techniques. Cr(VI) removal studies were compared for chitin and CHt@M.K. through adsorption. It was found that the adsorption capacity of CHt@M.K. is 278.88 mg/g, almost double that of chitin, at pH 5.0 in just 120 min of adsorption. Isotherm models like Langmuir, Freundlich, Temkin and Dubinin-Radushkevich were investigated to comprehend the adsorption process. It was revealed that Langmuir adsorption isotherm is most suitable to elucidate Cr(VI) adsorption on CHt@M.K. The adsorption kinetics indicate that pseudo first order was followed, indicating that the physisorption was the process that limited the sorption process rate. The positive enthalpy change (20.23 kJ/mol) and positive entropy change (0.083 kJ/mol K) showed that the adsorption process was endothermic and more random at the solid-liquid interface. The negative free energy change over entire temperature range was an indicator of spontaneity of the process. Apart from all these, the non-covalent interactions between Cr(VI) and composite were explained by quantum calculations based models.

Selective adsorption of heavy metal ions from industrial effluent is important for healthy ecosystem development. However, the selective adsorption of heavy metal pollutants by biochar using lignin as raw material is still a challenge. In this paper, the lignin carbon material (N-BLC) was synthesized by a one-step hydrothermal carbonization method using paper black liquor (BL) as raw material and triethylene diamine (TEDA) as nitrogen source. N-BLC (2:1) showed excellent selectivity for Cr(VI) in the binary system, and the adsorption amounts of Cr(VI) in the binary system were all greater than 150 mg/g, but the adsorption amounts of Ca(II), Mg(II), and Zn(II) were only 19.3, 25.5, and 6.3 mg/g, respectively. The separation factor (SF) for Cr(VI) adsorption was as high as 120.0. Meanwhile, FTIR, elemental analysis and XPS proved that the surface of N-BLC (2:1) contained many N- and O- containing groups which were favorable for the removal of Cr(VI). The adsorption of N-BLC (2:1) followed the Langmuir model and its maximum theoretical adsorption amount was 618.4 mg/g. After 5th recycling, the adsorption amount of Cr(VI) by N-BLC (2:1) decreased about 15%, showing a good regeneration ability. Therefore, N-BLC (2:1) is a highly efficient, selective and reusable Cr(VI) adsorbent with wide application prospects.

Modification of silica purified from the Merapi volcanic ash with magnetic material of Fe3O4 and attachment of cetyl triamine bromide (CTA-Br) on the magnetic cored has been performed to provide recoverable and positive surfaced of natural adsorbent. The magnetic cored was prepared via co-precipitation and CTA-Br attachment was conducted by a facile strategy. Then, the modified adsorbents were characterized by SEM, TEM, XRD, and FTIR instruments and examined for removing anionic Cr(VI) from the water media. The characterization data confirmed that crystals of Fe3O4 coated by SiO2 that has been bound with CTA-Br have been successfully formed. Additionally, increasing CTA-Br loaded gives thicker lamination on Fe3O4@SiO2/CTA-Br, but the CTA-Br loaded with higher than 0.25 mmol, leads to the coating peeled out. It is also demonstrated that Fe3O4@SiO2/CTA-Br prepared with CTA-Br 0.25 mmol is ideal for Cr(VI) anionic removal, regarding to the highest adsorption and very good separation or recovery process. Moreover, the optimal dose of Fe3O4@SiO2/CTA-Br in the Cr(VI) removal was observed at 0.25 g/20 mL under condition of pH 3 for 60 min. The adsorption of Cr(VI) well fits the Langmuir isotherm model with an adsorption capacity of 3.38 mg g-1 and is in a good agreement with pseudo-second order giving kinetic constant at 0.005 g mg-1 min-1. Thus, it is clear that the natural adsorbent material with recoverable properties for more efficient and wider application of removal Cr(VI) contaminant was expected from this study.

The fastest-growing microbe Vibrio natriegens is an excellent platform for bioproduction processes. Until now, this marine bacterium has not been examined for bioremediation applications, where the production of substantial amounts of biomass would be beneficial. V. natriegens can perform extracellular electron transfer (EET) to Fe(III) via a single porin-cytochrome circuit conserved in Vibrionaceae. Electroactive microbes capable of EET to Fe(III) usually also reduce toxic metals such as carcinogenic Cr(VI), which is converted to Cr(III), thus decreasing its toxicity and mobility. Here, the performance of V. natriegens was explored for the bioremediation of Cr(VI). At a density of 100 mg/mL, V. natriegens removed 5-20 mg/L Cr(VI) within 30 s and 100 mg/L Cr(VI) within 10 min. In comparison, the model bacterium Escherichia coli grown to a comparable cell density removed Cr(VI) 36 times slower. To eliminate Cr(VI), V. natriegens had to be metabolically active, and functional outer-membrane c-type cytochromes were required. At the end of the Cr(VI) removal process, V. natriegens had reduced all of it into Cr(III) while adsorbing more than half of the metallic ions. These results demonstrate that V. natriegens, with its fast metabolism, is a viable option for the rapid treatment of aqueous pollution with Cr.

The removal of Cr(VI) from aqueous solutions using microscale zerovalent iron (mZVI) shows promising potential. However, the surface passivation of mZVI particles hinders its widespread application. In this study, we prepared tannic acid (TA) modified mZVI composite (TA-mZVI) by a simple sonication method. The introduction of TA allowing TA-mZVI composite to adsorb Cr(VI) rapidly under electrostatic forces attraction, guarantying TA-mZVI exhibited remarkable Cr(VI) removal capacity with a maximum adsorption capacity of 106.1 mg⋅g-1. At an initial pH of 3, it achieved a rapid removal efficiency of 96.2% within just 5 min, which was 7.7 times higher than that of mZVI. Various characterizations, including XPS and CV analysis, indicated that the formation of TA-Fe complexes accelerates electron transfer. In addition, TA endows functional groups to TA-mZVI, raising the dispersion and stability and serves as a protective layer hindering passivation. Further mechanistic analysis revealed that Cr(VI) removal by TA-mZVI followed an adsorption-reduction-precipitation mechanism, with TA mitigating the surface passivation of mZVI and facilitating the reduction of most Cr(VI) to Cr(III). Batch cyclic experiments revealed that TA-mZVI exhibited satisfactory performance, maintaining over 85% Cr(VI) removal even after five cycles and minimally affected by various coexisting ions. With notable advantages in cost-effectiveness, ease-synthesis and recovery, this work provides a great promise for developing efficient reactive adsorbent for addressing Cr(VI) contamination in aqueous solutions.