Efficient remediation of different concentrations of Cr-contaminated soils by nano zero-valent iron modified with carboxymethyl cellulose and biochar.

Nano zero-valent iron (nZVI) is widely used in soil remediation due to its high reactivity. However, the easy agglomeration, poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation, especially in high concentration of Cr-contaminated soil. Herein, we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI. Along with the presence of biochar, 97.0% and 96.6% Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation. In addition, the immobilization efficiency of Cr(VI) only decreased by 5.1% through CMC-nZVI/BC treatment after 10 weeks aging in air, attributing to the strong antioxidation ability. As for the surrounding Cr-contaminated groundwater, the Cr(VI) removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics. CMC-nZVI/BC could efficiently remove 85% of Cr(VI) in about 400 hr when the initial Cr(VI) concentration was 40 mg/L and the flow rate was 0.5 mL/min. This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.

Enhanced remediation of Cr(VI)-contaminated soil by modified zero-valent iron with oxalic acid on biochar.

Hexavalent chromium (Cr(VI)) is carcinogenic and widely presented in soil. In this study, modified zero-valent iron (ZVI) with oxalic acid on biochar (OA-ZVI/BC) was prepared using wet ball milling method for the remediation of Cr(VI)-contaminated soil. Microscopic characterizations showed that ZVI were distributed on the biochar uniformly and confirmed the enhanced interface interaction between biochar and ZVI by wet ball milling. Electrochemical analysis indicated the strong electron transfer ability and enhanced corrosion behavior of OA-ZVI/BC. Moreover, inhibitory efficiencies of Cr(VI) removal with the addition of 1,10-phenanthroline suggested abundant Fe2+ generation in OA-ZVI/BC, which might facilitate the reduction of Cr(VI) to Cr(III). Theory calculation further demonstrated the ZVI modified by oxalic acid was more susceptible to solid-solid interfacial reactions with Cr(VI), and more electrons were transferred to Cr(VI). When applied to Cr(VI)-contaminated soil, OA-ZVI/BC could passivate 96.7 % total Cr(VI) and maintained for 90 days. The toxicity characteristic leaching procedure (TCLP) and simple based extraction test (SBET) were used to evaluate the leaching toxicity and bioaccessibility of Cr(VI), respectively. The TCLP-Cr(VI) decreased to 0.11 mg·L-1 after OA-ZVI/BC treatment, much lower than that of soils with ZVI/BC and OA-ZVI remediation (1.5 mg·L-1 and 4.1 mg·L-1). The bioaccessibility of Cr(VI) reduced by 93.5 % after 3-month remediation. Sequential extraction showed that Cr fractions in the soil after OA-ZVI/BC remediation was converted from acetic acid-extractable (HOAc-extractable) to more stable forms (e.g., residual and oxidizable forms). Benefiting from the synergies of oxalic acid, biochar and wet ball milling, OA-ZVI/BC exhibited an excellent performance on the remediation of Cr(VI)-contaminated soil, whose mechanisms involved adsorption, reduction (Fe0/Fe2+, Fe2+/Fe3+) and co-precipitation. This study herein develops a promising ZVI technology in the remediation of heavy metal-contaminated soil.

Ball milling enhanced Cr(VI) removal of zero-valent iron biochar composites: Functional groups response and dominant reduction species.

Zero-valent iron biochar composites (ZVI/BC) have been widely used to remove Cr(VI) from water. However, the application of ZVI/BC prepared by the carbothermal reduction was limited by the non-uniform dispersion of ZVI on the biochar surface. In this work, ball milling technique was introduced to modify ZVI/BC. Results showed that after ball milling, the maximum Langmuir adsorption capacity for Cr(VI) was 117.7 mg g-1 (298 K) which was 2.08 times higher than ZVI/BC. The initial adsorption rate of the Elovich model increased from 4.57 × 102 mg g-1 min-1 to 3.74 × 109 mg g-1 min-1 after ball milling. Dispersibility of ZVI on biochar surface and contact between ZVI and biochar were improved by the ball milling, thus accelerating the electron transfer. Besides, ball milling increased the content of oxygen-containing functional groups in biochar, contributing to the chemisorption of Cr(VI). The response sequence of oxygen-containing functional groups was analyzed by two-dimensional correlation spectroscopy, indicating that Cr(VI) preferentially complexed with phenolic -OH. Shielding experiments showed that Fe (0) was the dominant reducing species with a contribution of 73.4%, followed by surface-bound Fe(II) (21.3%) and dissolved Fe2+ (5.24%). Density functional theory calculations demonstrated that ball milled ZVI/BC improved the adsorption affinity and electron transfer flux towards Cr(VI) by introducing phenolic -OH and Fe (0). Combining all the textural characterization, the Cr(VI) removal mechanism of the ball milled ZVI/BC could be proposed as adsorption, reduction, and precipitation. Eventually, stable Cr-Fe oxides (FeOCr2O3 and Cr1·3Fe0·7O3) were formed. This work not only provides a simple method to modify ZVI/BC to remove Cr(VI) in water efficiently and rapidly, but also improves the mechanistic insight into the Cr(VI) removal by iron-carbon composites via the response sequence of functional group analysis and the quantitative analysis of reducing species.