The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.

Metal oxide-modified biochar showed excellent adsorption performance in wastewater treatment. Iron nitrate and potassium permanganate were oxidative modifiers through which oxygen-containing groups and iron–manganese oxides could be introduced into biochar. In this study, iron–manganese (Fe–Mn) oxide-modified biochar (BC-FM) was synthesized using rice straw biochar, and the adsorption process, removal effect, and the mechanism of cadmium (Cd) adsorption on BC-FM in wastewater treatment were explored through batch adsorption experiments and characterization (SEM, BET, FTIR, XRD, and XPS). Adsorption kinetics showed that the maximum adsorption capacity of BC-FM for Cd(II) was 120.77 mg/g at 298 K, which was approximately 1.5–10 times the amount of adsorption capacity for Cd(II) by potassium-modified or manganese-modified biochar as mentioned in the literature. The Cd(II) adsorption of BC-FM was well fit by the pseudo-second-order adsorption and Langmuir models, and it was a spontaneous and endothermic process. Adsorption was mainly controlled via a chemical adsorption mechanism. Moreover, BC-FM could maintain a Cd removal rate of approximately 50% even when reused three times. Cd(II) capture by BC-FM was facilitated by coprecipitation, surface complexation, electrostatic attraction, and cation-π interaction. Additionally, the loaded Fe–Mn oxides also played an important role in the removal of Cd(II) by redox reaction and ion exchange in BC-FM. The results suggested that BC-FM could be used as an efficient adsorbent for treating Cd-contaminated wastewater.

Selenium (Se) is regarded as a trace element for humans, but it is toxic in excess. In natural environments, the mobility of Se is dominantly controlled by the Se oxyanions with high solubility such as selenite (Se(IV)). Se(IV) is often associated with the omnipresent ferrihydrite and coexisting organic matter. However, there is little information on the dynamic interactions among Se(IV), fulvic acid, and ferrihydrite. This study investigated the influence of fulvic acid on ferrihydrite-Se(IV) coprecipitates (Fh-Se) transformation for 8 days and the subsequent behavior of Se(IV) at varied pH (5.0, 7.5, and 10.0). Results showed that fulvic acid had different effects on Fh-Se transformation at varied pH values. Fh-Se transformation was promoted by fulvic acid at initial pH 5.0 whereas it was inhibited at initial pH 10.0. Interestingly, at initial pH 7.5, Fh-Se transformation was promoted at a low C/Fe ratio while it was suppressed at a high C/Fe ratio. Besides, fulvic acid induced the generation of more extractable Se(IV) at initial pH 5.0 and more coprecipitated Se(IV) at initial pH 7.5 and blocked the release of Se(IV) at initial pH 10.0. Fulvic acid possibly interacted with Se(IV) via carboxyl complexation and weakened the inhibition of Se(IV) on Fh-Se transformation. Thus, fulvic acid increased the transformation rate of Fh-Se. These findings help to uncover the environmental behavior of Se(IV) and organic matter during ferrihydrite transformation.

Currently, alleviating antimony (Sb) contamination in aqueous solutions is crucial for restoring and recovering ecological and environmental health. Due to its toxicity, bioaccumulation and mobile characteristics, developing an efficient technique for antimony decontamination is imperative. Herein, we prepared a Fe–Cu-chitosan (FCC) composite by a one-step coprecipitation method, in which nanoscale Fe/Cu acts as the active sites and the whole structure is exhibited as porous microscale particles. A Fe/Cu proportion of 2/1 (FCC-2/1) was determined to be the optimum proportion for antimony adsorption, specifically 34.5 mg g⁻¹ for Sb(III) and 26.8 mg g⁻¹ for Sb(V) (initial concentration: 5.0 mg L⁻¹). Spectral characterization, batch experiments and density functional theory (DFT) simulations were applied to determine the adsorption mechanism, in which surface hydroxyls (-OH) were responsible for antimony complexion and Fe–Cu coupling was a major contributor to adsorption enhancement. According to kinetic analysis, Cu provided an electrostatic attraction during the adsorption process, which facilitated the transportation of antimony molecules to the material interface. In the meantime, the FCC electronic structure was modified due to the optimization of the Fe–Cu interface coupling. Based on the Mullikan net charge, the intrinsic Fe–O–Cu bond might favor interfacial electronic redistribution. When the antimony molecule contacted the adsorption interface, the electrons transferred swiftly as Fe/Cu 3d and O 2p orbital hybridization occurred, thus inducing a stabilizing effect. This work may offer a new perspective for binary oxide construction and its adsorption mechanism analysis.

Iron-based materials have been widely investigated because of their high surface reactivity, which has shown potential for the remediation of metal(loid)s in groundwater. However, the disadvantages of structural stability and economic feasibility always limit their application in permeable reactive barrier (PRB) technology. In this study, zeolite-supported iron particles (Zeo-Fe) were synthesized by an innovative low-cost physical preparation method that is suitable for mass production. The removal efficiency and mechanism of typical metal(loid)s (Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺) were subsequently investigated using various kinetic and equilibrium models and characterization methods. The results of scanning electron microscopy and energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) confirmed that zero valent iron (Fe⁰) and oxidation product (Fe₃O₄) were successfully loaded and efficiently dispersed on zeolite. The synthesized Zeo-Fe exhibited excellent adsorption and redox capacities for the cations Pb²⁺, Cd²⁺ and anions Cr⁶⁺, As³⁺. The increase in the pH resulting from Fe⁰ corrosion also enhanced the precipitation of Fe-metal(loid)s. The maximum removal capacity for Pb²⁺, Cd²⁺, Cr⁶⁺ and As³⁺ was up to 70.00, 9.12, 2.35 and 0.36 mg/g, respectively. The removal processes were well described by the pseudo-second-order kinetic model for Pb²⁺ and Cd²⁺, Lagergren pseudo first-order kinetics model for As³⁺ and double phase first order kinetics model l for Cr⁶⁺. Cr⁶⁺ was rapidly reduced to Cr³⁺ by the Fe⁰ stabilized on Zeo-Fe, and the oxidation of As³⁺ to As⁵⁺ was attributed to the Fe⁰/Fe²⁺ oxidation process at the interface over time, which was further demonstrated by the mineral phase and element valence analyses of reacted Zeo-Fe. The removal mechanism for metal(loid)s was a combination of physical and chemical processes, including adsorption, co-precipitation and reduction-oxidation. Conclusively, Zeo-Fe has been shown to have potential as an effective and economical material for removing various metal(loid)s used in PRB.

Cropland contamination by toxic trace metal (loid)s (TTMs) has attracted increasing attention due to the serious consequential threat to crop quality and human health. Mitigation of plant TTM stress by silica amendment has been proposed recently. However, the relationship between the siliceous structure of phytoliths and TTMs in plants, and the environmental implications of phytolith-occluded trace metal (loid)s (PhytTMs) remain unclear. This study assessed the accumulation of five metal (loid)s, including lead (Pb), zinc (Zn), cadmium (Cd), copper (Cu) and arsenic (As), in the organic tissues and phytoliths of wheat grown in a mixed-TTM contaminated soil under both lightly and heavily contaminated conditions. The results show that the concentrations of plant TTMs and PhytTMs were significantly (p < 0.05) positively correlated, and higher in heavily contaminated wheats than those in lightly contaminated ones. The bio-enrichment factors between phytoliths and organic tissues were higher for As (1.83), Pb (0.27) and Zn (0.30) than for Cd (0.03) and Cu (0.14), implying that As, Pb and Zn were more readily co-precipitated with silicon (Si) in phytolith structures than Cd and Cu. Network analysis of the relationship between soil and plant elements with PhytTMs showed that severe contamination could impact the homeostasis of elements in plants by altering the translocation of TTMs between soils, plants, and phytoliths. The accumulation of TTMs in phytoliths was affected by the capacity of Si deposition in tissues and chelation of TTMs with silica, which could impact the role of PhytTMs in global biogeochemical TTM cycles.

High-arsenic wastewater derived from the metallurgical industry of nonferrous minerals is one of the most dangerous arsenic (As) sources that usually follow the emission of massive hazardous arsenic-bearing wastes. Considering the properties of red mud (RM), we propose an alternative and environmentally friendly method for the efficient remediation of high-arsenic wastewater using RM through formation of AlAsO₄@silicate precipitate, aiming at ''zero-emission of hazardous solid waste''. The results show nearly 100% of arsenic could be stepwisely removed from high-arsenic wastewater and reduce the arsenic concentration from 6100 mg/L to 40 μg/L using RM at room temperature. The highest arsenic removal capacity of RM reaches 101.5 mg/g at a RM-to-wastewater ratio of 40 g/L due to the superior arsenic adsorption and the co-precipitation of arsenate and Al³⁺ to form insoluble aluminum arsenate. The silicate shell of arsenic-loaded RM created at an alkaline condition acts as an arsenic stabilizer, resulting in a leached arsenic concentration of 1.2 mg/L in TCLP tests. RM acts as a highly effective arsenic remover and stabilizer for the disposal of high-arsenic wastewater. It shows great potential for the remediation of wastewater containing heavy metals with varying concentrations to produce clean water available for industrial purpose.

Industrial by-products provide materials for remediation measures. In this study, a silicon-iron amendment was prepared from residue originating from acid-extracted copper (Cu) tailings based on thermal activation at temperatures ranging from 550 °C to 1150 °C for 30 min with the use of additives (CaO, Na₂CO₃, NaOH). The remediation performance of the amendment was evaluated through soil incubation and greenhouse pot experiments with vetiver (Vetiveria zizanioides). The results showed that the highest levels of soluble Si (6.11% of the total Si) and Fe (2.3% of the total Fe) in the amendment were achieved with thermal activation at 1150 °C for 30 min using an optimal ratio between residue and additives (residue: CaO: Na₂CO₃: NaOH = 1: 0.4: 0.4: 0.2). Heavy metal release indicated that the amendment could be safely used for soil remediation. The incubation experiments showed that the DTPA-extractable Cd, Cr and Pb in contaminated soils decreased with increasing amendment rate, which was not observed for As. The amendment-induced decrease in the Cd, Cr and Pb availability in contaminated soils could be explained by pH-change induced immobilization, Fe-induced chemisorption, Si-induced co-precipitation, and Ca-induced ion exchange. Correlation analysis suggested that there were significant negative correlations between DTPA-extractable Cd, Cr and Pb and the pH, Fe, Si, and Ca in soil pore water and soil. The most suitable amendment rate was determined to be 1% by balancing the efficacy and wise utilization of the amendment. The pot experiment demonstrated that the amendment promoted the vetiver growth and stimulated the accumulation of Cd and Cr in the roots. The amendment was proved to be promising for the phytostabilization of Cd, Cr and Pb in contaminated soils. Further investigations are required to determine whether the amendment is a tool for the long-term remediation of multi-metal-contaminated soils at the field scale.

Potentially toxic metals have become a viable threat to the ecosystem due to their carcinogenic nature. Biochar has gained substantial interest due to its redox-mediated processes and redox-active metals. Biochar has the capacity to directly adsorb the pollutants from contaminated environments through several mechanisms such as coprecipitation, complexation, ion exchange, and electrostatic interaction. Biochar's electron-mediating potential may be influenced by the cyclic transition of surface moieties and conjugated carbon structures. Thus, pyrolysis configuration, biomass material, retention time, oxygen flow, and heating time also affect biochar's redox properties. Generally, reactive oxygen species (ROS) exist as free radicals (FRs) in radical and non-radical forms, i.e., hydroxyl radical, superoxide, nitric oxide, hydrogen peroxide, and singlet oxygen. Heavy metals are involved in the production of FRs during redox-mediated reactions, which may contribute to ROS formation. This review aims to critically evaluate the redox-mediated characteristics of biochar produced from various biomass feedstocks under different pyrolysis conditions. In addition, we assessed the impact of biochar-assisted FRs redox-mediated processes on heavy metal immobilization and mobility. We also revealed new insights into the function of FRs in biochar and its potential uses for environment-friendly remediation and reducing the dependency on fossil-based materials, utilizing local residual biomass as a raw material in terms of sustainability.

Iron (III) co-precipitation with dissolved organic matter (DOM) is pervasive in many natural environments. However, the effects of DOM on the formation of Fe(III) hydroxysulfate (FHS) and its environmental implications are poorly understood. In this study, fulvic acid (FA) was used as a model DOM compound, and experiments were devised to investigate the effects of FA on the formation of FHS. In addition, the Pb(II) adsorption capabilities of FHSs biosynthesized under various FA dosages, including kinetics and sorption isotherm experiments, were conducted. These experiments showed that co-precipitation of FA promoted the formation of Fe-FA composites, FA-doped schwertmannite, and small particles of jarosite. Co-precipitates are more enriched in carboxyl (–COOH) functional groups due to their preferential binding with FHS. The adsorption kinetics, isotherms and mechanisms of Pb onto the biosynthesized FHSs were then comprehensively characterized and modeled. Though the specific surface area decreased with increasing FA loading, the introduction of FA into FHSs increased Pb(II) adsorption, with the highest concentration of FA addition improving the removal capacity of Pb(II) to 91.54%. Kinetics studies and intra-particle diffusion models indicated that the adsorption of Pb(II) onto the FHSs was correlated with the number of active sites, and two adsorption steps: surface adsorption and the diffusion of Pb(II) in channels inside the biosynthesized FHSs, are suggested. The adsorption mechanism was attributed to cation exchange between Pb(II) and –OH and –COOH functional groups, and the co-precipitated FA provided additional sites for Pb(II) adsorption by FHS.