This paper evaluates a novel sorbent for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic fracturing wastewater (FWW). A series of iron-biochar (Fe-BC) composites with different Fe/BC impregnation mass ratios (0.5:1, 1:1, and 2:1) were prepared by mixing forestry wood waste-derived BC powder with an aqueous FeCl3 solution and subsequently pyrolyzing them at 1000 °C in a N2-purged tubular furnace. The porosity, surface morphology, crystalline structure, and interfacial chemical behavior of the Fe-BC composites were characterized, revealing that Fe chelated with CO bonds as COFe moieties on the BC surface, which were subsequently reduced to a CC bond and nanoscale zerovalent Fe (nZVI) during pyrolysis. The performance of the Fe-BC composites was evaluated for simultaneous removal of potentially toxic elements (Cu(II), Cr(VI), Zn(II), and As(V)), inherent cations (K, Na, Ca, Mg, Ba, and Sr), hetero-chloride (1,1,2-trichlorethane (1,1,2-TCA)), and total organic carbon (TOC) from high-salinity (233 g L-1 total dissolved solids (TDS)) model FWW. By elucidating the removal mechanisms of different contaminants, we demonstrated that Fe-BC (1:1) had an optimal reducing/charge-transfer reactivity owing to the homogenous distribution of nZVI with the highest Fe0/Fe2+ ratio. A lower Fe content in Fe-BC (0.5:1) resulted in a rapid exhaustion of Fe0, while a higher Fe content in Fe-BC (2:1) caused severe aggregation and oxidization of Fe0, contributing to its complexation/(co-)precipitation with Fe2+/Fe3+. All of the synthesized Fe-BC composites exhibited a high removal capacity for inherent cations (3.2-7.2 g g-1) in FWW through bridging with the CO bonds and cation-π interactions. Overall, this study illustrated the potential efficacy and mechanistic roles of Fe-BC composites for (pre-)treatment of high-salinity and complex FWW.

As a waste‐derived soil amendment with a long history, biochar has received extensive attention for its capability to improve soil fertility/health; remove or immobilize contaminants in soil, water and air; and mitigate climate change. With the aim of producing engineered biochars with excellent performances, new trends in biochar pyrolytic production and modification strategies have emerged. This review critically summarizes novel pyrolysis methods (e.g., microwave‐assisted pyrolysis, co‐pyrolysis and wet pyrolysis) and modification approaches (e.g., mineral modification, photocatalytic modification, electrochemical modification) with a focus on (a) the mechanisms involved in environmental remediation processes including soil immobilization, contaminant adsorption and catalytic oxidation; (b) effects of feedstock and pyrolysis conditions on physicochemical properties; (c) sustainability considerations in novel modification and pyrolysis strategies; and (d) the feasibility of extrapolating the results from wastewater treatment to soil remediation. It is argued that in order to achieve the maximum net environmental benefits, ‘greener’ modification methods are warranted, and the risks associated with pyrolysis of contaminated feedstock in soil amendment and contaminant sorption can be minimized through various novel approaches (e.g., co‐pyrolysis). Furthermore, novel pyrolysis methods can be combined with emerging modification strategies to synthesize more ‘effective’ biochars. Considering the similar aims of modification (e.g., increase surface area, introduce oxygen‐containing functional groups, increase aromaticity), the applicability of several novel approaches could in future can be expanded from contaminant adsorption/degradation in aqueous media to soil remediation/fertility improvement.

Stabilization/solidification (S/S) is a low-cost and high-efficiency remediation method for contaminated soils, however, conventional cement-based S/S method has environmental constraints and sustainability concerns. This study proposes a low-carbon, cement-free, clay-based approach for simultaneous S/S of As and Pb in the contaminated soil, and accordingly elucidates the chemical interactions between alkali-activated clay binders and potentially toxic elements. Quantitative X-ray diffraction and 27Al nuclear magnetic resonance analyses indicated that the addition of lime effectively activated the hydration of kaolinite clay, and the presence of limestone further enhanced the polymerization of hydrates. X-ray photoelectron spectroscopy showed that approximately 19% of As[III] was oxidized to As[V] in the alkali-activated clay system, which reduced toxicity and facilitated immobilization of As. During the cement-free S/S process, As and Pb consumed Ca(OH)2 and precipitated as Ca3(AsO4)2·4H2O and Pb3(NO3)(OH)5, respectively, accounting for the low leachability of As (7.0%) and Pb (5.4%). However, the reduced amount of Ca(OH)2 decreased the degree of hydration of clay minerals, and the pH buffering capacity of the contaminated soil hindered the pH increase. Sufficient dosage of lime was required for ensuring satisfactory solidification and contaminant immobilization of the clay-based S/S products. The leachability of As and Pb in high-Ca S/S treated soil samples was reduced by 96.2% and 98.8%, respectively. This is the first study developing a green and cement-free S/S of As- and Pb-contaminated soil using clay minerals as an environmentally compatible binding material.