Mechanochemical synthesis of cysteine-gum acacia intermolecular complex for multiple metal(loid) sequestration from herbal extracts.

The ubiquitous heavy metal(loid)s (HMs) contamination has triggered great concern about food safety, while sequestration and separation of trace HMs from herbal extracts still calls for appropriate sorbent materials. In this work, gum acacia was modified by cysteine to form a cysteine-acacia intermolecular complex (Cys-GA complex) via facile mechanochemical synthesis, aiming at capturing multiple HMs simultaneously. Preliminary screening confirms the superiority of Cys-CA complex for both cationic and anionic HMs, and determines an optimum Cys/GA mass ratio of 9:1 to achieve high removal capacities for Pb(II) (938 mg g-1), Cd(II) (834 mg g-1), As(V) (496 mg g-1), and Cr(VI) (647 mg g-1) in simulated aqueous solution. The analysis on HMs-exhausted Cys-GA complex indicates that Pb(II), As(V), and Cr(VI) tend to be removed through chelation, electrostatic attraction, and reduction, while Cd(II) can only be chelated or adsorbed by electrostatic interaction. The batch experiments on commercial herbal (e.g. Panax ginseng, Glycine max, Sophora flavescens, Gardenia jasminoides, Cyclocarya paliurus, and Bamboo leaf) extracts indicate that Cys-GA complex can reduce HMs concentration to attain acceptable level that comply with International Organization for Standardization, with negligible negative effect on its active ingredients. This work provides a practical and convenient strategy to purify HMs-contaminated foods without introducing secondary pollution.

Zero-valent iron-peroxydisulfate as synergistic co-milling agents for enhanced mechanochemical destruction of 2,4-dichlorophenol: Coupling reduction with oxidation.

Mechanochemical (MC) remediation with zero-valent iron (ZVI) as co-milling agent enables the non-combustion and solvent-free disposal of solid halogenated organic pollutants (HOPs) via solid-phase reaction, but suffers from incomplete dechlorination (especially for less chlorinated chemicals). Herein, a reduction-oxidation coupling strategy using ZVI and peroxydisulfate as synergistic (ZVI-PDS) co-milling agents was investigated, with 2,4-dichlorophenol (2,4-DCP) as probe contaminant. By revisiting the MC destruction process of 2,4-DCP by ZVI, the contribution of both reductive and oxidative routes is confirmed, and the inefficient •OH generation is addressed. With ball-to-material and reagent-to-pollutant mass ratios of 30:1 and 13:1, respectively, ZVI-PDS achieves higher dechlorination ratio (86.8%) for 2,4-DCP within 5 h, outcompeting sole ZVI (40.3%) or PDS (33.9%), due to the accumulation of numerous SO4•-. As suggested by a two-compartment kinetic model, the optimal ZVI/PDS molar ratio of 4:1 is determined, which balances the relative contribution of reductive/oxidative routes and leads to a maximum mineralization efficiency of 77.4%. The analysis on product distribution verifies the generation of dechlorinated, ring-opening and minor coupling products (with low acute toxicity). This work validates the necessity to couple reduction with oxidation in MC destruction for solid HOPs, and may provide information on reagent formulation.