Catalytic hydrolysis: A novel role of zero-valent iron in haloacetonitrile degradation and transformation in unbuffered systems

Highlights: • Haloacetamides and haloacetic acids were dominant products of HANs in ZVI system. • ZVI promoted HAN hydrolysis via catalysis rather than via redox or dehalogenation. • Notably, increased initial pH enhanced HAN degradation in unbuffered ZVI system. • The calculated cytotoxicity and genotoxicity decreased by 88% and 85% during HAN removal. Efforts to remove highly toxic haloacetonitriles (HANs) is an important step to reduce health risks associated with disinfection by product exposure. Zero valent iron (ZVI) is a versatile material, whose reductant, sorbent and coagulant role has been well understood. However, their catalytic role is less known. In this study, the degradation and transformation of HANs in ZVI system were investigated. Significant decreases of the four HANs in ZVI system were observed, and haloacetamides and haloacetic acids (hydrolysis products of HANs) were the dominant transformation products of HANs. However dehalogenated HANs, Fe (II) and Fe (III) were rarely detected after reaction, indicating that the ZVI acted as a catalyst to promote the hydrolysis of HANs, rather than other previously reported causes (dehalogenation or redox reaction). The HAN degradation rates were dramatically affected by the initial pH, ZVI doses and initial HAN concentration. Kinetic analysis indicated that HAN removal was enhanced with the increase of initial pH (5–9), ZVI doses (1–10 g/L), and initial HAN concentration (25–200 μg/L). ZVI induced the transformation of HANs to haloacetamides, haloacetic acids and other de-halogenated compounds, which reduced the cytotoxicity and genotoxicity by 88% and 85%, respectively. This study helped to understand the fate of HAN during the transmission in cast iron pipes, and provided a theoretical foundation for future HAN control and monitoring efforts.