Sorption mechanisms of diphenylarsinic acid on ferrihydrite, goethite and hematite using sequential extraction, FTIR measurement and XAFS spectroscopy.

Abstract Diphenylarsinic acid (DPAA) is an organoarsenic compound derived from abandoned chemical weapons. DPAA sorption by iron (hydr)oxides is of considerable importance but remains largely unexplored. The current study aimed at investigating the sorption mechanisms of DPAA on ferrihydrite, goethite and hematite using both macroscopic sorption kinetics and sequential extraction procedure (SEP) as well as microscopic Fourier transformed infrared (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopic techniques. Sorption kinetics studies show that >93% of added DPAA (4–100 mg L−1) was sorbed on ferrihydrite and hematite within 5 min, while only 84% of added DPAA (100 mg L−1) was sorbed on goethite after 24 h. The sequential extraction results and FTIR measurements reveal that DPAA formed simultaneously inner- and outer-sphere complexes on goethite and hematite, but predominantly inner-sphere complexes on ferrihydrite with limited formation of outer-sphere complexes (<15%). A combination of SEP, FTIR and EXAFS techniques further enables identification of the interfacial reactions between DPAA and solid surfaces of iron (hydr)oxides and the mechanisms involved. Results indicate that DPAA interacted with these iron (hydr)oxides via (1) electrostatic attraction or hydrogen bonding, (2) surface complexation and (3) complexation embedded inside the mineral particles. EXAFS studies further demonstrate that DPAA formed mainly bidentate binuclear corner-sharing (2 C) complexes regardless of the iron substrate, with As-Fe distances at 3.19–3.32 Å. Comparison of these results with available data in the literature on inorganic, methyl and phenyl arsenics (As) suggests that it is the phenyl group substitution that finally determines the predominance of 2 C complexes. Results from the present study will improve our knowledge of DPAA interaction with solid surfaces and may help in the prediction of the environmental fate and environmental risk management of DPAA in the soil-water system. Graphical abstract Unlabelled Image Highlights • We first investigated DPAA sorption on goethite and hematite. • DPAA formed both inner- and outer-sphere bonds on goethite and hematite. • DPAA formed predominantly inner-sphere bonds on ferrihydrite. • Inner-sphere bond was formed via complexation on the surface and embedded inside. • The dominant inner-sphere bonds of DPAA were identified as bidentate binuclear. [ABSTRACT FROM AUTHOR]