Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

Meng Zhu, Yongming Luo, Ruyi Yang, Shoubiao Zhou, Juqin Zhang, Mengyun Zhang, Peter Christie, Elizabeth L. Rylott

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Front. Environ. Sci. Eng. ›› 2020, Vol. 14 ›› Issue (4) : 58. DOI: 10.1007/s11783-020-1237-x
RESEARCH ARTICLE
RESEARCH ARTICLE

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

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Highlights

• DPAA sorption data was found to fit the Freundlich equation.

Kf was significantly positive correlated with oxalate-extractable Fe2O3.

• Ligand exchange was the main mechanism for DPAA sorption on soils.

• Bidentate binuclear and monodentate mononuclear DPAA bonds were identified.

Abstract

Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, Kf, was significantly and positively correlated with oxalate-extractable Fe2O3. The Kf values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the Kf values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in Kf to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (2C) and monodentate mononuclear (1V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that 2C and 1V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of 1V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.

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Keywords

Diphenylarsinic acid / EXAFS / Fe (hydr)oxide / Soil organic matter / Sorption mechanism

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Meng Zhu, Yongming Luo, Ruyi Yang, Shoubiao Zhou, Juqin Zhang, Mengyun Zhang, Peter Christie, Elizabeth L. Rylott. Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy. Front. Environ. Sci. Eng., 2020, 14(4): 58 https://doi.org/10.1007/s11783-020-1237-x

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 41807117 and 41230858), the Cultivation Project on Excellent Undergraduates’ Thesis (design, create) of Anhui Normal University (No. pyjh2018487) and the Innovation and Entrepreneurship Training Project for College Students (No. 201910370072). The EXAFS data were obtained at the BL14W1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF). We thank Dr. Xu Wang at SSRF for help with EXAFS data analysis.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-020-1237-x and is accessible for authorized users.

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