Arsenic speciation in picromerite K2Mg(SO4)2•6H2O: Electron paramagnetic resonance and synchrotron X-ray absorption spectroscopic characterizations and implications for organic fertilizers

Abstract

Picromerite K2Mg(SO4)2•6H2O (also known as schoenite, schönite, or sulfate of potash) formed from alkaline lakes by evaporation is an increasingly important chlorine-free fertilizer and has been used to produce other organic fertilizers such as arcanite K2SO4 and boussingaultite (NH4)2Mg(SO4)2•6H2O. Picromerite and boussingaultite, two Tutton’s salts, are also common secondary solid phases in diverse types of mine tailings and play important roles in controlling the mobility and bioavailability of various heavy metal(loid)s, including arsenic. In this study, picromerite crystals containing 64 ppm As have been synthesized at ambient conditions from aqueous solutions by slow evaporation. Arsenic K-edge X-ray absorption near-edge-structure (XANES) and extended X-ray absorption fine structure (EXAFS) data show that the dominant oxidation state is +5 and that As5+ occupies the S site in picromerite. Single-crystal and powder electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated picromerite reveal three arsenic-associated oxyradicals: AsO42−, AsO32−, and AsO22−. The orientations of the principal 75As hyperfine directions of the AsO32− and AsO22− radicals match the bonding directions of the SO42− groups in the picromerite structure, further supporting substitutions of their respective diamagnetic precursors AsO43- and AsO33- for the sulfate group. These AsO42−, AsO32−, and AsO22− radicals in picromerite are similar but not identical to their counterparts in boussingaultite and gypsum, suggesting that sulfate minerals are capable of sequestrating both arsenate and arsenite, with important implications for understanding the fate and bioavailability of arsenic associated with agricultural applications of organic fertilizers.