Optimizing calcium materials for minimizing arsenate phytoavailability in upland arable soil based on geochemical...

This study aimed to evaluate the reducing effects of calcite and phosphogypsum on arsenate [As(V)] availability to plants and elucidate the mechanisms of As(V) immobilization. The concentration of available As(V) to plants in upland arable soils with 1% calcite and phosphogypsum decreased to 17.4% and 36.9%, respectively, compared to the control. As(V) phytoavailability depends on the soil pH and calcium materials. The process of stabilizing As(V) (F3; anion exchange) with phosphogypsum is faster and easier compared to that with calcite (F4; bind to carbonate), but it results in a less stable form. New Ca-As(V) minerals (Ca₅2(HAsO₄)x(AsO₄)∙yH₂O, Ca₅H₂x(AsO₄)∙yH₂O, or Ca₃2(AsO₄)∙10 H₂O) were identified in X-ray diffraction (XRD) patterns with calcite treatment. Precipitation, the primary mechanism induced by calcite, was activated at a soil pH above 8.0. Based on the deconvolution of calcium and sulfur X-ray photoelectron spectroscopy spectra and the peak shift in the XRD pattern in phosphogypsum, the substitution in which SO₄^2- is exchanged with HAsO₄^2- is the primary mechanism for As(V) immobilization. Substitution induced by phosphogypsum is a suitable reaction in upland arable soils, the predominant form of As(V) in the soil, with a pH range of 5-7.