Mobilization and methylation of mercury with sulfur addition in paddy soil: Implications for integrated water-sulfur management in controlling Hg accumulation in rice

Sulfur-fertilizer is commonly applied in croplands and in immobilizing Hg in contaminated soil. However, there is still great uncertainty and controversy concerning Hg transportability and transformation when supplying sulfur in paddies with complex conditions. Herein, we explored the effect of adding sulfate in paddy soil at different rice growth stages on soil Hg release and MeHg accumulation in rice and uncovered the correlation between sulfur induced MeHg production and the dynamically changed soil E_h, dissolved Fe, and dissolved organic carbon (DOC). In specific, sulfate addition at early stages (flooding period) triggered the decrease of E_h and increase of DOC and dissolved Fe, which in turn promoted Hg release and favored MeHg generation (increased by 235.19-555.07% vs control). Interestingly, adding sulfate at late stages (drainage condition), as compared with that at early stages, alleviated Hg release and MeHg production accompanied by the increase of E_h and decrease of dissolved Fe and DOC. The microcosmic experiment further confirmed the reduction of sulfate to sulfide promoted the change of E_h, thereby stimulating HgS dissolution in soil extract. The results give clues on the rational application of sulfur-fertilizer and through the water-sulfur fertilizer management considering the correspondingly changed soil conditions to diminish Hg bioavailability and MeHg production in paddies and paddy-like environments.