Effects of thiolation and methylation on arsenic sorption to geothermal sediments

Arsenic (As) from deep crust is transported by geothermal waters to the earth surface and retained by sediment through adsorption, which depends significantly on the occurring As species. Adsorption of oxyarsenic species (i.e. arsenite [iAs(III)] and arsenate [iAs(V)]) on pure minerals was intensively investigated, yet studies with natural sediments and less known As species are scarce. To fill this gap, we investigated adsorption kinetics of nine different As species onto three typical geothermal sediments with different sedimentary organic matter (SOM) and iron (Fe) levels under anaerobic, sulfidic conditions (pH = 6). A multispecies pseudo-second-order (MPSO) model was applied to extract the adsorption rates of individual As species. Results showed that only the sediment with both high SOM and high Fe exhibited considerable As adsorption capacity. Air exposure or rise of either SOM or Fe levels in sediment favoured de-thiolation of aqueous thioarsenates, except for dimethylated thioarsenates. The overall adsorbed amount of the spiked As was affected by concurrent (de-)thiolation of the initial species, and the rates of their adsorption to the high SOM and high Fe sediment decreased in the order of tetrathioarsenate (TetraTA) > monothioarsenate (MTA) > iAs(V) > monomethyl arsenate (MMA) > dimethyl arsenate (DMA) > iAs(III) > monomethyl monothioarsenate (MMMTA) > dimethyl monothioarsenate (DMMTA) > dimethyl dithioarsenate (DMDTA). The fastest and slowest adsorption were suggested for inorganic thioarsenates and methylated thioarsenates, respectively. Therefore, under typical geothermal scenarios, thiolation of inorganic As would not necessarily increase its mobility, but the formation of methylated oxyarsenates and their further thiolation would endow geothermal As with strong migration ability.