Effects of arsenic incorporation on jarosite dissolution rates and reaction products

摘要

Batch dissolution experiments were undertaken on synthetic arsenojarosites at pH 2, pH 8, and in ultra-pure water to better understand the influence of As incorporation on the kinetics and reaction products of jarosite dissolution. Incongruent jarosite dissolution was observed in all experiments. Arsenojarosite lacks the pH dependency observed in K-jarosite dissolution, likely the result of surface arsenate-iron complexes preventing protonation at low pH and repelling hydroxyls at high pH. The stronger bonding of arsenate to iron, compared to sulfate to iron, leads to an enrichment of surface layer arsenate-iron complex sites, inhibiting the dissolution of jarosite with time. The secondary reaction products formed during the dissolution of arsenojarosite include maghemite, goethite, and hematite in ultra-pure water, and ferrihydrite in pH 8 Tris buffered solution. Maghemite initially forms and transitions to hematite with time in ultra-pure water, but increasing arsenic concentrations slow this transition. At pH >3.5, arsenic from the dissolution of arsenojarosite adsorbs onto newly formed reaction products. Arsenic also inhibits the formation of goethite and reduces the crystallinity of the observed maghemite reaction products. The coprecipitation of iron oxides with increasing amounts of arsenic results in a change from spherical to " worm-like" aggregate morphology and provides a sink for arsenic released during arsenojarosite dissolution. This study shows that in open systems with a flush of fresh solution, arsenic incorporation in jarosite results in an increase in dissolution rates. In closed systems, however, increasing surface arsenate-iron complexes inhibit further dissolution of the underlying bulk material, causing a reduction in dissolution rates as arsenic incorporation increases.