Organic amendments temporarily change arsenic speciation and bioaccessibility in a lead and arsenic co‐contaminated urban soil

Abstract Organic amendments often reduce the bioaccessibility of soil lead (Pb) but not that of soil arsenic (As). The effect of Pb on As bioaccessibility is rarely studied in co‐contaminated soils. In a field study, we assessed the effect of mushroom compost, leaf compost, noncomposted biosolids, and composted biosolids amendments on As speciation in a co‐contaminated (As and Pb) soil at 7, 349, and 642 days after amending soils and the change of As speciation during an in vitro bioaccessibility extraction (gastric solution, pH 2.5) using bulk X‐ray absorption near‐edge structure spectroscopy. Soil was contaminated by coal combustion and other diffuse sources and had low As bioaccessibility (7%–12%). Unamended soil had As(III) sorbed onto pyrite (As(III)‐pyrite; ∼60%) and As(V) adsorbed onto Fe oxy(hydr)oxides (As(V)‐Fh; ∼40%). In amended soils, except in composted biosolids‐amended soils, at 7 days, As(V)‐Fh decreased to 15%–26% and redistributed into As(III)‐Fh and/or As(III)‐pyrite. This transformation was most pronounced in mushroom compost amended soil resulting in a significant (46%) increase of As bioaccessibility compared to the unamended soil. Composted biosolids‐amended soils had relatively stable As(V)‐Fh. Lead arsenate formed during the in vitro extraction in amended soils, except in composted biosolids‐amended soils. Arsenic speciation and bioaccessibility were similar in 349‐ and 642‐day in all the amended and unamended soils. Reduction of As(V)‐Fh to As(III) forms in the short term in three of the amended soils showed the potential to increase As bioaccessibility. The formation of stable lead arsenate during the in vitro extraction would counteract the short‐term increase of As bioaccessibility in those amended soils.