Attenuation of barium, strontium, cobalt, and nickel plumes formed during microbial iron-reduction in a crude-oil-contaminated aquifer

We assessed the spatial distribution of 35 elements in aquifer sediments and groundwater of a crude-oil-contaminated aquifer and show evidence of the dissolution of barium (Ba), strontium (Sr), cobalt (Co), and nickel (Ni) during hydrocarbon oxidation coupled to historic microbial Fe(III)-reduction near the oil. Trace element plumes occur in the crude-oil-contaminated aquifer, where 50% Co, 47% Ni, 24% Ba, and 15% Sr have been mobilized from the sediment near the oil into groundwater, resulting in dissolved masses >33, 18, three, and two times greater than estimated dissolved masses prior to contamination, respectively. Ba²⁺ and Ni²⁺ concentrations exceeded the World Health Organization’s drinking-water guidelines of 700 and 20 μg/L, respectively. Sediments attenuate trace element plumes in two geochemically distinct zones, resulting in <0.01% total trace element masses dissolved in groundwater, despite the substantial mobilization near the oil body. Geochemical modeling of the modern Fe(III)-reducing zone suggests trace elements are likely attenuated via coprecipitation with/without sorption on iron carbonate precipitates. In the suboxic transition zone at the leading edge of the plume, Fe(III)-hydroxides sorb Ba²⁺, Sr²⁺, Co²⁺, and Ni²⁺. This study emphasizes that slow but persistent biogeochemical activity can substantially alter aquifer chemistry over decadal timeframes, a phenomenon we term biogeochemical gradualism.