Underlying lithology controls trace metal mobilization during redox fluctuations

Abstract

Redox state fluctuations are a primary mechanism controlling the mobilization of trace metals in soils. However, underlying lithology may modulate the effect that redox fluctuations have on trace metal mobility by influencing soil particle size and mineral composition. To investigate the relationships among trace metal behavior, lithology, and redox state, we subjected surface soils from two intensely weathered soil profiles formed on contrasting lithologies to consecutive, 8-day redox cycles. A suite of metals (Al, Mn, Fe, Ti, Rb, Zr, Nb, Mo, REEs, Pb, Th, U) were quantified in the aqueous phase (<10 nm) and solution (<415 nm, including colloids) from soil slurries. In soil formed on volcaniclastic bedrock with high clay content and a high abundance of short-range-ordered Fe-(oxyhydr)oxides phases (e.g. nano-goethite; quantified by Mössbauer spectroscopy), reducing events and colloidal dynamics drove trace metal mobilization. In contrast, in soil formed on granite bedrock with lower clay content and a low abundance of short-range-ordered Fe-(oxyhydr)oxides phases (nano-goethite and lepidocrocite), overall trace metal mobilization was lower, and mobilization was not predictable from redox state. Molybdenum isotopes were also measured through redox cycles but did not exhibit redox-dependent behavior. This study provides direct evidence that lithology remains an overarching factor governing the characteristics of metal mobility in soils, even after extended and intense chemical weathering and soil development processes.