Trace metals and metalloids and Ga/Al ratios in grey shale weathering profiles along a climate gradient and in batch reactors

Abstract

Shale is an important lithology globally due to its wide spatial abundance and potentially high trace metal and metalloid (TMM) geochemistry, which can be potentially inherited by its overlying soils. Unlike other soils, shale-derived soils inherit organic matter and oxides (Fe and Mn) which promote accumulation and retention of both geogenic and exogeneous TMMs. Here, we explore TMMs in seven grey shales weathering profiles along a north–south transect spanning the western flank of the Appalachian Mountains from New York to Tennessee. Overall, total TMM concentrations in the grey shales and their soils were below concentrations known to be toxic and below concentrations observed in black shales. Tau values show that shale-derived soils are net accumulators of many TMMs (As, Cd, Co, Cu, Ni, Pb, Sb, Sn and Zn) but others (Cr, W, and V) showed a net depletion. Many of the TMMs had high proportions (5–50%) that were sequestered in reducible phases (amorphous and crystalline Fe oxides) but few TMMs were associated with oxidizable phases (organic matter, reduced minerals). Sulfides and oxides (Mn nor Fe) were not detected by X-ray diffraction (<2% g/g). TMM accumulation and release during weathering was not extensively related to climate or soil development/age as we hypothesized, potentially due to localized effects of vegetation, geomorphology, pollution, and physicochemical parameters of the shale. Our laboratory batch reactor experiments indicated that some TMMs had highest release rates under oxic, acidic conditions with organic acids present (Cr, Ga, Sn, Sb, and W) implying aluminosilicate dissolution control or under slightly acidic, reduced conditions (As, Cd, Co, Cu, Ni, Pb, V, and Zn), suggesting association with geogenic oxides. Total Ga/Al ratios in rock to soil profiles were not varying significantly across the climate-soil development gradient, despite batch reactor acidic conditions generating low Ga/Al ratios. This implies weathering of shales is dominated by processes that do not fractionate Ga/Al ratio (organic or inorganic colloid production) as our laboratory results suggests oxic, acidic aluminosilicate weathering should generate a high Ga/Al solid phase.