Soil solution chemistry depends largely on mineralogy and organic matter properties of soil horizons with which they interact. Differing lithologies within a given catchment area can influence variability in soil cation exchange capacities and affect solute transport. Zero-tension and tension lysimeters were used to evaluate the fast transport of solutes in the topsoil vs. slow diffusional matrix flow at the subsoil of three contrasting lithology catchments in a mid-elevation mountain forest. Our aim was to test the feasibility of lysimeters' hydrochemical data as a gauge for legacy subsoil pollution. Due to contrasting lithologies, atmospheric legacy pollution prevailing at the soil-regolith interface is differently yet consistently reflected by beryllium, lead, and chromium soil solution concentrations of the three catchments. Geochemical (dis)equilibrium between the soil and soil matrix water governed the hydrochemistry of the soil solutions at the time of collection, potentially contributing to decreased dissolved concentrations with increased depths at sites with higher soil pH. A complementary isotopic δ18O runoff generation model constrained potential seasonal responses and pointed to sufficiently long water-regolith interactions as to permit important seasonal contributions of groundwater enriched in chemical species to the topsoil levels. Our study also reflects subsoil equilibration with atmospheric solutes deposited at the topsoil and thus provides guidance for evaluating legacy pollution in soil profiles derived from contrasting lithology.

Department of Biological Sciences Virginia Tech 926 West Campus Drive Blacksburg VA 24061 USA

Department of Environmental Geochemistry and Biogeochemistry Czech Geological Survey Geologická 6 152 00 Prague 5 Czechia

Institute of Soil Biology and Biogeochemistry Biology Centre of the Czech Academy of Sciences Na Sádkách 7 37005 České Budějovice Czechia

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