Vegetation canopy effects on total and dissolved Cl, Br, F and I concentrations in soil and their fate along the hydrological flow path.

Although halogens are omnipresent in the environment, detailed understanding of processes involving chlorine (Cl), bromine (Br), fluorine (F) and iodine (I) in the terrestrial halogen cycle is still sparse. Our objectives were to (i) assess vertical depth profiles of total and water-extractable inorganic halogen concentrations (Cl, Br, F, I) in solid soil, (ii) test the effect of a tree canopy, and (iii) follow the fate of dissolved inorganic halogens along the hydrological flow path. More than 200 soil samples and ecosystem solutions (rainwater, soil solution, adit and creek water) collected in the Schwarzwald, SW Germany, were analyzed by combustion ion chromatography and ion chromatography for total and inorganic halogen concentrations. We found decreasing Cl concentrations with increasing soil depth which were indicative of biological chlorination of organic matter and nutrient uplift, both associated with Cl accumulation in upper soil horizons. Vertical patterns of total Br, F and I were contrary to Cl concentrations and were related significantly (positively) to pedogenic oxides, revealing their dependence on abiotic processes. The presence of a canopy at our study site resulted in significantly higher halogen concentrations in throughfall compared to rainfall and higher Br concentrations in the organic layer. We attribute this difference to leaching from leaves and needles and wash-off of dry deposition. There were hardly any differences in halogen concentrations along the hydrological flow path except for significantly higher inorganic I concentrations in soil solution compared to rainfall due to equilibrium reactions between the soil solution and the solid soil phase. Highest inorganic F concentrations of up to 0.2 mg L were detected in creek water samples and may originate from the weathering of fluorite-bearing veins. Our study indicates halogen-specific processes underlying Cl, Br, I and F cycling in ecosystems.