Bromine species fluxes from Lake Constance's catchment, and a preliminary lake mass balance

190 t yr−1 of total dissolved bromine (TDBr) was delivered to the lake via 14 rivers and precipitation, with the rivers Alpenrhein (84 t TDBr yr−1) and the Schussen (50 t TDBr yr−1) providing the largest sources. The estimated particulate bromine flux contributed an extra 24-26 t Br yr−1. In comparison, only 40 t TDBr yr−1 was deposited to the lake's catchment by precipitation, and thus ∼80% of the riverine TDBr flux came from soils and rocks. Bromide was the dominant species accounting for, on average, 78% of TDBr concentrations and 93% of TDBr flux to the lake. Despite some high concentrations in the smaller lowland rivers, DOBr was only a minor component of the total riverine bromine flux (∼12 t yr−1, 7%), most of which came from the rivers Schussen, Bregenzer Ach and Argen. In contrast, most of the bromine in the sediment traps was bound to organic matter, and showed a clear seasonal pattern in concentrations, with a maximum in winter and minimum in summer. The summer minimum is thought to be due to dilution of a high Br autochthonous component by low bromine mineral and organic material from the catchment, which is supported by Ti, Zr and Br/Corg data. In the lake bromine was irreversibly lost to the sediments, with best flux estimates based on mass-balance and sediment trap data of +50-90 μg Br m−2 d−1. Overall, it appears that bromine is not simply a cyclic salt in the case of Lake Constance, with a clear geological component and dynamic lacustrine biogeochemistry.