Sources and transfer mechanisms of dissolved organic matter during storm and inter-storm conditions in a lowland headwater catchment: constraints from high-frequency molecular data

Abstract

Abstract. The transfer of dissolved organic matter (DOM) at soil–river interfaces controls the biogeochemistry of micropollutants and the equilibrium between continental and oceanic C reservoirs. Then determining the transfer mechanisms of DOM is of main importance for ecological and geochemical reasons. Is stream DOM the result of the flushing of pre-existing soil DOM reservoirs activated by the modification of water flow paths? The evolution of the chemical composition of stream DOM investigated by thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide (TMAH) coupled to a gas chromatograph and mass spectrometer (THM-GC-MS) during inter-storm conditions and five storm events with a high-frequency sampling gives new insights on this question. In inter-storm conditions, stream DOM is inherited from the flushing of soil DOM, while during storm events, the modification of the distribution of chemical biomarkers allows the identification of three additional mechanisms. The first one corresponds to the destabilization of microbial biofilms by the increase in water velocity resulting in the fleeting export of a microbial pool. The second mechanism corresponds to the erosion of soils and river banks leading to a partition of organic matter between particles and dissolved phase. The third mechanism is linked to the increase in water velocity in soils that could induce the erosion of macropore walls, leading to an in-soil partitioning between soil microparticles and dissolved phase. The contribution of this in-soil erosive process would be linked to the magnitude of the hydraulic gradient following the rise of water table and could persist after the recession, which could explain why the return to inter-storm composition of DOM does not follow the same temporal scheme as the discharge. Those results are of main importance to understand the transfer of nutrients and micropollutants at the soil–river interfaces during the hot moments that are storm events.