High-frequency measurements explain quantity and quality of dissolved organic carbon mobilization in a headwater catchment

Abstract. Increasing dissolved organic carbon (DOC) concentrations and exports from headwater catchments impact the quality of downstream waters and pose challenges to water supply. The importance of riparian zones for DOC export from catchments in humid, temperate climates has generally been acknowledged, but the hydrological controls and biogeochemical factors that govern mobilization of DOC from riparian zones remain elusive. A high-frequency dataset (15 min resolution for over 1 year) from a headwater catchment in the Harz Mountains (Germany) was analyzed for dominant patterns in DOC concentration ( CDOC ) and optical DOC quality parameters SUVA 254 and S275−295 (spectral slope between 275 and 295 nm) on event and seasonal scales. Quality parameters and CDOC systematically changed with increasing fractions of high-frequency quick flow ( Qhf ) and antecedent hydroclimatic conditions, defined by the following metrics: aridity index (AI 60 ) of the preceding 60 d and the quotient of mean temperature ( T30 ) and mean discharge ( Q30 ) of the preceding 30 d, which we refer to as discharge-normalized temperature (DNT 30 ). Selected statistical multiple linear regression models for the complete time series ( R2=0.72 , 0.64 and 0.65 for CDOC , SUVA 254 and S275−295 , resp.) captured DOC dynamics based on event ( Qhf and baseflow) and seasonal-scale predictors (AI 60 , DNT 30 ). The relative importance of seasonal-scale predictors allowed for the separation of three hydroclimatic states (warm and dry, cold and wet, and intermediate). The specific DOC quality for each state indicates a shift in the activated source zones and highlights the importance of antecedent conditions and their impact on DOC accumulation and mobilization in the riparian zone. The warm and dry state results in high DOC concentrations during events and low concentrations between events and thus can be seen as mobilization limited, whereas the cold and wet state results in low concentration between and during events due to limited DOC accumulation in the riparian zone. The study demonstrates the considerable value of continuous high-frequency measurements of DOC quality and quantity and its (hydroclimatic) key controlling variables in quantitatively unraveling DOC mobilization in the riparian zone. These variables can be linked to DOC source activation by discharge events and the more seasonal control of DOC production in riparian soils.