Linkage between the temporal and spatial variability of dissolved organic matter and whole-stream metabolism

Dissolved organic matter (DOM) is an important resource for microbes, thus affecting whole-stream metabolism. However, the factors influencing its chemical composition and thereby also its bio-availability are complex and not thoroughly understood. It was hypothesized that whole-stream metabolism is linked to DOM composition and that the coupling of both is influenced by seasonality and different land-use types. We tested this hypothesis in a comparative study on two pristine forestry streams and two non-forestry streams. The investigated streams were located in the Harz Mountains (central Europe, Germany). The metabolic rate was measured with a classical two-station oxygen change technique and the variability of DOM with fluorescence spectroscopy. All streams were clearly net heterotrophic, whereby non-forestry streams showed a higher primary production, which was correlated to irradiance and phosphorus concentration. We detected three CDOM components (C1, C2, C3) using parallel factor (PARAFAC) analysis. We compared the excitation and emission maxima of these components with the literature and correlated the PARAFAC components with each other and with fluorescence indices. The correlations suggest that two PARAFAC components are derived from allochthonous sources (C1, C3) and one is derived autochthonously (C2). The chromophoric DOM matrix was dominated by signals of humic-like substances with a highly complex structure, followed by humic-like, fulfic acids, low-molecular-weight substances, and with minor amounts of amino acids and proteins. The ratios of these PARAFAC components (C1 : C2, C1 : C3, C3 : C2) differed with respect to stream types (forestry versus non-forestry). We demonstrated a significant correlation between gross primary production (GPP) and signals of autochthonously derived, low-molecular-weight humic-like substances. A positive correlation between P/R (i.e. GPP/daily community respiration) and the fluorescence index FI suggests that the amount of autochthonously produced DOM increased overall with increasing GPP. In accordance with the coupling between DOM and the metabolism, our data also indicate that the composition of DOM is subject to seasonal fluctuations. We concluded that temporal and spatial differences in DOM composition are driven by whole-stream metabolism, in addition to pronounced effects coming from allochthonous sources.