Rivers and tidal flats as sources of dissolved organic matter and trace metals in the German Bight (North Sea)

The German Bight in the southern North Sea receives nutrients, dissolved organic matter (DOM), and trace metals from rivers, porewater reflux, and porewater outwelling. We studied the marine, riverine, and porewater sources analyzing molecular transformations of solid-phase extracted (SPE) DOM in the German Bight. We applied a combination of ultrahigh-resolution mass spectrometry (FT-ICR-MS) with quantitative data of dissolved organic sulfur (DOS), dissolved black carbon (DBC), dissolved trace metals (Ba, Co, Gd, Mo, Mn, W), and nutrients (nitrite, nitrate, phosphate, silicate). While aromatic DOM and DBC mainly originated from the rivers, nitrogen-containing, more saturated DOM was enriched offshore suggesting greater contributions of marine (algal) sources. Except for dissolved Mo, rivers were the primary source of trace metals and nutrients. However, tidal flats contributed to dissolved nutrient (e.g., dissolved phosphate), trace metal and DOS inventories of the southern North Sea. The input of DOS from intertidal flats was identified by the molecular index derived from sulfidic porewaters (I_SuP), non-conservative behavior of elemental sulfur-to-carbon ratio and sulfur content of molecular formulae (from FT-ICR-MS). Dissolved Mn and Si were removed in the German Bight, likely due to precipitation as Mn(hydr)oxides and biological uptake, respectively. Preliminary estimates suggest that DOS from porewater outwelling is approximately four times higher than DOS discharged by the three main rivers in the region. Our study therefore highlights the need to consider porewater discharge in addition to riverine sources to comprehensively assess elemental budgets within the complex interplay and transformations of DOM, nutrients, and trace metals in coastal ecosystems.