Spatial variation in the origin and reactivity of dissolved organic matter in Oregon-Washington coastal waters

Combining stable carbon isotopic signatures (δ 13 C-DOC) and optical properties of dissolved organic matter (DOM), we examined spatial variability in the sources and reactivity of DOM from Oregon-Washington coastal waters, with a particular focus on evaluating whether these measurements may reliably trace terrigenous DOM in coastal oceans. We sampled four stations on the continental shelf and four stations on the continental slope near the mouth of the Columbia River, with sampling depths ranging from 0 to 1,678 m. Nitrate and phosphate concentrations were largely controlled by organic matter (OM) regeneration although the river plume may have led to excess nitrates in relation to phosphates near the river mouth and/or the surface. Four fluorescence components (C1 to C4) were identified by using excitation emission matrices-parallel factor analysis. C1 and C2 were assigned as humic-like components which represented degraded DOM rather than OM of allochthonous or autochthonous origin. C3 and C4 were both labile, protein-like components representing autochthonous contributions, while C4 was more sensitive to diagenesis. In the shallow water layer (salinity ≤32.5 and depth ≤50 m), the variation in absorption properties (SUVA 254 and ɛ 280 ), fluorescence index, freshness index ( β / α ), percent fluorescence of C3, and δ 13 C-DOC revealed that the Columbia River plume exported DOM that was characterized by greater aromaticity, higher molecular weight, and being more decomposed than marine, autochthonous DOM. However, these signatures of terrigenous DOM disappeared rapidly with increasing depth and offshore distance. In the intermediate and deep water layers (salinity >32.5), the DOM indices were most driven by diagenesis, with changes in percent fluorescence components indicating increasing accumulation of humic DOM relative to protein-like DOM with depth. Principal component analysis that collectively assessed the DOM indices suggests that diagenesis was the primary factor driving the spatial variability of DOM properties in the study region, underlining challenges in tracing allochthonous DOM in coastal waters.