Measuring dissolved organic matter in estuarine and marine waters: size-exclusion chromatography with various detection methods

Environmental contextDissolved organic matter (DOM), a key parameter in aquatic biogeochemistry, is difficult to characterise owing to its variable composition and structure. We report a chromatographic method with carbon, nitrogen and absorbance detection able to record the size distribution of DOM and changes in its composition. The method could be used to identify additional sources to river or coastal waters as well as monitoring the DOM size/reactivity continuum in open oceans. AbstractWe studied the performance and limitations of size-exclusion chromatography with organic carbon, ultraviolet and organic nitrogen detectors (SEC-OCD-UVD-OND) for characterising dissolved organic matter (DOM) in estuarine and marine waters. We identified a strong salt effect on dissolved organic carbon (DOC) determination; however, calibration gave good results at salinity levels close to those of the sample analysed (ΔS ± 2 psu (practical salinity units)), with limited matrix effects, enabling an accurate measurement of DOC, as demonstrated by an intercalibration exercise. The repeatability, reproducibility and limit of detection (3 ppb for both carbon and nitrogen) for the three detectors demonstrated the robustness of the method for a wide range of natural waters, including carbon-rich freshwaters and deep seawaters with low carbon content (6000 ppb-C to 300 ppb-C). Deeper analysis of the SEC demonstrated that proteins and polysaccharides are partly fractionated within the column, and that terrestrial humic substances, isolated on a XAD-8 resin, can also be eluted in both fractions associated with biopolymers and low-molecular-weight neutrals. Application of the method to the study of DOM along a macrotidal estuary that was influenced by agricultural activities revealed significant changes in its composition despite a conservative DOC distribution. Distinct origins and qualities of high-molecular-weight (>500 kDa) organic compounds were identified for riverine and marine end-members. A new diagram to track changes in DOM lability is proposed to complete the humic-substances diagram.