Photochemical and microbial degradation of dissolved lignin phenols: Implications for the fate of terrigenous dissolved organic matter in marine environments

Molecular level characterizations of dissolved lignin were conducted in Mississippi River plume waters to study the impact of various removal mechanisms (photooxidation, microbial degradation, and flocculation) on dissolved organic material (DOM) concentrations and compositions. Prior to analysis, dissolved (<0.2-μm pore size) samples were size fractionated by ultrafiltration into high molecular weight (HMW; >1 kDalton) and low molecular weight (LMW; <1 kDalton) components. At salinities <25 psu, flocculation and microbial degradation were the primary factors affecting lignin concentrations. At salinities >25 psu, photooxidation was a dominant factor influencing lignin compositions and concentrations. Diagnostic indicators of photooxidation include a sharp decrease in the percentage of lignin in the HMW size fraction, changes in ratios of syringyl to vanillyl phenols, and increases in LMW acid:aldehyde ratios for both vanillyl and syringyl phenols. A 10-day incubation experiment with plume water indicated rates of microbial degradation of dissolved lignin that were ∼30% of photooxidation rates in surface waters. These results highlight the importance of microbial as well as photochemical processes in the cycling of terrigenous DOM in coastal waters. Neither flocculation nor microbial degradation significantly altered lignin composition, suggesting that composition is primarily determined by source and photochemical transformation. Overall, high removal rates indicate the potential importance of terrigenous DOM as a carbon and nutrient source in the coastal ocean. Strong correlations between absorption coefficients at 350 nm and dissolved lignin demonstrate the potential for using absorption to trace terrigenous DOM in coastal environments with significant riverine input.