Amino acid and amino sugar compositional changes during in vitro degradation of algal organic matter indicate rapid bacterial re-synthesis

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Amino acids (AA) and, more recently, amino sugars (AS) in marine or lacustrine sediments have been increasingly used as paleoproxies. In order to assess AA and AS compositional changes during simulated microbial degradation, as well as to understand the importance of amino-compound re-synthesis by microbes during early diagenesis, decomposition experiments (300 days) were performed with algal (Fragilaria crotonensis) organic matter (OM)/quartz-sand mixtures under controlled redox conditions. Despite expected greater overall degradability under oxic conditions, decomposition kinetics of the bulk algal OM, as well as the total particulate AA and AS were similar under oxic and anoxic conditions, following exponential decay kinetics consistent with the observed mobilization and transfer of large parts of the particulate organic carbon (C) and nitrogen (N) into the dissolved inorganic and organic C and N pools. Carbon-normalized AA and AS yields suggest relative enrichment of amino compounds during partial decomposition, indicating the production and accumulation of microbial biomass during early diagenesis, independent of the redox environment. Moreover, AA and AS compositional changes, such as the relative enrichment of the AA glycine and the AS muramic acid (MurA), and the decrease in the molar ratio of glucosamine and galactosamine (GlcN:GalN) during degradation in both redox systems, were consistent with significant bacterial re-synthesis and the preferential preservation of bacterial biomaterial with increasing diagenesis. Large disparities between different bacterial amino-sugar based estimates of bacterial contribution indicate that bacterial end-member compositions are not currently known well enough to make these bacterial-biomarker constraints quantitative. However, the overall trends are consistent, indicating substantial turnover of eukaryotic into bacterial OM on short time scales of weeks to months. Together these results suggest that the influence of bacterial reworking in conserving sedimentary OM via its transfer into more refractory OM pools may be substantially greater than previously appreciated. We also investigated established amino-compound based indicators of OM degradation, bacterial synthesis, and sediment reactivity. Despite discrepancies, which we attribute to different susceptibilities of the respective indicators towards degradational changes on different time-scales, the tested indices were overall consistent with past data. These results therefore confirm their value as universal indicators of OM diagenesis. Together, our data highlight the vital role of bacterial reworking on the composition of sedimentary OM, with important implications for the alteration of primary geochemical signatures during early sedimentary diagenesis and their use as proxies in paleoenvironmental studies.