Amino acid biogeo- and stereochemistry in coastal Chilean sediments

The spatial distribution of total hydrolysable amino acids (THAA) and amino acid enantiomers ( d- and l-forms) was investigated in sediments underlying two contrasting Chilean upwelling regions: at ∼23 °S off Antofagasta and at ∼36 °S off Concepción. The contribution of amino acids to total organic carbon (%T AAC: 7–14%) and total nitrogen (%T AAN: 23–38%) in surface sediments decreased with increasing water depth (from 126 to 1350 m) indicating that organic matter becomes increasingly decomposed in surface sediments at greater water depth. Changes in the ratio between the protein amino acid aspartate and its non-protein degradation product β-alanine confirmed this observation. Furthermore, estimates of THAA mineralization showed that sedimentary amino acid reactivity decreased with both increasing water depth as well as progressive degradation status of the organic matter that was incorporated into the sediment. Reactivity of organic matter in the sediment was also assessed using the Degradation Index (DI) developed by [Dauwe, B., Middelburg, J.J., 1998. Amino acids and hexosamines as indicators of organic matter degradation state in North Sea sediments. Limnol. Oceanogr. 43, pp. 782–798.]. Off Concepción, DI was successfully applied to examine the degradation status of sedimentary organic matter at different water depths. However, unexpected results were obtained at the Antofagasta stations as DI increased with sediment depth, suggesting more degraded organic matter at the surface than deeper in the cores. The contribution of peptidoglycan amino acids to THAA was estimated from the concentrations of d-aspartate, d-glutamic acid, d-serine, and d-alanine. Peptidoglycan amino acids accounted for >18% of THAA in all investigated samples. In surface sediments peptidoglycan amino acids accounted for a progressively larger fraction of THAA at increasing water depths (up to >26%). Further, the contribution of peptidoglycan amino acids to THAA increased with increased sediment depth and age (up to 288-year-old) reaching up to 59%. Independent estimates based on d-amino acid concentrations in selected laboratory strains, bacterial counts and the sedimentary concentrations of d-amino acids indicate that a large fraction of the measured d-amino acids (>47 to >97%) originated from cell wall residues rather than from enumerated cells.