Examining compound-specific nitrogen isotopic composition of amino acids (δ15NAA) as a new proxy for sedimentary organic N
Abstract:The stable nitrogen (N) isotopic (δ15N) signature of marine sedimentary N (δ15Nbulk) is commonly applied as a proxy for the δ15N of sinking particulate organic matter (δ15NPOMsink), and by extension the δ15N of marine primary production. Although a general correspondence between the δ15Nbulk and δ15NPOMsink exists in shallow water, diagenesis or mixtures of N sources can affect this relationship. For instance, diagenesis δ15Nbulk enrichment as a function of water depth (Robinson et al., 2012), and terrestrial N sources can constitute a large portion of total sedimentary N near continental margins (Schubert & Calvert, 2001). Compound-specific amino acid analysis (δ15NAA) represents a new approach to address these issues. Proteins and peptides comprise the majority of N-containing molecules in living organisms; hence δ15NAA may be a direct proxy for organic N-δ15N (δ15NON). However, the relationship between δ15NAA data and major sedimentary N fractions has not been evaluated.
We analyzed δ15NAA and the δ15N composition of major operationally defined N fractions and their relative contribution to total N from marine POM and shallow sediments collected in Santa Barbara Basin (SBB). Fractions analyzed include bulk, acid-soluble (AS), acid-insoluble (AI), and total hydrolysable amino acid (THAA). Average sedimentary δ15NTHAA and δ15NAS are enriched relative to δ15Nbulk by 2.9‰ and 1.0‰, respectively and δ15NAI is depleted relative to δ15Nbulk by ~1.5‰. The δ15NAS and δ15NTHAA are closest to subsurface nitrate δ15N (~8‰) in SBB, consistent with a primary N source, while depleted δ15NAI values are consistent with a dominant terrestrial N source. Together, these findings help to characterize the mixture of ON compounds, including hydrolysable AA, found in fresh biomass and suggest that δ15NTHAA represents a valuable new molecular level proxy for sedimentary proteinaceous material, but requires calibration to reconstruct δ15N of source N.