Description: Burial of organic carbon in marine sediments has a profound influence in marine biogeochemical cycles and provides a sink for greenhouse gases such as CO2 and CH4. However, tracing organic carbon from primary production sources as well as its transformations in the sediment record remains challenging. Here we examine a novel but growing tool for tracing the biosynthetic origin of amino acid carbon skeletons, based on naturally occurring stable carbon isotope patterns in individual amino acids (δ13CAA). We focus on two important aspects for δ13CAA utility in sedimentary paleoarchives: first, the fidelity of source diagnostic of algal δ13CAA patterns across different oceanographic growth conditions, and second, the ability of δ13CAA patterns to record the degree of subsequent microbial amino acid synthesis after sedimentary burial. Using the marine diatom Thalassiosira weissflogii, we tested under controlled conditions how δ13CAA patterns respond to changing environmental conditions, including light, salinity, temperature, and pH. Our findings show that while differing oceanic growth conditions can change macromolecular cellular composition, δ13CAA isotopic patterns remain largely invariant. These results emphasize that δ13CAA patterns should accurately record biosynthetic sources across widely disparate oceanographic conditions. We also explored how δ13CAA patterns change as a function of age, total nitrogen and organic carbon content after burial, in a marine sediment core from a coastal upwelling area off Peru. Based on the four most informative amino acids for distinguishing between diatom and bacterial sources (i.e., isoleucine, lysine, leucine and tyrosine), bacterially derived amino acids ranged from 10 to 15 % in the sediment layers from the last 5000 years, and up to 35 % during the last glacial period. The greater bacterial contributions in older sediments indicate that bacterial activity and amino acid resynthesis progressed, approximately as a function of sediment age, to a substantially larger degree than suggested by changes in total organic nitrogen and carbon content. It is uncertain whether archaea may have contributed to sedimentary δ13CAA patterns we observe, and controlled culturing studies will be needed to investigate whether δ13CAA patterns can differentiate bacterial from archeal sources. Further research efforts are also needed to understand how closely δ13CAA patterns derived from hydrolyzable amino acids represent total sedimentary proteineincous material, and more broadly sedimentary organic nitrogen. Overall, however, both our culturing and sediment studies suggest that δ13CAA patterns in sediments will represent a novel proxy for understanding both primary production sources, and the direct bacterial role in the ultimate preservation of sedimentary organic matter.

Description: Despite the importance of the nitrogen (N) cycle on marine productivity, little is known about variability in N sources and cycling in the ocean in relation to natural and anthropogenic climate change. Beyond the last few decades of scientific observation, knowledge depends largely on proxy records derived from nitrogen stable isotopes (δ15N) preserved in sediments and other bioarchives. Traditional bulk δ15N measurements, however, represent the combined influence of N source and subsequent trophic transfers, often confounding environmental interpretation. Recently, compound-specific analysis of individual amino acids (δ15N-AA) has been shown as a means to deconvolve trophic level versus N source effects on the δ15N variability of bulk organic matter. Here, we demonstrate the first use of δ15N-AA in a paleoceanographic study, through analysis of annually secreted growth rings preserved in the organic endoskeletons of deep-sea gorgonian corals. In the Northwest Atlantic off Nova Scotia, coral δ15N is correlated with increasing presence of subtropical versus subpolar slope waters over the twentieth century. By using the new δ15N-AA approach to control for variable trophic processing, we are able to interpret coral bulk δ15N values as a proxy for nitrate source and, hence, slope water source partitioning. We conclude that the persistence of the warm, nutrient-rich regime since the early 1970s is largely unique in the context of the last approximately 1,800 yr. This evidence suggests that nutrient variability in this region is coordinated with recent changes in global climate and underscores the broad potential of δ15N-AA for paleoceanographic studies of the marine N cycle.