Compound specific amino acid δ13C patterns in a deep-sea proteinaceous coral: Implications for reconstructing detailed δ13C records of exported primary production

Deep-sea proteinaceous corals represent high-resolution paleoarchives, extending biogeochemical time series far beyond recent instrumental data. While recent studies have applied compound specific amino acid δ15N (δ15N-AA) measurements of their organic skeletal layers to investigate Holocene nitrogen cycling, potential applications of amino acid δ13C (δ13C-AA) in proteinaceous corals have not yet been examined. Here we developed δ13C-AA analysis in deep-sea bamboo coral (Isidella sp.) from the Monterey Canyon to reconstruct exported primary production over an ~ 80 year record. Preserved deep-sea coral essential amino acid δ13C-AA patterns (δ13C-EAA) closely matched those expected from natural and cultured phytoplankton, supporting the hypothesis that deep-sea coral δ13C-EAA values represent unaltered signatures of exported primary production sources. The coral bulk δ13C record showed cyclic 0.5‰ variations over the last century, with a shift to lower δ13C values in the early 1960s. Variations in coral δ13C-EAA values closely followed bulk δ13C signatures, although both the range and the magnitude of change in the bulk δ13C record were highly attenuated compared to the δ13C-EAA record. Our results indicate that δ13C-EAA in proteinaceous corals represent a new, direct proxy for δ13C in primary production that is more sensitive and accurate than bulk δ13C. To test this idea, we used existing phytoplankton δ13C-AA data to calculate an offset between bulk δ13C and δ13C-EAA. When applied to our data, a reconstructed record of δ13C values for exported organic matter was consistent with regional phytoplankton dynamics and expected trophic transfer effects, suggesting significant AA resynthesis only in the non-essential AA pool. Together, these results indicate that δ13C-EAA in deep-sea proteinaceous corals provide a powerful new long-term, high resolution tool for investigating variations in exported primary production and biogeochemistry.