Amino acid nitrogen isotopic fractionation patterns as indicators of heterotrophy in plankton, particulate, and dissolved organic matter

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Bulk nitrogen (N) isotope signatures have long been used to investigate organic N source and food web structure in aquatic ecosystems. This paper explores the use of compound-specific δ15N patterns of amino acids (δ15N-AA) as a new tool to examine source and processing history in non-living marine organic matter. We measured δ15N-AA distributions in plankton tows, sinking particulate organic matter (POM), and ultrafiltered dissolved organic matter (UDOM) in the central Pacific Ocean. δ15N-AA patterns in eukaryotic algae and mixed plankton tows closely resemble those previously reported in culture. δ15N differences between individual amino acids (AA) strongly suggest that the sharply divergent δ15N enrichment for different AA with trophic transfer, as first reported by [McClelland, J.W. and Montoya, J.P. (2002) Trophic relationships and the nitrogen isotopic composition of amino acids. Ecology83, 2173 2180], is a general phenomenon. In addition, differences in δ15N of individual AA indicative of trophic transfers are clearly preserved in sinking POM, along with additional changes that may indicate subsequent microbial reworking after incorporation into particles. We propose two internally normalized δ15N proxies that track heterotrophic processes in detrital organic matter. Both are based on isotopic signatures in multiple AA, chosen to minimize potential problems associated with any single compound in degraded materials. A trophic level indicator (ΔTr) is derived from the δ15N difference between selected groups of AA based on their relative enrichment with trophic transfer. We propose that a corresponding measure of the variance within a sub-group of AA (designated ΣV) may indicate total AA resynthesis, and be strongly tied to heterotrophic microbial reworking in detrital materials. Together, we hypothesize that ΔTr and ΣV define a two dimensional trophic “space”, which may simultaneously express relative extent of eukaryotic and bacterial heterotrophic processing. In the equatorial Pacific, ΔTr indicates an average of 1.5 2 trophic transfers between phytoplankton and sinking POM at all depths and locations. The ΣV parameter suggests that substantial variation may exist in bacterial heterotrophic processing between differing regions and time periods. In dissolved material δ15N-AA patterns appear unrelated to those in POM. In contrast to POM, δ15N-AA signatures in UDOM show no clear changes with depth, and suggest that dissolved AA preserved throughout the oceanic water column have undergone few, if any, trophic transfers. Together these data suggest a sharp divide between processing histories, and possibly sources, of particulate vs. dissolved AA.

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