Sources and transformation of dissolved and particulate organic nitrogen in the North Pacific Subtropical Gyre indicated by compound-specific δ15N analysis of amino acids
Abstract
This study explores the use of compound-specific nitrogen isotopes of amino acids (δ15NAA) of coupled dissolved and particulate organic nitrogen (DON, PON) samples as a new approach to examine relative sources, transformation processes, and the potential coupling of these two major forms of N cycle in the ocean water column. We measured δ15NAA distributions in high-molecular-weight dissolved organic nitrogen (HMW DON) and suspended PON in the North Pacific Subtropical Gyre (NPSG) from surface to mesopelagic depths. A new analytical approach achieved far greater δ15NAA measurement precision for DON than earlier work, allowing us to resolve previously obscured differences in δ15NAA signatures, both with depth and between ON pools. We propose that δ15N values of total hydrolysable amino acids (THAA) represents a proxy for proteinaceous ON δ15N values in DON and PON. Together with bulk δ15N values, this allows δ15N values and changes in bulk, proteinaceous, and "other-N" to be directly evaluated.
These novel measurements suggest three main conclusions. First, the δ15NAA signatures of both surface and mesopelagic HMW DON suggest mainly heterotrophic bacterial sources, with mesopelagic HMW DON bearing signatures of far more degraded material compared to surface material. These results contrast with a previous proposal that HMW DON δ15NAA patterns are essentially "pre-formed" by cyanobacteria in the surface ocean, undergo little change with depth. Second, different δ15NAA values and patterns of HMW DON vs. suspended PON in the surface NPSG suggest that sources and cycling of these two N reservoirs are surpisingly decoupled. Based on molecular δ15N signatures, we propose a new hypothesis that production of surface HMW DON is ultimately derived from subsurface nitrate, while PON in the mixed layer is strongly linked to N2 fixation and N recycling. In contrast, the comparative δ15NAA signatures of HMW DON vs. suspended PON in the mesopelagic also suggest a possible PON source for some HMW DON in the mid-water column. Together, these results suggest that conversion of relatively labile ON to less labile DON by heterotrophic bacteria (a "microbial nitrogen pump") may be the key pathway for production and alteration of DON in both the surface and the mesopelagic oligotrophic ocean. Finally, in contrast to THAA, δ15N values of the other-N were substantially less affected by heterotrophic alteration, which may be consistent with a larger than expected contribution of amino sugars, or other less labile nitrogenous organic molecules.- Publication:
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Geochimica et Cosmochimica Acta
- Pub Date:
- January 2018
- DOI:
- 10.1016/j.gca.2017.07.036
- Bibcode:
- 2018GeCoA.220..329Y
- Keywords:
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- Dissolved organic nitrogen;
- Amino acids;
- Compound-specific nitrogen isotope analysis;
- Microbial nitrogen pump