Dominant heterocyclic composition of dissolved organic nitrogen in the ocean: A new paradigm for cycling and persistence

Broek, Taylor A. B.; McCarthy, Matthew D.; Ianiri, Hope L.; Vaughn, John S.; Mason, Harris E.; Knapp, Angela N.

doi:10.1073/pnas.2305763120

Dominant heterocyclic composition of dissolved organic nitrogen in the ocean: A new paradigm for cycling and persistence

Journal Article · Tue Nov 28 00:00:00 EST 2023 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2305763120· OSTI ID:2469752

^[1]; McCarthy, Matthew D. ^[2]; ^[3]; Vaughn, John S. ^[4]; ^[5]; ^[6]

University of California, Santa Cruz, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Woods Hole Oceanographic Institution, Falmouth, MA (United States)
University of California, Santa Cruz, CA (United States)
University of California, Santa Cruz, CA (United States); U.S. Geological Survey Pacific Coastal and Marine Science Center, Santa Cruz, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Florida State University, Tallahassee, FL (United States)

Marine dissolved organic nitrogen (DON) is one of the planet’s largest reservoirs of fixed N, which persists even in the N-limited oligotrophic surface ocean. The vast majority of the ocean’s total DON reservoir is refractory (RDON), primarily composed of low molecular weight (LMW) compounds in the subsurface and deep sea. However, the composition of this major N pool, as well as the reasons for its accumulation and persistence, are not understood. Past characterization of the analytically more tractable, but quantitatively minor, high molecular weight (HMW) DON fraction revealed a functionally simple amide-dominated composition. While extensive work in the past two decades has revealed enormous complexity and structural diversity in LMW dissolved organic carbon, no efforts have specifically targeted LMW nitrogenous molecules. Here, we report the first coupled isotopic and solid-state NMR structural analysis of LMW DON isolated throughout the water column in two ocean basins. Together these results provide a first view into the composition, potential sources, and cycling of this dominant portion of marine DON. Our data indicate that RDON is dominated by 15N-depleted heterocyclic-N structures, entirely distinct from previously characterized HMW material. This fundamentally new view of marine DON composition suggests an important structural control for RDON accumulation and persistence in the ocean. The mechanisms of production, cycling, and removal of these heterocyclic-N-containing compounds now represents a central challenge in our understanding of the ocean’s DON reservoir.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2469752

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 49 Vol. 120; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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