The >5,000‐year radiocarbon age (14C‐age) of much of the 630 ± 30 Pg C oceanic dissolved organic carbon (DOC) reservoir remains an enigma in the marine carbon cycle. The fact that DOC is significantly older than dissolved inorganic carbon at every depth in the ocean forms the basis of our current framing of the marine DOC cycle, where some component persists over multiple cycles of ocean mixing. As a result,14C‐depleted, aged DOC is hypothesized to be present as a uniform reservoir with a constant14C signature and concentration throughout the water column. However, key requirements of this model, including direct observations of DOC with similar14C signatures in the surface and deep ocean, have never been met. Despite decades of research, the distribution of Δ14C values in marine DOC remains a mystery. Here, we applied a thermal fractionation method to compare operationally defined refractory DOC (RDOC) from different depths in the North Pacific Ocean. We found that RDOC shares chemical characteristics (as recorded by OC bond strength) throughout the water column but does not share the same14C signature. Our results support one part of the current paradigm—that RDOC is comprised of structurally related components throughout the ocean that form a “background” reservoir. However, in contrast to the current paradigm, our results are consistent with a vertical concentration gradient and a vertical and inter‐ocean Δ14C gradient for RDOC. The observed Δ14C gradient is compatible with the potential addition of pre‐aged DOC to the upper ocean.
The composition and cycling dynamics of marine dissolved organic carbon (DOC) have received increased interest in recent years; however, little research has focused on the refractory, low molecular weight (LMW) component that makes up the majority of this massive C pool. We measured stable isotopic (δ13C), radioisotopic (Δ14C), and compositional (C/N,13C solid‐state NMR) properties of separately isolated high molecular weight (HMW) and LMW DOC fractions collected using a coupled ultrafiltration and solid phase extraction approach from throughout the water column in the North Central Pacific and Central North Atlantic. The selective isolation of LMW DOC material allowed the first investigation of the composition and cycling of a previously elusive fraction of the DOC pool. The structural composition of the LMW DOC material was homogeneous throughout the water column and closely matched carboxylic‐rich alicyclic material that has been proposed as a major component of the marine refractory DOC pool. Examination of offsets in the measured parameters between the deep waters of the two basins provides the first direct assessment of changes in the properties of this material with aging and utilization during ocean circulation. While our direct measurements largely confirm hypotheses regarding the relative recalcitrance of HMW and LMW DOC, we also demonstrate a number of novel observations regarding the removal and addition of DOC during global ocean circulation, including additions of fresh carbohydrate‐like HMW DOC to the deep ocean and large‐scale removal of both semilabile HMW and recalcitrant LMW DOC.
more » « less- NSF-PAR ID:
- 10455792
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Global Biogeochemical Cycles
- Volume:
- 34
- Issue:
- 6
- ISSN:
- 0886-6236
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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