Based on the C‐14 data of Druffel et al. (2021,
What Is Refractory Organic Matter in the Ocean?
About 20% of the organic carbon produced in the sunlit surface ocean is transported into the ocean’s interior as dissolved, suspended and sinking particles to be mineralized and sequestered as dissolved inorganic carbon (DIC), sedimentary particulate organic carbon (POC) or “refractory” dissolved organic carbon (rDOC). Recently, the physical and biological mechanisms associated with the particle pumps have been revisited, suggesting that accepted fluxes might be severely underestimated ( Boyd et al., 2019 ; Buesseler et al., 2020 ). Perhaps even more poorly understood are the mechanisms driving rDOC production and its potential accumulation in the ocean. On the basis of recent conflicting evidence about the relevance of DOC degradation in the deep ocean, we revisit the concept of rDOC in terms of its “refractory” nature in order to understand its role in the global carbon cycle. Here, we address the problem of various definitions and approaches used to characterize rDOC (such as turnover time in relation to the ocean transit time, molecule abundance, chemical composition and structure). We propose that rDOC should be operationally defined. However, we recognize there are multiple ways to operationally define rDOC; thus the main focus for unifying future studies should be to explicitly state how rDOC is being defined and the analytical window used for measuring rDOC, rather than adhering to a single operational definition. We also conclude, based on recent evidence, that the persistence of rDOC is fundamentally dependent on both intrinsic (chemical composition and structure, e.g., molecular properties), and extrinsic properties (amount or external factors, e.g., molecular concentrations, ecosystem properties). Finally, we suggest specific research questions aimed at stimulating research on the nature, dynamics, and role of rDOC in Carbon sequestration now and in future scenarios of climate change.
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- Award ID(s):
- 2023500
- PAR ID:
- 10293017
- Date Published:
- Journal Name:
- Frontiers in Marine Science
- Volume:
- 8
- ISSN:
- 2296-7745
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract https://doi.org/10.1029/2021gl092904 ) along the Eastern Pacific Rise, dissolved organic carbon (DOC) in the deep ocean is old and thus refractory. Their data in combination with previous He‐3 data indicate that the source of this aged DOC is from the hot waters emanating from hydrothermal vents along the ridge axis. The isotopic and structural composition of the source DOC is unknown, which requires a concerted effort by the marine organic chemistry community to elucidate these chemical forms. -
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Abstract 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.
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Abstract 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.
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Abstract The global ocean sequesters a large amount of reduced carbon in dissolved organic molecules that can persist for centuries to millennia. The persistence of dissolved organic carbon (DOC) in the deep ocean has been attributed to inherently refractory molecules and to low concentrations of molecules, but the relative roles of molecular properties and molecular concentrations remain uncertain. We investigate both of these possibilities using bioassay experiments with unfiltered seawater collected from five depths (50–1500 m) at the Bermuda Atlantic Time‐Series Study site. The microbial utilization of compositionally distinct forms of seawater DOC at in situ and elevated concentrations was determined. Microbial utilization of in situ organic carbon ranged from 6% to 7% in surface waters to 0% in deep water after 180 d. Additions of surface plankton‐derived DOC (~18 μmol L−1), which was enriched in amino acids and carbohydrates, revealed substantial (50–75%) removal of the added DOC at all depths within 7 d. In sharp contrast, additions of C‐18 isolated deep‐sea DOC (~20 μmol L−1) showed insignificant or minimal utilization at all depths after 7 or 180 d, even when primed with labile substrates. These experiments demonstrate microbial communities from varying depths and environments in the ocean could rapidly utilize elevated concentrations of plankton‐derived DOC, whereas these same microbes failed to utilize elevated concentrations of C‐18 DOC. These results indicate molecular properties are the primary control on the microbial utilization of DOC in the ocean. Our findings imply a dynamic DOC reservoir with a flexible capacity for carbon sequestration in the global ocean.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3389/fmars.2021.642637
