Constraining The Radiocarbon Distribution Within Major Components of Marine Dissolved Organic Carbon

Dissolved organic carbon (DOC) is one of the largest active carbon pools on Earth with a carbon inventory similar to that of the atmosphere. The sources and cycling of DOC in the ocean is not well-constrained. However, knowledge of the cycling and annual flux of carbon through DOC is critical to understanding the global carbon cycle and feedback mechanisms in the global climate system. Natural-abundance radiocarbon and stable carbon isotopic values can be used to infer the sources and cycling of DOC in the oceans. Past measurements for the most part have been made on bulk DOC, which represents an average of all DOC components. There is, however, good evidence that the actual range of values within the average is quite large, and recent serial oxidation measurements of the surface and deep ocean total DOC [1, 2, 3] reveal isotopic heterogeneity in the DOC pool with a radiocarbon-enriched modern component and a radiocarbon-depleted older component co-cycling in the surface ocean. Also, modeled data from the serial oxidation of the total DOC suggest the presence of a significant amount of modern DOC in the deep ocean [3]. In this study, we used a detailed size and chemical fractionation approach to examine the isotopic distribution within different size and molecular constituents of DOC. We also used a novel thermal serial oxidation approach to link the isotopic diversity of DOC to its concurrent major structural composition in order to build upon and refine the insights from the total DOC isotopic work. Our data show that, in the deep ocean, a major component of the heteropolysaccharide (HPS)-rich DOC isolated by ultrafiltration has radiocarbon value similar to co-occurring DIC indicating either a chemosynthetic source or conservative transport. In contrast, the fraction of DOC rich in the carboxylic -rich compounds isolated by solid phase extraction was much older than the DIC and also exhibit remarkable isotopic diversity in its constituent organic compounds. Our data improves our understanding of the cycling of oceanic DOC and allows for a more constrained modeling of the DOC cycle. Cited work1. Beaupre et al. 2007. Limnology and Oceanography: Methods 5: 174-184. 2. Beaupre and Druffel 2012. Geophysical Research Letters 39, L18602, doi:10.1029/2012GL052974 3. Follet et al. 2014. PNAS 111: 16706-16711.