Photochemical reactivity of ancient marine dissolved organic carbon

Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 39 (2012): L18602, doi:10.1029/2012GL052974.Marine dissolved organic carbon (DOC) is the largest reservoir of reduced carbon in seawater and persists up to 4,000–6,000 conventional radiocarbon (14C) years on average. Photochemical degradation has been suggested as a geochemical sink for these long-lived molecules, yet there have been no studies relating photochemical lability to the 14C-ages of surface DOC. We observed apparent second order (2°) kinetics with respect to DOC and a strong trend from Δ14C-enriched to depleted values during exhaustive photomineralization of surface marine DOC with high energy UV light. Geochemically, these results suggest that surface DOC is an isotopically-heterogeneous mixture of molecules for which photochemical lability and 14C ages are correlated. Photochemical mineralization may therefore be an important control on the persistence of 14C-depleted DOC in the ocean.This study was supported under NSF grant OCE-0961980 to E. R. M. Druffel.2013-03-2