Dissolved organic carbon (DOC), operationally defined as the carbon contained in that fraction of organic matter in water which passes through a 0.2-1 μm filter, is the largest pool (ca. 0.6 × 10 18 g C) of organic matter in the oceans and is approximately equal in size to atmospheric CO 2 (Hedges 1992). Despite its abundance in the global carbon cycle and nearly a century of research, the majority (> 60% -80%) of DOC has remained molecularly uncharacterized (Hedges 1992) and its biogeochemical fluxes incompletely resolved. Global riverine input of ~0.2 Gt DOC per year (Meybeck 1982) is sufficient to support its radiocarbon ( 14 C) based oceanic residence time, yet composition (Meyers-Schulte and Hedges 1986; Opsahl and Benner 1997) and stable carbon ( 13 C) isotopic signature (Williams and Gordon 1970) measurements suggest the majority of marine DOC is autochthonous, ultimately originating from primary production in the euphotic zone. Furthermore, while the 4000 -6000 y 14 C ages reported for deep marine DOC suggest that a major proportion cycles on very long time scales and ages in situ during deep water transit (Bauer et al. 1992;Williams and Druffel 1987), the source of apparent chemical resilience and the removal processes necessary to produce these ages remain unknown. The published body of Δ 14 C values has been critical to understanding marine DOC biogeochemistry, yet it contains relatively few measurements because of methodological difficulties associated with low DOC concentrations, an overwhelming proportion of salts, and high blanks.The marine DOC ultraviolet (UV) extraction method (Armstrong et al. 1966;Williams 1968; Williams and Gordon 1970; Williams et al. 1969), and subsequent refinements (Bauer et al. 1998a;Druffel et al. 1989) that co-evolved with smaller sample size requirements of accelerator mass spectrometry (AMS) 14 C measurement, has been particularly wellsuited for isotopic analysis of marine DOC. It is amenable to batch reactors capable of oxidizing the large seawater aliquots required to collect enough DOC for isotopic analysis. It is a minimally invasive technique, involving only acidification and sparging of dissolved inorganic carbon (DIC) from filtered seawater prior to photochemical oxidation of DOC to CO 2 , thus minimizing the risk of contamination. Lastly, replicate analyses by Bauer et al. (1998a) demonstrated that good reproducibility (with single standard deviations of ± 1 μM and ± 3‰ to 6‰ for concentration and Δ 14 C measurements, respectively) accompanies low blanks (< 1.5 μM). Based on these techniques, a modified method for UV extraction of bulk marine nonvolatile DOC for isotopic analysis has been developed using simple, novel devices to decrease the analytical blank to ~0.2 μM, and reduce the
AbstractWe report the development of a modified, low blank, ultraviolet oxidation and vacuum line system to convert marine dissolved organic carbon into carbon dioxide for concentration, Δ 14 C, and δ 13 C analyses. The system performs quantitatively and precisely with preserv...