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Abstract The biogeochemical fluxes that cycle oxygen (O2) play a critical role in regulating Earth’s climate and habitability. Triple-oxygen isotope (TOI) compositions of marine dissolved O2 are considered a robust tool for tracing oxygen cycling and quantifying gross photosynthetic O2 production. This method assumes that photosynthesis, microbial respiration, and gas exchange with the atmosphere are the primary influences on dissolved O2 content, and that they have predictable, fixed isotope effects. Despite its widespread use, there are major elements of this approach that remain uncharacterized, including the TOI dynamics of respiration by marine heterotrophic bacteria and abiotic O2 sinks such as the photochemical oxidation of dissolved organic carbon (DOC). Here, we report the TOI fractionation for O2 utilization by two model marine heterotrophs and by abiotic photo-oxidation of representative terrestrial and coastal marine DOC. We demonstrate that TOI slopes associated with these processes span a significant range of the mass-dependent domain (λ = 0.499 to 0.521). A sensitivity analysis reveals that even under moderate productivity and photo-oxidation scenarios, true gross oxygen production may deviate from previous estimates by more than 20% in either direction. By considering a broader suite of oxygen cycle reactions, our findings challenge current gross oxygen production estimates and highlight several paths forward to better understanding the marine oxygen and carbon cycles. 

In sunlit waters, photodegradation of dissolved organic matter (DOM) yields completely oxidized carbon ( i.e. , CO 2 ) as well as a suite of partially oxidized compounds formed from oxygen incorporation ( i.e. , partial photo-oxidation). Of these two groups of DOM photo-products, more studies focus on CO 2 (a greenhouse gas) than on partially oxidized DOM, which is likely a diverse group of compounds with poorly constrained roles in aquatic carbon cycling or biogeochemistry. The objective of this study is to address knowledge gaps on the prevalence, products, and pathways of DOM partial photo-oxidation. Here we traced the photochemical incorporation of isotopically labelled 18 O 2 into DOM isolated from Alaskan Arctic surface waters using high-resolution mass spectrometry. Complete and partial photo-oxidation of DOM was also quantified as CO 2 production and O 2 consumption. The majority of 18 O-containing partial oxidation photo-products were classified as carboxylic rich alicyclic molecules (CRAM) and overlapped in composition with previously reported photo-products known to result from the oxidation of DOM by singlet oxygen. These results support a previously proposed hypothesis that photo-oxidation by singlet oxygen may contribute to the formation of CRAM, a compound class of DOM ubiquitously observed in surface waters. The novel application of an isotopic tracer for oxygen incorporation with a mass balance approach to quantify complete and partial photo-oxidation of DOM revealed that less than one mol of O 2 is required to produce one mol of CO 2 . A sensitivity analysis based on this new knowledge demonstrated that the magnitude of DOM partial photo-oxidation may be underestimated by up to four-fold. Consequently, partial photo-oxidation likely plays a more prominent role in shaping DOM composition in sunlit waters of the Arctic than previously understood. Therefore, partial photo-oxidation should be increasingly incorporated into the experimental framework of studies focused on DOM composition in surface waters. 

ABSTRACT This study describes a procedural blank assessment of the ultraviolet photochemical oxidation (UV oxidation) method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). A retrospective compilation of Fm and δ 13 C results for secondary standards (OX-II, glycine) between 2009 and 2018 indicated that a revised blank correction was required to bring results in line with accepted values. The application of a best-fit mass-balance correction yielded a procedural blank of 22.0 ± 6.0 µg C with Fm of 0.30 ± 0.20 and δ 13 C of –32.0 ± 3.0‰ for this period, which was notably higher and more variable than previously reported. Changes to the procedure, specifically elimination of higher organic carbon reagents and improved sample and reactor handling, reduced the blank to 11.0 ± 2.75 µg C, with Fm of 0.14 ± 0.10 and δ 13 C of –31.0 ± 5.5‰. A thorough determination of the entire sample processing blank is required to ensure accurate isotopic compositions of seawater DOC using the UV oxidation method. Additional efforts are needed to further reduce the procedural blank so that smaller DOC samples can be analyzed, and to increase sample throughput. 

Microbes and sunlight convert terrigenous dissolved organic matter (DOM) in surface waters to greenhouse gases. Prior studies show contrasting results about how biological and photochemical processes interact to contribute to the degradation of DOM. In this study, DOM leached from the organic layer of tundra soil was exposed to natural sunlight or kept in the dark, incubated in the dark with the natural microbial community, and analyzed for gene expression and DOM chemical composition. Microbial gene expression (metatranscriptomics) in light and dark treatments diverged substantially after 4 hours. Gene expression suggested that sunlight exposure of DOM initially stimulated microbial growth by (a) replacing the function of enzymes that degrade higher molecular weight DOM such as enzymes for aromatic carbon degradation, oxygenation, and decarboxylation, and (b) releasing low molecular weight compounds and inorganic nutrients from DOM. However, growth stimulation following sunlight exposure of DOM came at a cost. Sunlight depleted the pool of aromatic compounds that supported microbial growth in the dark treatment, ultimately causing slower growth in the light treatment over 5 days. These first measurements of microbial metatranscriptomic responses to photo-alteration of DOM provide a mechanistic explanation for how sunlight exposure of terrigenous DOM alters microbial processing and respiration of DOM.