Description: Marine dissolved organic matter (DOM) is one of the largest active organic carbon reservoirs on Earth, and changes in its pool size or composition could have a major impact on the global carbon cycle. Ocean acidification is a potential driver for these changes because it influences marine primary production and heterotrophic respiration. We simulated ocean acidification as expected for a “business-as-usual” emission scenario in the year 2100 in an unprecedented long-term mesocosm study. The large-scale experiments (50 m3 each) covered a full seasonal cycle of marine production in a Swedish Fjord. Five mesocosms were artificially enriched in CO2 to the partial pressure expected in the year 2100 (900 μatm), and five more served as controls (400 μatm). We applied ultrahigh-resolution mass spectrometry to monitor the succession of 7360 distinct DOM formulae over the course of the experiment. Plankton blooms had a clear effect on DOM concentration and molecular composition. This succession was reproducible across all 10 mesocosms, independent of CO2 treatment. In contrast to the temporal trend, there were no significant differences in DOM concentration and composition between present-day and year 2100 CO2 levels at any time point of the experiment. On the basis of our results, ocean acidification alone is unlikely to affect the seasonal accumulation of DOM in productive coastal environments.

Description: Coagulation of dissolved organic matter (DOM) by hydrolyzing metals is an important environmental process with particular relevance, e.g., for the cycling of organic matter in metal-rich aquatic systems or the flocculation of organic matter in wastewater treatment plants. Often, a nonremovable fraction of DOM remains in solution even at low DOM/metal ratios. Because coagulation by metals results from interactions with functional groups, we hypothesize that noncoagulating fractions have a distinct molecular composition. To test the hypothesis, we analyzed peat-derived dissolved organic matter remaining in solution after mixing with salts of Ca, Al, and Fe using 15 T Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Addition of metals resulted in a net removal of DOM. Also a reduction of molecular diversity was observed, as the number of peaks from the ESI-FT-ICR-MS spectra decreased. At DOM/metal ratios of ∼9 Ca did not show any preference for distinct molecular fractions, while Fe and Al removed preferentially the most oxidized compounds (O/C ratio 〉0.4) of the peat leachate. Lowering DOM/metal ratios to ∼1 resulted in further removal of less oxidized as well as more aromatic compounds (“black carbon”). Molecular composition in the residual solution after coagulation was more saturated, less polar, and less oxidized compared to the original peat leachate and exhibited a surprising similarity with DOM of marine origin. By identifying more than 9200 molecular formulas we can show that structural properties (saturation and aromaticity) and oxygen content of individual DOM molecules play an important role in coagulation with metals. We conclude that polyvalent cations not only alter the net mobility but also the very molecular composition of DOM in aquatic environments.

Description: With almost 700 Pg of carbon, marine dissolved organic carbon (DOC) stores more carbon than all living biomass on Earth combined. However, the controls behind the persistence and the spatial patterns of DOC concentrations on the basin scale remain largely unknown, precluding quantitative assessments of the fate of this large carbon pool in a changing climate. Net removal rates of DOC along the overturning circulation suggest lifetimes of millennia. These net removal rates are in stark contrast to the turnover times of days to weeks of heterotrophic microorganisms, which are the main consumers of organic carbon in the ocean. Here, we present a dynamic “MICrobial DOC” model (MICDOC) with an explicit representation of picoheterotrophs to test whether ecological mechanisms may lead to observed decadal to millennial net removal rates. MICDOC is in line with 〉40,000 DOC observations. Contrary to other global models, the reactivity of DOC fractions is not prescribed, but emerges from a dynamic feedback between microbes and DOC governed by carbon and macronutrient availability. A colimitation of macronutrients and organic carbon on microbial DOC uptake explains 〉70% of the global variation of DOC concentrations, and governs characteristic features of its distribution. Here, decadal to millennial net removal rates emerge from microbial processes acting on time scales of days to weeks, suggesting that the temporal variability of the marine DOC inventory may be larger than previously thought. With MICDOC, we provide a foundation for assessing global effects on DOC related to changes in heterotrophic microbial communities in a future ocean Plain Language Summary The ocean stores more carbon as dissolved organic compounds (DOC) than all animals and plants on land and the oceans combined. However, numerical models used for future climate scenarios lack an implementation of processes transforming DOC back to CO 2 by marine microorganisms. Here, we present a global dynamical ocean model that explicitly considers the processes of DOC degradation by marine microorganisms. In the present ocean, the availability of organic carbon but also nitrogen and phosphorus control the amount of carbon stored as DOC, as the lack of these nutrients inhibits its degradation by bacteria. The identification of these ecological controls allows a quantitative assessment of the fate of this large carbon reservoir in the future. The findings indicate that the marine DOC reservoir is potentially more dynamic than previously thought, since decadal to millennial scale net removal rates might be a result of microbial processes acting on shorter time scales Key Points A model to reconcile millennial‐scale bulk dissolved organic carbon degradation rates and short‐term microbial turnover times is presented Macronutrient colimitation can explain observed concentration patterns of dissolved organic carbon in the surface ocean Continuous microbial reworking suggests a higher temporal variability of the marine dissolved organic matter inventory than previously thought