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: Deep-sea dissolved organic matter (DOM) constitutes a huge carbon reservoir in the worlds' oceans that – despite its abundance – is virtually unused as a substrate by marine heterotrophs. Heating within hydrothermal systems induces major molecular modifications of deep-sea DOM. Here, we tested the hypothesis that hydrothermal heating of deep-sea DOM enhances bioavailability. Aliquots of DOM extracted from the deep North Pacific (North Equatorial Pacific Intermediate Water; NEqPIW) were re-dissolved in artificial seawater and subjected to temperatures of 100 and 200 °C (40 MPa) using Dickson-type reactors. In agreement with earlier findings we observed a temperature-related drop in dissolved organic carbon (DOC) concentration (−6.1% at 100 °C, −21.0% at 200 °C) that predominantly affected the solid-phase extractable (SPE-DOC) fraction (−18.2% at 100 °C, −51.4% at 200 °C). Fourier-transform ion cyclotron resonance mass spectrometric (FT-ICR-MS) analysis confirmed a temperature-related reduction of average molecular mass, O/C ratios, double bond equivalents (DBE) and a relative increase in aromaticity (AImod). This thermally altered DOM was added (25 μmol L−1 DOC) to deep-water samples from the South West Pacific (Kermadec Arc, RV Sonne / SO253, 32° 37.706′ S | 179° 38.728′ W) and incubated with the prevailing natural microbial community. After 16 days at 4 °C in the dark, prokaryotic cell counts in incubations containing the full spectrum of thermally-degraded DOM (extractable and non-extractable compounds) had increased considerably (on average 21× for DOM100°C and 27× for DOM200°C). In contrast, prokaryotic growth in incubations to which only solid-phase extractable thermally-altered DOM was added was not enhanced compared to control incubations. The experiments demonstrate that temperature-driven degradation of deep-sea recalcitrant DOM within hydrothermal systems turns fractions of it accessible to microbes. The thermally-produced DOM compounds that stimulate microbial growth are not retained on reversed-phase resins (SPE-DOM) and are likely low-molecular mass organic acids. Despite the comprehensive compositional modifications of the solid-phase extractable (SPE-DOM) fraction through heating, it remains inaccessible to microbes at the investigated concentration levels. The microbial incubation resulted in only minor and mostly insignificant overall changes in SPE-DOM molecular composition and concentration.

Description: Marine permeable sediments are important sites for organic matter turnover in the coastal ocean. However, little is known about their role in trapping dissolved organic matter (DOM). Here, we examined DOM abundance and molecular compositions (9804 formulas identified) in subtidal permeable sediments along a near- to offshore gradient in the German North Sea. With the salinity increasing from 30.1 to 34.6 PSU, the DOM composition in bottom water shifts from relatively higher abundances of aromatic compounds to more highly unsaturated compounds. In the bulk sediment, DOM leached by ultrapure water (UPW) from the solid phase is 54 ± 20 times more abundant than DOM in porewater, with higher H/C ratios and a more terrigenous signature. With 0.5 M HCl, the amount of leached DOM (enriched in aromatic and oxygen-rich compounds) is doubled compared to UPW, mainly due to the dissolution of poorly crystalline Fe phases (e.g., ferrihydrite and Fe monosulfides). This suggests that poorly crystalline Fe phases promote DOM retention in permeable sediments, preferentially terrigenous, and aromatic fractions. Given the intense filtration of seawater through the permeable sediments, we posit that Fe can serve as an important intermediate storage for terrigenous organic matter and potentially accelerate organic matter burial in the coastal ocean.