Beschreibung: Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature which is ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into RDOM was shown experimentally, implying that microorganisms produce far more RDOM than needed to sustain the global pool. By assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, we show that most of the newly formed RDOM is molecularly different from deep sea RDOM. Only 〈0.4% of the net community production was channeled into RDOM molecularly undistinguishable from deep sea DOM. Our study provides novel experimentally derived molecular evidence and data for global models on the production, turnover and accumulation of marine DOM.

Beschreibung: Dissolved organic matter (DOM) is the main substrate and energy source for heterotrophic bacterioplankton. To understand the interactions between DOM and the bacterial community (BC), it is important to identify the key factors on both sides in detail, chemically distinct moieties in DOM and the various bacterial taxa. Next-generation sequencing facilitates the classification of millions of reads of environmental DNA and RNA amplicons and ultrahigh-resolution mass spectrometry yields up to 10,000 DOM molecular formulae in a marine water sample. Linking this detailed biological and chemical information is a crucial first step toward a mechanistic understanding of the role of microorganisms in the marine carbon cycle. In this study, we interpreted the complex microbiological and molecular information via a novel combination of multivariate statistics. We were able to reveal distinct relationships between the key factors of organic matter cycling along a latitudinal transect across the North Sea. Total BC and DOM composition were mainly driven by mixing of distinct water masses and presumably retain their respective terrigenous imprint on similar timescales on their way through the North Sea. The active microbial community, however, was rather influenced by local events and correlated with specific DOM molecular formulae indicative of compounds that are easily degradable. These trends were most pronounced on the highest resolved level, that is, operationally defined 'species', reflecting the functional diversity of microorganisms at high taxonomic resolution.

Beschreibung: Aerosol, seawater, and floodwater samples were taken during the 2017 California Thomas Fire and subsequent flash flood event. These samples were used to examine how fire-flood sequences affect metal and black carbon delivery to coastal waters, such as the Santa Barbara Basin (SBB). On day 11 of the Thomas Fire, aerosols sampled at sea level under a smoke plume over the SBB found high levels of PM2.5, levoglucosan, and black carbon (average: 49 μg/m^3, 1.05 μg/m^3, 14.93 μg/m^3, respectively) and both soluble and total aerosol metal concentrations were consistent with a forest fire signature. Metal, nutrient, and chlorophyll a concentrations in surface seawater (average: 2.42 nM Fe, 0.14 µM phosphate, and 0.44 µgChla/L) were similar to concentrations during non-fire conditions, thus we could not establish fire-related increases in the SBB surface waters. On days 37 to 40 of the fire, before, during, and after a flash flood in the Ventura River, dissolved organic carbon, dissolved black carbon, and dissolved metal concentrations were positively correlated with discharge. Our findings confirm that black carbon and metals were released by the Thomas Fire and transported by both atmospheric and fluvial pathways.

Beschreibung: Shallow submarine hydrothermal systems are extreme environments with unique biogeochemical conditions, originating from the interaction of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids represent one of the marine sources of essential trace elements like iron, the flux of which is controlled by dissolved organic matter (DOM) in and between terrestrial and marine ecosystems. However, the selectivity of the DOM with iron in marine environments is not well understood. Here we characterized at a molecular level the marine hydrothermal iron?DOM interaction using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our study site was a shallow-water hydrothermal system off Dominica Island (Lesser Antilles, Caribbean Sea), where reduced fluids were strongly enriched in dissolved Fe and Si as compared to surface seawater. The dissolved organic carbon (DOC) concentration was lower in the hydrothermal fluids, most likely due to low-DOC meteoric water influence, but also suggesting biotic or abiotic processes consuming or depleting DOC when seawater is re-circulated through the sediment. The formation of hydrous ferric oxides upon aeration of the hydrothermal fluids for 10 h leads to an 8% decrease in DOC, indicating co-precipitation of iron and DOM. Re-solubilization of iron precipitates revealed increased relative abundance of aromatic compounds in co-precipitated DOM, which is in accordance with iron-coagulation observed in terrestrial environments. In conclusion, we provide evidence of co-precipitation of DOM with iron at hydrothermal systems as a selective process, which characteristically alters the molecular composition of DOM released with hydrothermal fluids.

Beschreibung: Shallow submarine hydrothermal systems are extreme environments with strong redox gradients at the interface of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids are often depleted in sulfate when compared to surrounding seawater and can contain high concentrations of hydrogen sulfide (H2S). It is well known that sulfur in its various oxidation states plays an important role in processing and transformation of organic matter. However, the formation and the reactivity of dissolved organic sulfur (DOS) in the water column at hydrothermal systems are so far not well understood. We investigated DOS dynamics and its relation to the physicochemical environment by studying the molecular composition of dissolved organic matter (DOM) in three contrasting shallow hydrothermal systems off Milos (Eastern Mediterranean), Dominica (Caribbean Sea) and Iceland (North Atlantic). We used ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the DOM on a molecular level. The molecular information was complemented with general geochemical data, quantitative dissolved organic carbon (DOC) and DOS analyses as well as isotopic measurements (d2H, d18O and F14C). In contrast to the predominantly meteoric fluids from Dominica and Iceland, hydrothermal fluids from Milos were mainly fed by recirculating seawater. The hydrothermal fluids from Milos were enriched in H2S and DOS, as indicated by high DOS/DOC ratios and by the fact that 〉90% of all assigned DOM formulas that were exclusively present in the fluids contained sulfur. In all three systems, DOS from hydrothermal fluids had on average lower O/C ratios (0.26?0.34) than surrounding surface seawater DOS (0.45?0.52), suggesting shallow hydrothermal systems as a source of reduced DOS, which will likely get oxidized upon contact with oxygenated seawater. Evaluation of hypothetical sulfurization reactions suggests DOM reduction and sulfurization during seawater recirculation in Milos seafloor. The four most effective potential sulfurization reactions were those exchanging an O atom by one S atom in the formula or the equivalent + H2S reaction, correspondingly exchanging H2O, H2 and/or O2 by a H2S molecule. Our study reveals novel insights into DOS dynamics in marine hydrothermal environments and provides a conceptual framework for molecular-scale mechanisms in organic sulfur geochemistry.