Production and transformation of dissolved neutral sugars and amino acids by bacteria in seawater

Dissolved organic matter (DOM) in the ocean consists of a heterogeneous mixture of molecules, most of which are of unknown origin. Neutral sugars and amino acids are among the few recognizable biomolecules in DOM, and the molecular composition of these biomolecules is shaped primarily by biological production and degradation processes. This study provides insight into the bioavailability of biomolecules as well as the chemical composition of DOM produced by bacteria. The molecular compositions of combined neutral sugars and amino acids were investigated in DOM produced by bacteria and in DOM remaining after 32 days of bacterial degradation. Results from bioassay incubations with natural seawater (sampled from water masses originating from the surface waters of the Arctic Ocean and the North Atlantic Ocean) and artificial seawater indicate that the molecular compositions following bacterial degradation are not strongly influenced by the initial substrate or bacterial community. The molecular composition of neutral sugars released by bacteria was characterized by a high glucose content (47 mol %) and heterogeneous contributions from other neutral sugars (3–14 mol %). DOM remaining after bacterial degradation was characterized by a high galactose content (33 mol %), followed by glucose (22 mol %) and the remaining neutral sugars (7–11 mol %). The ratio of D-amino acids to L-amino acids increased during the experiments as a response to bacterial degradation, and after 32 days, the D/L ratios of aspartic acid, glutamic acid, serine and alanine reached around 0.79, 0.32, 0.30 and 0.51 in all treatments, respectively. The striking similarity in neutral sugar and amino acid compositions between natural (representing marine semi-labile and refractory DOM) and artificial (representing bacterially produced DOM) seawater samples, suggests that microbes transform bioavailable neutral sugars and amino acids into a common, more persistent form

Origin, accumulation and fate of dissolved organic matter in an extreme hypersaline shallow lake

Hypersaline endorheic aquatic systems (H-SEAS) are lakes/shallow playas in arid and semiarid regions that undergo extreme oscillations in salinity and severe drought episodes. Although their geochemical uniqueness and microbiome have been deeply studied, very little is known about the availability and quality of dissolved organic matter (DOM) in the water column. A H-SEAS from the Monegros Desert (Zaragoza, NE Spain) was studied during a hydrological wetting-drying-rewetting cycle. DOM analysis included: (i) a dissolved organic carbon (DOC) mass balance; (ii) spectroscopy (absorbance and fluorescence) and (iii) a molecular characterization with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The studied system stored a large amount of DOC and under the highest salinity conditions, salt-saturated waters (i.e., brines with salinity > 30%) accumulated a disproportionate quantity of DOC, indicating a significant in-situ net DOM production. Simultaneously, during the hydrological transition from wet to dry, the DOM pool showed strong alterations of it molecular composition. Spectroscopic methods indicated that aromatic and degraded DOM was rapidly replaced by fresher, relatively small, microbial-derived moieties with a large C/N ratio. FT-ICR-MS highlighted the accumulation of small, saturated and oxidized molecules (molecular O/C > 0.5), with a remarkable increase in the relative contribution of highly oxygenated (molecular O/C > 0.9) compounds and a decrease of aliphatic and carboxyl-rich alicyclic moleculesThese results indicated that H-SEAS are extremely active in accumulating and processing DOM, with the notable release of organic solutes probably originated from decaying microplankton under large osmotic stress at extremely high salinitie

Marine sequestration of carbon in bacterial metabolites.

Linking microbial metabolomics and carbon sequestration in the ocean via refractory organic molecules has been hampered by the chemical complexity of dissolved organic matter (DOM). Here, using bioassay experiments and ultra-high resolution metabolic profiling, we demonstrate that marine bacteria rapidly utilize simple organic molecules and produce exometabolites of remarkable molecular and structural diversity. Bacterial DOM is similar in chemical composition and structural complexity to naturally occurring DOM in sea water. An appreciable fraction of bacterial DOM has molecular and structural properties that are consistent with those of refractory molecules in the ocean, indicating a dominant role for bacteria in shaping the refractory nature of marine DOM. The rapid production of chemically complex and persistent molecules from simple biochemicals demonstrates a positive feedback between primary production and refractory DOM formation. It appears that carbon sequestration in diverse and structurally complex dissolved molecules that persist in the environment is largely driven by bacteria

The influence of salinity on the molecular and optical properties of surface microlayers in a karstic estuary

Sea-surface microlayers and the corresponding underlying waters of the karstic Krka Estuary (Croatia) were studied with respect to optical and molecular properties of dissolved organic matter (DOM). Solid-phase extracted DOMwas separated by reversed-phase chromatography and analyzedwith ultra-high resolution Fourier transformion cyclotron resonance mass spectrometry (FT-ICRMS). The number and summedmagnitudes of FT-ICR MS peaks, enriched in themicrolayer, increased with increasing salinity along the estuary. The molecular hydrogen to carbon ratio (as ameasure of polarity) of enriched compounds was higher for the low salinity samples than for a high salinity marine station, which we propose is a consequence of a salt-mediated separation mechanism. Absorption and fluorescence of all samples decreased along the estuarywith themicrolayer samples showing higher absorption than the underlying water. Chromatographic and FT-ICR MS data revealed a distinct shift towards a smaller molecular size in the microlayer compared to the underlyingwater. The redistribution of dissolved organic carbonwithin chromatographic fractions and the decrease inmolecular sizewas interpreted to result from photo-degradation and/or microbial reprocessing. Collision induced dissociation of selected FT-ICR MS mass peaks revealed the presence of sulfur containing anthropogenic surfactants enriched in themicrolayer. Molecular level investigation of estuarine surfacemicrolayers will help to better understand the highly dynamic character of these systems, the accumulation of natural organicmatter and anthropogenic pollutants and the role of surface microlayers for the sea-air energy exchange

Ageing and molecular changes of dissolved organic matter between two deep oceanic end members.

The global ocean contains a massive reservoir of dissolved organic carbon (DOC), rivaling the atmosphere's pool of CO2. The most recalcitrant fractions have mean radiocarbon ages of similar to 4,000years in the Atlantic to similar to 6,000years in the Pacific. Knowing the radiocarbon signatures of DOC and the molecular composition of dissolved organic matter (DOM) is crucial to develop understanding of the persistence and lifetime of the DOC pool. In this research, we collected samples from the deep North Pacific in August 2013 (aboard the RV Melville) to couple the Delta C-14 content of solid-phase-extracted DOM (Delta C-14-SPE-DOM) with its molecular composition in the ocean's oldest deep waters. We find that deep waters in this region held a mean Delta C-14-SPE-DOM value of -554 +/- 9 (similar to 6,400(14)Cyears), substantially more depleted than that in the deep Atlantic, which held a mean Delta C-14-SPE-DOM value of -445 +/- 5. While we find a more degraded molecular composition of DOM in the deep Pacific than the deep Atlantic, the molecular formulae within the Island of Stability (Lechtenfeld et al., 2014, ), are largely retained. These results imply that a fraction of deep DOM is resistant to removal and present in both the deep Atlantic and Pacific Oceans

Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory.

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. While molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (S/N ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 Pg S, exceeding all other marine organic sulfur reservoirs by an order of magnitude

Response to Comment on "Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory".

Dittmar et al. proposed thatmixing alone can explain our observed decrease inmarine dissolved organic sulfur with age. However, their simple model lacks an explanation for the origin of sulfur-depleted organic matter in the deep ocean and cannot adequately reproduce our observed stoichiometric changes. Using radiocarbon age also implicitlymodels the preferential cycling of sulfur that they are disputing

Origin, accumulation and fate of dissolved organic matter in an extreme hypersaline shallow lake

Hypersaline endorheic aquatic systems (H-SEAS) are lakes/shallow playas in arid and semiarid regions that undergo extreme oscillations in salinity and severe drought episodes. Although their geochemical uniqueness and microbiome have been deeply studied, very little is known about the availability and quality of dissolved organic matter (DOM) in the water column.. A H-SEAS from the Monegros Desert (Zaragoza, NE Spain) was studied during a hydrological wetting-drying-rewetting cycle. DOM analysis included: (i) a dissolved organic carbon (DOC) mass balance; (ii) spectroscopy (absorbance and fluorescence) and (iii) a molecular characterization with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The studied system stored a large amount of DOC and under the highest salinity conditions, salt-saturated waters (i.e., brines with salinity > 30%) accumulated a disproportionate quantity of DOC, indicating a significant in-situ net DOM production. Simultaneously, during the hydrological transition from wet to dry, the DOM pool showed strong alterations of it molecular composition. Spectroscopic methods indicated that aromatic and degraded DOM was rapidly replaced by fresher, relatively small, microbial-derived moieties with a large C/N ratio. FT-ICR-MS highlighted the accumulation of small, saturated and oxidized molecules (molecular O/C > 0.5), with a remarkable increase in the relative contribution of highly oxygenated (molecular O/C>0.9) compounds and a decrease of aliphatic and carboxyl-rich alicyclic moleculesThese results indicated that H-SEAS are extremely active in accumulating and processing DOM, with the notable release of organic solutes probably originated from decaying microplankton under large osmotic stress at extremely high salinities.Ministerio de Ciencia e Innovación (MCIN) /Agencia Estatal de InvestigaciónEuropean Regional Development Funds (EFRE - Europe Funds Saxony)Helmholtz AssociationDepto. de Biodiversidad, Ecología y EvoluciónFac. de Ciencias BiológicasTRUEpu

Origin, accumulation and fate of dissolved organic matter in an extreme hypersaline shallow lake

Hypersaline endorheic aquatic systems (H-SEAS) are lakes/shallow playas in arid and semiarid regions that undergo extreme oscillations in salinity and severe drought episodes. Although their geochemical uniqueness and microbiome have been deeply studied, very little is known about the availability and quality of dissolved organic matter (DOM) in the water column.. A H-SEAS from the Monegros Desert (Zaragoza, NE Spain) was studied during a hydrological wetting-drying-rewetting cycle. DOM analysis included: (i) a dissolved organic carbon (DOC) mass balance; (ii) spectroscopy (absorbance and fluorescence) and (iii) a molecular characterization with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The studied system stored a large amount of DOC and under the highest salinity conditions, salt-saturated waters (i.e., brines with salinity > 30%) accumulated a disproportionate quantity of DOC, indicating a significant in-situ net DOM production. Simultaneously, during the hydrological transition from wet to dry, the DOM pool showed strong alterations of it molecular composition. Spectroscopic methods indicated that aromatic and degraded DOM was rapidly replaced by fresher, relatively small, microbial-derived moieties with a large C/N ratio. FT-ICR-MS highlighted the accumulation of small, saturated and oxidized molecules (molecular O/C > 0.5), with a remarkable increase in the relative contribution of highly oxygenated (molecular O/C>0.9) compounds and a decrease of aliphatic and carboxyl-rich alicyclic moleculesThese results indicated that H-SEAS are extremely active in accumulating and processing DOM, with the notable release of organic solutes probably originated from decaying microplankton under large osmotic stress at extremely high salinities