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Despite its toxicity and versatile geochemistry, not much is known on the distribution, speciation and behaviour of Thallium (Tl) in the marine coastal environment, notably in estuaries. We here contribute to the discussion by presenting dissolved (<0.45 μm) and particulate data of Tl, Fe, Mn, as well as dissolved organic carbon (DOC) and dissolved Si for two transects through the Weser estuary during summer (July 2013) and winter (early March 2014). The results show that both, dissolved Tl (70–130 pM) and DOC (100–1000 μM) are elevated against average river concentrations, show the same distinct seasonality, decrease with increasing salinity and positively deviate from conservative mixing. Compared to that, dissolved Si displays almost conservative mixing with seawater while dissolved Fe and Mn are quickly removed in the estuarine turbidity maximum (ETM) classically located in the low salinity region of the estuary. The data further suggest that both, dissolved Tl and DOC exhibit only little loss at the ETM, and that Tl does not seem to cycle with Fe and Mn as was suggested for other estuaries. Moreover, reactive particulate Tl (as calculated from excess Tl enriched versus the lithogenic background) on the particles amount to only 20–50% of the dissolved Tl concentrations. This is in agreement with earlier studies underlining the low particle reactivity of Tl. However, the strong correlation between dissolved Tl and DOC is new and suggests a combined cycling through the estuary. Albeit being indirect, our observations support earlier suggestions of a possible association of Tl with organic ligands, and that Tl tends to remain in the dissolved phase when entering the ocean. [ABSTRACT FROM AUTHOR]

Phytoplankton spring blooms are typical features in coastal seas and provide heterotrophic bacteria with a rich blend of dissolved substrates. However, they are difficult to study in coastal seas in-situ. Here, we induced a phytoplankton spring bloom and followed its fate for 37 days in four 600 L-mesocosms. To specifically investigate the significance of phytoplankton-born dissolved organic carbon (DOC) we used artificial seawater with low DOC background and inoculated it with a 100 µm-prefiltered plankton community from the North Sea. A biphasic bloom developed, dominated by diatoms and Phaeocystis globosa respectively. In between, bacterial numbers peaked, followed by a peak in virus-like particles, implying that virus infection caused the collapse. Concentrations of dissolved free amino acids exhibited rapid changes, in particular during the diatom bloom and until the peak in bacterial abundance. Dissolved combined amino acids and neutral monosaccharides accumulated continuously, accounting for 22% of DOC as a mean and reaching levels as high as 44%. Bacterial communities were largely dominated by Bacteroidetes , especially the NS3a marine group (family Flavobacteriaceae), but Rhodobacteraceae and Gammaproteobacteria were also prominent members. Our study shows rapid organic matter and community composition dynamics that are hard to trace in natural coastal ecosystems. [ABSTRACT FROM AUTHOR]

Dissolved black carbon (DBC) is the largest known refractory organic carbon pool in the ocean. However, processes in estuaries connecting rivers (a significant DBC source) and oceans are underexplored. We carried out two sampling campaigns in the Jiulong River estuary (JRE) and conducted a dissolved organic matter (DOM) mixing experiment. DBC was quantified by the benzenepolycarboxylic acid (noted as DBC-BPCA) method and characterized with Fourier transform ion cyclotron resonance mass spectrometry (noted as DBC-FT). The molecular formulae of DBC-FT in the JRE were also compared with that in soil and atmospheric deposition. Overall, DBC-BPCA was removed during seaward dispersion. Soil- and deposition-derived molecules were identified in the DBC-FT of the JRE, confirming deposition inputs to estuarine DBC for the first time. The salinity-dependent decrease in the intensity normalized modified aromatic index (AImod) of DBC-FT and in DBC-BPCA revealed that DBC composition and concentration were primarily controlled by mixing. However, photodegradation and particle adsorption/flocculation may play a role in removing DBC depending on the concentration of total suspended matter (TSM). The two campaigns showed that high discharge increased both riverine input and estuarine output of DBC. However, the removal patterns of DBC-BPCA were minimally influenced by discharge. We further estimated that approximately 20% DBC-BPCA was lost in this estuary annually. Future studies should investigate the transformation of DBC in coastal bays and the open ocean where the residence time is longer and the transparency of bulk water is higher. [ABSTRACT FROM AUTHOR]

Among pollutants released from shipping, black carbon (BC), also known as soot carbon, is of great interest due to its impacts on climate, air quality, human health and ecosystems. BC emitted from ships may enter marine waters and partially transfer to the seawater dissolved phase. In this study, we investigated the optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) derived from BC particles (DOM BC) emitted by ships, which were compared to those of DOM BC of other origins (diesel-powered industrial machine, biomass burning, urban dust), and to terrestrial and marine DOM (DOM TER , DOM MAR). Ship and diesel DOM BC displayed higher ratios of fluorescence maximum intensity to dissolved organic carbon concentration (F max /DOC), higher specific UV absorbance at 254 nm (SUVA 254), and lower fluorescence emission wavelengths than the other tested materials. The parallel factor analysis (PARAFAC)-derived fluorophores of the ship and diesel DOM BC exhibited significant correlations with the concentration of dissolved black carbon (DBC), determined using the benzenepolycarboxylic acid (BPCA) method. Based on these results, we propose the Combustion indeX (COX), to help detecting and tracking ship/fuel combustion pollutions in marine waters. • Black carbon-derived DOM exhibits high F max /DOC ratios and SUVA 254. • Fluorescence and absorbance index of black carbon-derived DOM strongly depends on soot origin. • Specific signature of black carbon-derived DOM exists among natural FDOM found in coastal area. • A new fluorescence index can help to detect and track ship/fuel combustion pollutions in marine waters. [ABSTRACT FROM AUTHOR]

Fungi are ubiquitous in the ocean and hypothesized to be important members of marine ecosystems, but their roles in the marine carbon cycle are poorly understood. Here, we use 13C DNA stable isotope probing coupled with phylogenetic analyses to investigate carbon assimilation within diverse communities of planktonic and benthic fungi in the Benguela Upwelling System (Namibia). Across the redox stratified water column and in the underlying sediments, assimilation of 13C-labeled carbon from diatom extracellular polymeric substances (13C-dEPS) by fungi correlated with the expression of fungal genes encoding carbohydrate-active enzymes. Phylogenetic analysis of genes from 13C-labeled metagenomes revealed saprotrophic lineages related to the facultative yeast Malassezia were the main fungal foragers of pelagic dEPS. In contrast, fungi living in the underlying sulfidic sediments assimilated more 13C-labeled carbon from chemosynthetic bacteria compared to dEPS. This coincided with a unique seafloor fungal community and dissolved organic matter composition compared to the water column, and a 100-fold increased fungal abundance within the subseafloor sulfide-nitrate transition zone. The subseafloor fungi feeding on 13C-labeled chemolithoautotrophs under anoxic conditions were affiliated with Chytridiomycota and Mucoromycota that encode cellulolytic and proteolytic enzymes, revealing polysaccharide and protein-degrading fungi that can anaerobically decompose chemosynthetic necromass. These subseafloor fungi, therefore, appear to be specialized in organic matter that is produced in the sediments. Our findings reveal that the phylogenetic diversity of fungi across redox stratified marine ecosystems translates into functionally relevant mechanisms helping to structure carbon flow from primary producers in marine microbiomes from the surface ocean to the subseafloor. [ABSTRACT FROM AUTHOR]

The temporal dynamics of dissolved organic matter (DOM) are inherently linked with the functioning of aquatic ecosystems. Because DOM represents a complex mixture of millions of different compounds, the statistical analysis of DOM dynamics poses a huge challenge. Here, we present a statistical approach based on hierarchical clustering of time series that groups DOM compounds with synchronous dynamics. We applied this approach to time series of Fourier‐transform ion cyclotron resonance mass spectrometry data of DOM sampled over a period of 26 months near Helgoland, an island in the Southern North Sea. We identified three DOM clusters, which represented a total of 1392 different molecular formulae and showed distinct chemical properties and noticeably compound matches within the PubChem database. Correlations of the three DOM clusters with abundance data of prokaryote and phytoplankton species and with environmental parameters provided consistent indications on the potential origin of the clustered compounds. The first cluster integrated terrestrial DOM originating from riverine discharge reaching Helgoland waters. The second cluster was attributed to DOM related to phytoplankton and microbial activity, whereas the third cluster was interpreted as representing the marine refractory DOM background. Accordingly, while further partitioning divided each of the first two clusters into five sub‐clusters with distinct temporal dynamics and molecular characteristics, the third cluster persisted as a stable feature. Applying a purely mathematical approach, we thus confirmed the differential dynamics of individual DOM compounds and compound groups and showed that temporal dynamics of dissolved molecules are linked to their origin and transformation history. [ABSTRACT FROM AUTHOR]

Microalgae produce copious amounts of structurally diverse polysaccharides, some are bound within cells and cell walls, while others are secreted into the surrounding seawater. A fraction of the secreted polysaccharides assembles into particles promoting aggregation and in turn formation of aggregates increases the export of carbon into the deep ocean via sinking. However, specific polysaccharides contributing to particle formation and carbon export remain unknown. Here, we studied microalgae polysaccharide composition in a system of reduced complexity consisting of lab grown monospecific cultures of the centric diatom species Thalassiosira weissflogii and Chaetoceros socialis. We followed the abundance and dynamics of five specific polysaccharide types in the dissolved and particulate organic matter (DOM and POM) for two weeks. Polysaccharides were detected using monoclonal antibodies (mAbs) specific for β‐1,4‐mannan, β‐1,4‐xylan, arabinogalactan, and two fucose‐containing sulfated polysaccharide (FCSP) epitopes. Additionally, glycan composition of all samples was analyzed by monosaccharide analysis. The time series revealed polysaccharides partition differently between the dissolved and particulate carbon pools. β‐1,4‐xylan and β‐1,4‐mannan were mainly present in POM, possibly as cell wall polymers, while FCSPs were found in both DOM and POM. The data showed that the main glycan component secreted by diatoms was fucose‐containing polysaccharide, which accumulated in DOM over time. Roller tank experiments were used to induce aggregate formation finding FCSP transitioned from DOM to POM under aggregating conditions. These results suggest that diatom‐secreted FCSPs are involved in the formation of aggregates, which promote the formation of particles, and potentially carbon export. [ABSTRACT FROM AUTHOR]

This study addresses key processes in high-energy beach systems using an interdisciplinary approach. We assess spatial variations in subsurface pore water residence times, salinity, organic matter (OM) availability, and redox conditions and their effects on nutrient cycles as well as on microbial community patterns and microphytobenthos growth. At the study site on Spiekeroog Island, southern North Sea, beach hydrology is characterized by the classical zonation with an upper saline plume (USP), a saltwater wedge, and a freshwater discharge tube in between. Sediment and pore water samples were taken along a cross-shore transect from the dunes to the low-water line reaching sediment depths down to 5 m below sediment surface. Spatial variations in pore water residence time, salinity, and organic matter availability lead to steep redox and nutrient gradients. Vertical and horizontal differences in the microbial community indicate the influence of these gradients and salinity on the community structure. Modeled seawater flux through the USP and freshwater flux through the tube are on average 2.8 and 0.75 m 3 per day and meter of shoreline, respectively. Furthermore, ridge sediments at the lower beach discharge seawater at rates of 0.5 and 1.0 m 3 per day and meter of shoreline towards the runnel and seaside, respectively. Applying seawater and freshwater fluxes and representative nutrient concentrations for the discharge zones, nutrient fluxes to adjacent nearshore waters are 117 mmol NH 4 + , 55 mmol PO 4 3 − and 575 mmol Si(OH) 4 per day and meter of shoreline. We propose that this nutrient efflux triggers growth of microphytobenthos on sediment surfaces of the discharge zone. A first comparison of nutrient discharge rates of the beach site with a nearby sandy backbarrier tidal flat margin indicates that the beach system might be of less importance in supplying recycled nutrients to nearshore waters than the backbarrier tidal flat area. [ABSTRACT FROM AUTHOR]

Publisher's Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Correction to: Biogeochemistry https://doi.org/10.1007/s10533-022-00987-9 The percentage symbol in the equation was not correctly typed, it was changed from % to ‰. [Extracted from the article]

Dissolved organic matter (DOM) in the oceans is one of the largest pools of reduced carbon on Earth, comparable in size to the atmospheric CO2 reservoir. A vast number of compounds are present in DOM, and they play important roles in all major element cycles, contribute to the storage of atmospheric CO2 in the ocean, support marine ecosystems, and facilitate interactions between organisms. At the heart of the DOM cycle lie molecular-level relationships between the individual compounds in DOM and the members of the ocean microbiome that produce and consume them. In the past, these connections have eluded clear definition because of the sheer numerical complexity of both DOM molecules and microorganisms. Emerging tools in analytical chemistry, microbiology, and informatics are breaking down the barriers to a fuller appreciation of these connections. Here we highlight questions being addressed using recent methodological and technological developments in those fields and consider how these advances are transforming our understanding of some of the most important reactions of the marine carbon cycle. [ABSTRACT FROM AUTHOR]

The subtropical South Pacific Gyre (SPG) encompasses the largest oligotrophic region of the global ocean. In these remote waters dissolved organic matter (DOM) accumulates in the surface waters, though constituting a potential source of nutrients and energy to sustain microbial life. On a zonal transect across the SPG, we quantified bulk dissolved organic carbon (DOC) and assessed the DOM composition via ultrahigh resolution mass spectrometry (UHR-MS) of solid-phase extracted DOC (SPE-DOC) to elucidate the molecular-level reasons behind the apparent recalcitrance of the DOM prevailing in the SPG. We included a comparison between two individual formula assignment approaches to UHR-MS data in absorption and magnitude mode which yielded consistent results. DOC concentrations exceeding 100 μmol C L−1 in the warm and saline waters of the central gyre were higher than in the surface waters of the adjacent western South Pacific. Along the transect, concentrations of SPE-DOC were less variable than bulk DOC. Nevertheless, molecular-level investigation revealed that the composition of the DOM accumulated in the central SPG generally conformed to characteristics of surface ocean DOM, but all assessed properties were more pronounced. We found high abundances of potentially labile unsaturated aliphatic molecular formulas and a low calculated degradation index for the DOM of likely marine microbial origin. Markedly decreased molar N/C ratios in the central gyre indicated preferential microbial utilization of nitrogen-containing DOM. A distinct imprint of extensive photochemical reworking was manifested in the low aromaticity of the DOM in the photic layer. Over the whole water column, ageing of DOM was evident through the small, but significant contribution of SPE-DOC to apparent oxygen utilization as well as on molecular level. Our findings demonstrate that SPE-DOC captures carbon fractions relevant on timescales of seasons to timescales covering ocean circulation and biogeochemical processes in stable gyre systems are imprinted in the DOM molecular composition. • DOM concentration and composition were assessed in the South Pacific. • DOC accumulates in oligotrophic South Pacific Subtropical gyre. • DOM molecular composition reveals low N/C and imprint of photodegradation. • Solid-phase extracted DOM fraction suitable to trace DOM ageing across ocean basins. [ABSTRACT FROM AUTHOR]

Diatoms as important phytoplankton components interact with and are colonized by heterotrophic bacteria. This colonization has been studied extensively in the past but a distinction between the bacterial colonization directly on diatom cells or on the aggregated organic material, exopolymeric substances (EPS), was little addressed. Here we show that the diatom Thalassiosira rotula and EPS were differently colonized by strains of Roseobacteraceae and Flavobacteriaceae in two and tree partner treatments and an enriched natural bacterial community as inoculum. In two partner treatments, the algae and EPS were generally less colonized than in the three partner treatments. Two strains benefitted greatly from the presence of another partner as the proportions of their subpopulations colonizing the diatom cell and the EPS were much enhanced relative to their two partner treatments. Highest proportions of bacteria colonizing the diatom and EPS occurred in the treatment inoculated with the enriched natural bacterial community. Dissolved organic carbon, amino acids and carbohydrates produced by T. rotula were differently used by the bacteria in the two and three partner treatments and most efficiently by the enriched natural bacterial community. Our approach is a valid model system to study physico-chemical bacteria-diatom interactions with increasing complexity., (© 2023 The Authors. Environmental Microbiology published by Applied Microbiology International and John Wiley & Sons Ltd.)

The atmospheric wet deposition has been recognized as a significant allochthonous source of dissolved organic carbon (DOC) to the ocean. However, few studies have examined the biolability of rainwater dissolved organic matter (DOM) at the molecular level. Rainwater samples were collected and incubated with ambient microbes. DOC, UV-vis spectroscopy, formic acid (FA), acetic acid (AA), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS) were applied. Approximately 50 ± 16 % of rainwater DOC and ~90 % of FA and AA were bioconsumed within 28 days. The contribution of FA and AA to the total BDOC was ~30 %, which was the largest known biolabile fraction in rainwater DOC. In contrast, only approximately 15 % of formulae identified by FT-ICRMS were consumed, which were characterized by higher saturation, higher heteroatom content and lower modified aromaticity. Among the major high molecular weight secondary organic carbon (HWW-SOC)-like compounds, organosulfate contained the largest fraction of consumed formulae, while biogenic volatile organic-derived CHO compounds had the lowest. Our study for the first time provided both quantitative and qualitative understanding of the bioavailability of rainwater DOM, which is essential for understanding their effects on the biogeochemical cycles and the environmental health in the receiving waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The formation of sinking particles in the ocean, which promote carbon sequestration into deeper water and sediments, involves algal polysaccharides acting as an adhesive, binding together molecules, cells and minerals. These as yet unidentified adhesive polysaccharides must resist degradation by bacterial enzymes or else they dissolve and particles disassemble before exporting carbon. Here, using monoclonal antibodies as analytical tools, we trace the abundance of 27 polysaccharide epitopes in dissolved and particulate organic matter during a series of diatom blooms in the North Sea, and discover a fucose-containing sulphated polysaccharide (FCSP) that resists enzymatic degradation, accumulates and aggregates. Previously only known as a macroalgal polysaccharide, we find FCSP to be secreted by several globally abundant diatom species including the genera Chaetoceros and Thalassiosira. These findings provide evidence for a novel polysaccharide candidate to contribute to carbon sequestration in the ocean.

Ammonia-oxidizing archaea of the phylum Thaumarchaeota are among the most abundant marine microorganisms 1 . These organisms thrive in the oceans despite ammonium being present at low nanomolar concentrations 2,3 . Some Thaumarchaeota isolates have been shown to utilize urea and cyanate as energy and N sources through intracellular conversion to ammonium 4-6 . Yet, it is unclear whether patterns observed in culture extend to marine Thaumarchaeota, and whether Thaumarchaeota in the ocean directly utilize urea and cyanate or rely on co-occurring microorganisms to break these substrates down to ammonium. Urea utilization has been reported for marine ammonia-oxidizing communities 7-10 , but no evidence of cyanate utilization exists for marine ammonia oxidizers. Here, we demonstrate that in the Gulf of Mexico, Thaumarchaeota use urea and cyanate both directly and indirectly as energy and N sources. We observed substantial and linear rates of nitrite production from urea and cyanate additions, which often persisted even when ammonium was added to micromolar concentrations. Furthermore, single-cell analysis revealed that the Thaumarchaeota incorporated ammonium-, urea- and cyanate-derived N at significantly higher rates than most other microorganisms. Yet, no cyanases were detected in thaumarchaeal genomic data from the Gulf of Mexico. Therefore, we tested cyanate utilization in Nitrosopumilus maritimus, which also lacks a canonical cyanase, and showed that cyanate was oxidized to nitrite. Our findings demonstrate that marine Thaumarchaeota can use urea and cyanate as both an energy and N source. On the basis of these results, we hypothesize that urea and cyanate are substrates for ammonia-oxidizing Thaumarchaeota throughout the ocean.