Description: Over the last decades, the Arctic Ocean has suffered a substantial decline in sea ice cover due to global warming. The impacts of these variations on primary productivity, fluxes of dissolved and particulate organic matter (OM) and turnover at the seafloor are still poorly understood. Here we focus on the characteristics and dynamics of the pool of marine dissolved OM (DOM) in surface sediments of the Arctic Ocean. To investigate spatial and temporal variations of DOM in relation to particulate OM input and benthic microbial community parameters, sediment porewater and overlying bottom water were collected from the long-term observatory HAUSGARTEN in June 2013 and 2014. The study area in the Fram Strait, which is partially covered by sea ice, was sampled along a bathymetric transect (1050–5500 m water depth), from east to west (7°0.2′ E to 5°17′ W), and from south to north (78°37’ to 79°43’ N). Molecular data on solid phase extracted DOM obtained via Fourier Transform Ion Cyclotron Resonance Mass Spectrometric analysis and a suite of bulk chemical parameters were related to benthic biogeochemical data. Our results demonstrate a close coupling between the production and input of OM from the surface ocean to the seafloor, and the concentration and composition of DOC/DOM in the deep sea. Surface porewaters collected in 2013 from shallower stations (≤1500 m water depth) in the eastern Fram Strait, had a signal of a larger and more recent input of OM (higher concentrations of phytodetritus). This was associated with higher numbers of molecular formulas, abundances of unsaturated aliphatic and N-containing formulas, in concert with higher enzymatic activity, phospholipids, total organic carbon and protein content. In contrast, porewaters collected in 2014 from deeper stations and from the West, were associated with lower OM input, and showed higher abundances of aromatic and oxygen-poor compounds. Higher OM input was also reflected in higher DOC concentrations and fluxes from the sediment into the water column. Our study demonstrates that regional and temporal variations in OM input can quickly translate into changes in the quantity and quality of surface porewater DOM, the latter substantially altered by deep-sea sediment bacteria.

Description: Dissolved organic matter (DOM) is an omnipresent constituent of natural water bodies. Reuse and transformation of DOM compounds in the water column is driven by physicochemical and biological processes leading to the production of refractory DOM. Typically, breakdown of DOM chemical compounds into smaller or more condensed fragments is triggered by ultraviolet (UV) radiation. Here, we present a study on the photodegradation of DOM produced during an incubation experiment with a natural microbial community. At the end of the first incubation without UV irradiation, the samples from 3 mesocosms were filtered to remove microbes and particles and continuously exposed to UV radiation (280–365 nm). We investigated DOM in depth via monitoring of dissolved organic carbon (DOC) concentrations, DOM molecular characterization by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and excitation emission matrix spectroscopy (EEMS). Analysis of variance indicated no significant differences in the DOC concentration between treatments. Main peaks in the fluorescent DOM (FDOM) were photo-bleached by UV radiation, and an increase in the fluorescent intensity of selected peaks was observed on irradiated samples toward the end of the experiment. Parallel factor analysis (PARAFAC) indicated the presence of three main components in all treatments: C1 (Marine humic M), C2 (Bacterial produced humic C), C3 (Tyrosine), and an additional component in the dark incubation of mesocosm 3, C4 (Tryptophan). Despite an intensive filtration protocol through 0.7, 0.2 and 0.1 μm filters, low bacterial abundances were determined (〈2.5 × 10−3 cells mL−1). We observed a direct correlation between structural indices and the intensity of PARAFAC components. Average double bond equivalent and aromaticity were strongly positively correlated with PARAFAC components C1 and C2 for one or more mesocosm. Moreover, FT-ICR-MS showed that under the tested conditions, the refractory character of the DOM assessed as the similarity to a deep ocean DOM reference did not increase on molecular level. Thus, mechanisms other than photochemical transformations of relatively recent DOM are likely necessary to facilitate long-term stability of DOM in the oceans.

Description: The potential of marine dissolved organic matter (DOM) for free radical scavenging has been extensively evaluated, however, the quantitative assessment of the antioxidant potential has been recently measured for the first time. The linkage of the DOM antioxidant potential to its molecular composition has not yet been examined. Following this line, this article takes a step forward by assessing, throughout a polarity-mediated fractionation, (1) the antioxidant capacity and phenolic content and (2) the molecular characterization of DOM in a more exhaustive manner. (3) The DOM antioxidant potential and phenolic content was linked to the molecular composition of DOM, which was molecularly characterized using ultrahigh resolution Fourier transform Ion Cyclotron Resonance mass spectrometry (FT-ICR MS). Antioxidant activity and phenolic content were quantified by the free radical 2,2’-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS⋅) and the Folin-Ciocalteu methods, respectively. We considered three types of different natural DOM samples: the deep North Pacific Ocean, the oligotrophic surface of the North Pacific Ocean and porewater from the sulfidic tidal flats of the Wadden Sea. Bulk porewater and its individual polarity fractions presented the highest antioxidant activity and phenolic content. DOM from the water column samples had lower antioxidant activity and phenolic content than porewater, but exceeded what it is commonly found in macroalgae, microalgae, fruits and vegetables with cosmeceutical purposes. Our values were similar to published values for terrestrial DOM. The variations in bioactivity were dependent on polarity and molecular composition. The high resolution and high mass accuracy used to determine the molecular composition of marine DOM and the chemometric and multistatistical analyses employed have allowed to distinguish molecular categories that are related to the bioactive potential. As a future perspective, we performed cytotoxicity tests with human cells and propose marine DOM as a natural ingredient for the development of cosmeceutical products.

Description: Black carbon (BC) is a recalcitrant form of organic carbon (OC) produced by landscape fires. BC is an important component of the global carbon cycle because, compared to unburned biogenic OC, it is selectively conserved in terrestrial and oceanic pools. Here we show that the dissolved BC (DBC) content of dissolved OC (DOC) is twice greater in major (sub)tropical and high-latitude rivers than in major temperate rivers, with further significant differences between biomes. We estimate that rivers export 18 ± 4 Tg DBC year−1 globally and that, including particulate BC fluxes, total riverine export amounts to 43 ± 15 Tg BC year−1 (12 ± 5% of the OC flux). While rivers export ~1% of the OC sequestered by terrestrial vegetation, our estimates suggest that 34 ± 26% of the BC produced by landscape fires has an oceanic fate. Biogeochemical models require modification to account for the unique dynamics of BC and to predict the response of recalcitrant OC export to changing environmental conditions.

Description: Only few studies exist that investigate the dynamics of deep-sea dissolved organic matter (DOM) derived from hydrothermal vents. In this study, we provide first insight into the molecular composition of DOM associated with Indian Ocean hydrothermal systems covering the full range from hot focussed endmember fluids over diffuse fluids to open ocean hydrothermal plumes and deep seawater. We combined geochemical analyses with molecular characterization of DOM using ultra-high resolution mass spectrometry (FT-ICR-MS). We studied two vent systems with fluids venting 〉330 °C and up to 97% of hydrothermal endmember: the Kairei vents (Central Indian Ridge) with brine phase separation, and the newly discovered Pelagia vents (South-East Indian Ridge). The hot fluids in both systems were highly enriched in dissolved Fe, Si, K, Li, Mn and Zn compared to seawater. The molecular composition of DOM from hot fluids differed substantially from that of diffuse fluids and plumes, in which the composition was highly dominated by the seawater DOM signature. Low O/C ratio average in hot fluids (〈0.38) indicated potential input of more reduced (O-poor) DOM compounds from the vents into the surrounding seawater, independently of the vent location and of whether the fluid has undergone phase separation. To test the importance of pure thermal degradation, we compared our samples to fluids subjected to abiotic thermal degradation under laboratory conditions and we observed that our natural samples largely differed (〉94% Bray Curtis dissimilarity) from the experimental ones, suggesting additional degradation processes of organic compounds at the Indian Ocean hydrothermal systems.

Description: Molybdenum (Mo) and thallium (Tl) are known as conservative-type elements in open ocean settings, despite their involvement in bio-cycling processes. In coastal oceans like the southern North Sea, however, positive and negative anomalies of dissolved Mo and Tl concentrations occur during certain time periods of the year, which are characterized by intensive organic matter cycling. The main motivation of the present study was to identify potential drivers for the non-conservative behavior of Mo and Tl. For this purpose, we conducted an indoor mesocosm experiment with natural seawater and sediment (including a natural microorganism community) and applied close to natural light and tidal (diurnal) conditions. After an incubation time of 35 days, we initialized a storm event to examine its influence on organic matter as well as nutrient and trace metal cycling. The temporal pattern of the inorganic macronutrients (N-species, dissolved phosphorous, dissolved silicate) as well as dissolved and particulate organic matter was highly dependent on the interplay of the phytoplankton and its associated bacteria bloom. Our results suggest that the redox-sensitive trace metals manganese (Mn), vanadium (V) and iron (Fe) were involved in bio-cycling processes. While temporal pattern of dissolved Mn and V were likely induced by active (macro-)nutrient assimilation rather than redox induced phase changes, dissolved Fe was present as organo-metallic complex and shielded from the flocculation as metal oxide. Our results further reveal positive Mo and negative Tl anomalies, especially during pre-storm conditions. The additional input of Mo was derived from the oxidation of reducing bottom sediments. Thereby, the degree as well as the rate of Mo-input was dependent on the composition of the background sediment. In the water column Mo was not only present in its dissolved oxidized form but was also stabilized by organic (algae-detritus, ligands) and inorganic (aluminosilicates) binding partners, preventing its (re-)deposition. Negative Tl anomalies were found to be induced by its immobilization by organic (algae-detritus, ligands) and inorganic (aluminosilicates) carrier phases in the water column prior to its deposition and potential fixation in the sulfidic bottom sediments. Particles derived from the storm event did not have any considerable effect on dissolved organic nor inorganic compounds, as they (re-)deposited before significant remineralization processes could take place.

Description: 1. Plant diversity is an important driver of belowground ecosystem functions, such as root growth, soil organic matter (SOM) storage, and microbial metabolism, mainly by influencing the interactions between plant roots and soil. Dissolved organic matter (DOM), as the most mobile form of SOM, plays a crucial role for a multitude of soil processes that are central for ecosystem functioning. Thus, DOM is likely to be an important mediator of plant diversity effects on soil processes. However, the relationships between plant diversity and DOM have not been studied so far. 2. We investigated the mechanisms underlying plant diversity effects on concentrations of DOM using continuous soil water sampling across 6 years and 62 plant communities in a long‐term grassland biodiversity experiment in Jena, Germany. Furthermore, we investigated plant diversity effects on the molecular properties of DOM in a subset of the samples. 3. Although DOM concentrations were highly variable over the course of the year with highest concentrations in summer and autumn, we found that DOM concentrations consistently increased with plant diversity across seasons. The positive plant diversity effect on DOM concentrations was mainly mediated by increased microbial activity and newly sequestered carbon in topsoil. However, the effect of soil microbial activity on DOM concentrations differed between seasons, indicating DOM consumption in winter and spring, and DOM production in summer and autumn. Furthermore, we found increased contents of small and easily decomposable DOM molecules reaching deeper soil layers with high plant diversity. 4. Synthesis. Our findings suggest that plant diversity enhances the continuous downward transport of DOM in multiple ways. On the one hand, higher plant diversity results in higher DOM concentrations, on the other hand, this DOM is less degraded. The present study indicates, for the first time, that higher plant diversity enhances the downward transport of dissolved molecules that likely stimulate soil development in deeper layers and therefore increase soil fertility.

Description: Advective flows of seawater and fresh groundwater through coastal aquifers form a unique ecohydrological interface, the subterranean estuary (STE). Here, freshly produced marine organic matter and oxygen mix with groundwater, which is low in oxygen and contains aged organic carbon (OC) from terrestrial sources. Along the groundwater flow paths, dissolved organic matter (DOM) is degraded and inorganic electron acceptors are successively used up. Because of the different DOM sources and ages, exact degradation pathways are often difficult to disentangle, especially in high-energy environments with dynamic changes in beach morphology, source composition, and hydraulic gradients. From a case study site on a barrier island in the German North Sea, we present detailed biogeochemical data from freshwater lens groundwater, seawater, and beach porewater samples collected over different seasons. The samples were analyzed for physico-chemistry (e.g., salinity, temperature, dissolved silicate), (reduced) electron acceptors (e.g., oxygen, nitrate, and iron), and dissolved organic carbon (DOC). DOM was isolated and molecularly characterized via soft-ionization ultra-high-resolution mass spectrometry, and molecular formulae were identified in each sample. We found that the islands’ freshwater lens harbors a surprisingly high DOM molecular diversity and heterogeneity, possibly due to patchy distributions of buried peat lenses. Furthermore, a comparison of DOM composition of the endmembers indicated that the Spiekeroog high-energy beach STE conveys chemically modified, terrestrial DOM from the inland freshwater lens to the coastal ocean. In the beach intertidal zone, porewater DOC concentrations, lability of DOM and oxygen concentrations, decreased while dissolved (reduced) iron and dissolved silicate concentrations increased. This observation is consistent with the assumption of a continuous degradation of labile DOM along a cross-shore gradient, even in this dynamic environment. Accordingly, molecular properties of DOM indicated enhanced degradation, and “humic-like” fluorescent DOM fraction increased along the flow paths, likely through accumulation of compounds less susceptible to microbial consumption. Our data indicate that the high-energy beach STE is likely a net sink of OC from the terrestrial and marine realm, and that barrier islands such as Spiekeroog may act as efficient “digestors” of organic matter.