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The concentration of CO2 in the atmosphere is sensitive to changes in the depth at which sinking particulate organic matter is remineralized: often described as a change in the exponent “b” of the Martin curve. Sediment trap observations from deep and intermediate depths suggest there is a spatially heterogeneous pattern of b, particularly varying with latitude, but disagree over the exact spatial patterns. Here we use a biogeochemical model of the phosphorus cycle coupled with a steady-state representation of ocean circulation to explore the sensitivity of preformed phosphate and atmospheric CO2 to spatial variability in remineralization depths. A Latin hypercube sampling method is used to simultaneously vary the Martin curve independently within 15 different regions, as a basis for a regression-based analysis used to derive a quantitative measure of sensitivity. Approximately 30 % of the sensitivity of atmospheric CO2 to changes in remineralization depths is driven by changes in the subantarctic region (36 to 60∘ S) similar in magnitude to the Pacific basin despite the much smaller area and lower export production. Overall, the absolute magnitude of sensitivity is controlled by export production, but the relative spatial patterns in sensitivity are predominantly constrained by ocean circulation pathways. The high sensitivity in the subantarctic regions is driven by a combination of high export production and the high connectivity of these regions to regions important for the export of preformed nutrients such as the Southern Ocean and North Atlantic. Overall, regionally varying remineralization depths contribute to variability in CO2 of between around 5 and 15 ppm, relative to a global mean change in remineralization depth. Future changes in the environmental and ecological drivers of remineralization, such as temperature and ocean acidification, are expected to be most significant in the high latitudes where CO2 sensitivity to remineralization is also highest. The importance of ocean circulation pathways to the high sensitivity in subantarctic regions also has significance for past climates given the importance of circulation changes in the Southern Ocean.

In this study we analyzed sediment trap time series from five tropical sites to assess seasonal variations in concentrations and fluxes of long-chain diols (LCDs) and associated proxies with emphasis on the long-chain diol index (LDI) temperature proxy. For the tropical Atlantic, we observe that generally less than 2 % of LCDs settling from the water column are preserved in the sediment. The Atlantic and Mozambique Channel traps reveal minimal seasonal variations in the LDI, similar to the two other lipid-based temperature proxies TEX86 and U37K′. In addition, annual mean LDI-derived temperatures are in good agreement with the annual mean satellite-derived sea surface temperatures (SSTs). In contrast, the LDI in the Cariaco Basin shows larger seasonal variation, as do the TEX86 and U37K′. Here, the LDI underestimates SST during the warmest months, which is possibly due to summer stratification and the habitat depth of the diol producers deepening to around 20–30 m. Surface sediment LDI temperatures in the Atlantic and Mozambique Channel compare well with the average LDI-derived temperatures from the overlying sediment traps, as well as with decadal annual mean SST. Lastly, we observed large seasonal variations in the diol index, as an indicator of upwelling conditions, at three sites: in the eastern Atlantic, potentially linked to Guinea Dome upwelling; in the Cariaco Basin, likely caused by seasonal upwelling; and in the Mozambique Channel, where diol index variations may be driven by upwelling from favorable winds and/or eddy migration.

Cable bacteria are multicellular, filamentous microorganisms that are capable of transporting electrons over centimeter-scale distances. Although recently discovered, these bacteria appear to be widely present in the seafloor, and when active they exert a strong imprint on the local geochemistry. In particular, their electrogenic metabolism induces unusually strong pH excursions in aquatic sediments, which induces considerable mineral dissolution, and subsequent mineral reprecipitation. However, at present, it is unknown whether and how cable bacteria play an active or direct role in the mineral reprecipitation process. To this end we present an explorative study of the formation of sedimentary minerals in and near filamentous cable bacteria using a combined approach of electron microscopy and spectroscopic techniques. Our observations reveal the formation of polyphosphate granules within the cells and two different types of biomineral formation directly associated with multicellular filaments of these cable bacteria: (i) the attachment and incorporation of clay particles in a coating surrounding the bacteria and (ii) encrustation of the cell envelope by iron minerals. These findings suggest a complex interaction between cable bacteria and the surrounding sediment matrix, and a substantial imprint of the electrogenic metabolism on mineral diagenesis and sedimentary biogeochemical cycling. In particular, the encrustation process leaves many open questions for further research. For example, we hypothesize that the complete encrustation of filaments might create a diffusion barrier and negatively impact the metabolism of the cable bacteria.

Future deep-sea mining for polymetallic nodules in abyssal plains will negatively impact the benthic ecosystem, but it is largely unclear whether this ecosystem will be able to recover from mining disturbance and if so, to what extent and at what timescale. During the “DISturbance and reCOLonization” (DISCOL) experiment, a total of 22 % of the seafloor within a 10.8 km2 circular area of the nodule-rich seafloor in the Peru Basin (SE Pacific) was ploughed in 1989 to bury nodules and mix the surface sediment. This area was revisited 0.1, 0.5, 3, 7, and 26 years after the disturbance to assess macrofauna, invertebrate megafauna and fish density and diversity. We used this unique abyssal faunal time series to develop carbon-based food web models for each point in the time series using the linear inverse modeling approach for sediments subjected to two disturbance levels: (1) outside the plough tracks; not directly disturbed by plough, but probably suffered from additional sedimentation; and (2) inside the plough tracks. Total faunal carbon stock was always higher outside plough tracks compared with inside plough tracks. After 26 years, the carbon stock inside the plough tracks was 54 % of the carbon stock outside plough tracks. Deposit feeders were least affected by the disturbance, with modeled respiration, external predation, and excretion rates being reduced by only 2.6 % inside plough tracks compared with outside plough tracks after 26 years. In contrast, the respiration rate of filter and suspension feeders was 79.5 % lower in the plough tracks after 26 years. The “total system throughput” (T..), i.e., the total sum of modeled carbon flows in the food web, was higher throughout the time series outside plough tracks compared with the corresponding inside plough tracks area and was lowest inside plough tracks directly after the disturbance (8.63 × 10−3 ± 1.58 × 10−5 mmol C m−2 d−1). Even 26 years after the DISCOL disturbance, the discrepancy of T.. between outside and inside plough tracks was still 56 %. Hence, C cycling within the faunal compartments of an abyssal plain ecosystem remains reduced 26 years after physical disturbance, and a longer period is required for the system to recover from such a small-scale sediment disturbance experiment.

Coastal areas are impacted by multiple natural and anthropogenic processes and experience stronger pH fluctuations than the open ocean. These variations can weaken or intensify the ocean acidification signal induced by increasing atmospheric pCO2. The development of eutrophication-induced hypoxia intensifies coastal acidification, since the CO2 produced during respiration decreases the buffering capacity in any hypoxic bottom water. To assess the combined ecosystem impacts of acidification and hypoxia, we quantified the seasonal variation in pH and oxygen dynamics in the water column of a seasonally stratified coastal basin (Lake Grevelingen, the Netherlands). Monthly water-column chemistry measurements were complemented with estimates of primary production and respiration using O2 light–dark incubations, in addition to sediment–water fluxes of dissolved inorganic carbon (DIC) and total alkalinity (TA). The resulting data set was used to set up a proton budget on a seasonal scale. Temperature-induced seasonal stratification combined with a high community respiration was responsible for the depletion of oxygen in the bottom water in summer. The surface water showed strong seasonal variation in process rates (primary production, CO2 air–sea exchange), but relatively small seasonal pH fluctuations (0.46 units on the total hydrogen ion scale). In contrast, the bottom water showed less seasonality in biogeochemical rates (respiration, sediment–water exchange), but stronger pH fluctuations (0.60 units). This marked difference in pH dynamics could be attributed to a substantial reduction in the acid–base buffering capacity of the hypoxic bottom water in the summer period. Our results highlight the importance of acid–base buffering in the pH dynamics of coastal systems and illustrate the increasing vulnerability of hypoxic, CO2-rich waters to any acidifying process.

Changes in marine net primary productivity (PP) and export of particulate organic carbon (EP) are projected over the 21st century with four global coupled carbon cycle-climate models. These include representations of marine ecosystems and the carbon cycle of different structure and complexity. All four models show a decrease in global mean PP and EP between 2 and 20% by 2100 relative to preindustrial conditions, for the SRES A2 emission scenario. Two different regimes for productivity changes are consistently identified in all models. The first chain of mechanisms is dominant in the low- and mid-latitude ocean and in the North Atlantic: reduced input of macro-nutrients into the euphotic zone related to enhanced stratification, reduced mixed layer depth, and slowed circulation causes a decrease in macro-nutrient concentrations and in PP and EP. The second regime is projected for parts of the Southern Ocean: an alleviation of light and/or temperature limitation leads to an increase in PP and EP as productivity is fueled by a sustained nutrient input. A region of disagreement among the models is the Arctic, where three models project an increase in PP while one model projects a decrease. Projected changes in seasonal and interannual variability are modest in most regions. Regional model skill metrics are proposed to generate multi-model mean fields that show an improved skill in representing observation-based estimates compared to a simple multi-model average. Model results are compared to recent productivity projections with three different algorithms, usually applied to infer net primary production from satellite observations.

Shelf seas are among the most active biogeochemical marine environments and the East Siberian Sea is a prime example. This sea is supplied by seawater from both the Atlantic and Pacific Oceans and has a substantial input of river runoff. All of these waters contribute chemical constituents, dissolved and particulate, but of different signatures. Sea ice formation during the winter season and melting in the summer has a major impact on physical as well as biogeochemical conditions. The internal circulation and water mass distribution is significantly influenced by the atmospheric pressure field. The western region is dominated by input of river runoff from the Laptev Sea and an extensive input of terrestrial organic matter. The microbial decay of this organic matter produces carbon dioxide (CO2) that oversaturates all waters from the surface to bottom relative to atmospheric level, even when primary production, inferred from low surface water nutrients, has occurred. The eastern surface waters were under-saturated with respect to CO2 illustrating the dominance of marine primary production. The drawdown of dissolved inorganic carbon equals a primary production of ~0.8 ± 2 mol C m−2, which when multiplied by half the area of the East Siberian Sea, ~500 000 km2, results in an annual primary production of 0.4 (± 1) × 1012 mol C or ~4 (± 10) × 1012 gC. Microbial decay occurs through much of the water column, but dominates at the sediment interface where the majority of organic matter ends up, thus more of the decay products are recycled to the bottom water. High nutrient concentrations and fugacity of CO2 and low oxygen and pH were observed in the bottom waters. Another signature of organic matter decomposition, methane (CH4), was observed in very high but variable concentrations. This is due to its seabed sources of glacial origin or modern production from ancient organic matter, becoming available due to sub-sea permafrost thaw and formation of so-called taliks. The decay of organic matter to CO2 as well as oxidation of CH4 to CO2 contribute to a natural ocean acidification making the saturation state of calcium carbonate low, resulting in under-saturation of all the bottom waters with respect to aragonite and large areas of under-saturation down to 50 % with respect to calcite. Hence, conditions for calcifying organisms are very unfavorable.

Over the past couple of decades it has become apparent that air-land-sea interactions in the Arctic have a substantial impact on the composition of the overlying atmosphere (ACIA, 2004). The Arctic Ocean is small (only ~4 % of the total World Ocean), but it is surrounded by offshore and onshore permafrost which is thawing at increasing rates under warming conditions, releasing carbon dioxide (CO2) into the water and atmosphere. The Arctic Ocean shelf where the most intensive biogeochemical processes have occurred occupies 1/3 of the ocean. The East Siberian Sea (ESS) shelf is the shallowest and widest shelf among the Arctic seas, and the least studied. The objective of this study was to highlight the importance of different factors that impact the carbon system (CS) as well as the CO2 flux dynamics in the ESS. CS variables were measured in the ESS in September 2003 and, 2004 and in late August–September 2008. It was shown that the western part of the ESS represents a river- and coastal-erosion-dominated heterotrophic ocean margin that is a source for atmospheric CO2. The eastern part of the ESS is a Pacific-water-dominated autotrophic area, which acts as a sink for atmospheric CO2. Our results indicate that the year-to-year dynamics of the partial pressure of CO2 in the surface water as well as the air-sea flux of CO2 varies substantially. In one year the ESS shelf was mainly heterotrophic and served as a moderate summertime source of CO2 (year 2004). In another year gross primary production exceeded community respiration in a relatively large part of the ESS and the ESS shelf was only a weak source of CO2 into the atmosphere (year 2008). It was shown that many factors impact the CS and CO2 flux dynamics (such as river runoff, coastal erosion, primary production/respiration, etc.), but they were mainly determined by the interplay and distribution of water masses that are basically influenced by the atmospheric circulation. In this contribution the air-sea CO2 fluxes were evaluated in the ESS based on measured CS characteristics, and summertime fluxes were estimated. It was shown that the total ESS shelf is a net source of CO2 for the atmosphere in a range of 0.4 × 1012 to 2.3 × 1012 g C.

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe)-oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ.Here we combine detailed geochemical analyses of the sediment and porewater with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P), and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. In line with previous studies in the Black Sea, we show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g., vivianite) are converted to sulfide phases, leading to an enrichment in solid-phase S and the release of phosphate to the porewater. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward-diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front.Our model results further demonstrate that downward-migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM ( ∼ 1–100 pmol cm−3 d−1) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction and reactivation of less reactive Fe oxides by methanogens, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the porewater at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate, and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Recently, long filamentous bacteria have been reported conducting electrons over centimetre distances in marine sediments. These so-called cable bacteria perform an electrogenic form of sulfur oxidation, whereby long-distance electron transport links sulfide oxidation in deeper sediment horizons to oxygen reduction in the upper millimetres of the sediment. Electrogenic sulfur oxidation exerts a strong impact on the local sediment biogeochemistry, but it is currently unknown how prevalent the process is within the seafloor. Here we provide a state-of-the-art assessment of its global distribution by combining new field observations with previous reports from the literature. This synthesis demonstrates that electrogenic sulfur oxidation, and hence microbial long-distance electron transport, is a widespread phenomenon in the present-day seafloor. The process is found in coastal sediments within different climate zones (off the Netherlands, Greenland, the USA, Australia) and thrives on a range of different coastal habitats (estuaries, salt marshes, mangroves, coastal hypoxic basins, intertidal flats). The combination of a widespread occurrence and a strong local geochemical imprint suggests that electrogenic sulfur oxidation could be an important, and hitherto overlooked, component of the marine cycle of carbon, sulfur and other elements.