Sulphur and Carbon Isotopes as Tracers of Past Sub-seafloor Microbial Activity

Microbial life below the seafloor has changed over geological time, but these changes are often not obvious, as they are not recorded in the sediment. Sulphur (S) isotope values in pyrite extracted from a Plio- to Holocene sequence of the Peru Margin (Ocean Drilling Program, ODP, Site 1229) show a down-core pattern that correlates with the pattern of carbon (C) isotopes in diagenetic dolomite. Early formation of the pyrite is indicated by the mineralogical composition of iron, showing a high degree of pyritization throughout the sedimentary sequence. Hence, the S-record could not have been substantially overprinted by later pyrite formation. The S- and C-isotope profiles show, thus, evidence for two episodes of enhanced microbial methane production with a very shallow sulphate-methane transition zone. The events of high activity are correlated with zones of elevated organic C content in the stratigraphic sequence. Our results demonstrate how isotopic signatures preserved in diagenetic mineral phases provide information on changes of past biogeochemical activity in a dynamic sub-seafloor biosphere

Effect of temperature rise and ocean acidification on growth of calcifying tubeworm shells (Spirorbis spirorbis): an in situ benthocosm approach

The calcareous tubeworm Spirorbis spirorbis is a widespread serpulid species in the Baltic Sea, where it commonly grows as an epibiont on brown macroalgae (genus Fucus). It lives within a Mg-calcite shell and could be affected by ocean acidification and temperature rise induced by the predicted future atmospheric CO2 increase. However, Spirorbis tubes grow in a chemically modified boundary layer around the algae, which may mitigate acidification. In order to investigate how increasing temperature and rising pCO2 may influence S. spirorbis shell growth we carried out four seasonal experiments in the Kiel Outdoor Benthocosms at elevated pCO2 and temperature conditions. Compared to laboratory batch culture experiments the benthocosm approach provides a better representation of natural conditions for physical and biological ecosystem parameters, including seasonal variations. We find that growth rates of S. spirorbis are significantly controlled by ontogenetic and seasonal effects. The length of the newly grown tube is inversely related to the initial diameter of the shell. Our study showed no significant difference of the growth rates between ambient atmospheric and elevated (1100 ppm) pCO2 conditions. No influence of daily average CaCO3 saturation state on the growth rates of S. spirorbis was observed. We found, however, net growth of the shells even in temporarily undersaturated bulk solutions, under conditions that concurrently favoured selective shell surface dissolution. The results suggest an overall resistance of S. spirorbis growth to acidification levels predicted for the year 2100 in the Baltic Sea. In contrast, S. spirorbis did not survive at mean seasonal temperatures exceeding 24 °C during the summer experiments. In the autumn experiments at ambient pCO2, the growth rates of juvenile S. spirorbis were higher under elevated temperature conditions. The results reveal that S. spirorbis may prefer moderately warmer conditions during their early life stages but will suffer from an excessive temperature increase and from increasing shell corrosion as a consequence of progressing ocean acidification

Factors controlling the carbon isotope composition of dissolved inorganic carbon and methane in marine porewater: An evaluation by reaction-transport modelling

Carbon isotope compositions of dissolved inorganic carbon (DIC) and methane (CH4) in porewater of marine sediments at seafloor temperatures show very large variation covering a δ13C range from −100‰ to +35‰. These extreme values are the result of isotope fractionation during microbial carbon metabolism, but the combined effect of all factors controlling the isotope distributions is still not completely understood. We used a model approach to evaluate the effects of reaction and transport on carbon isotope distributions in modern sediment porewater under steady state. Simulated δ13CDIC profiles typically show negative values in the sulphate reduction zone and more positive values in the methanogenic zone. With increasing depth in the methanogenic zone, δ13C values approach a distribution where the offset of δ13CDIC from δ13C of total organic carbon (TOC) to more positive values is similar to the offset of δ13CCH4 to more negative values (δ13CDIC and δ13CCH4 approach a symmetric distribution relative to δ13CTOC). The model never exceeds this symmetry of the DIC-CH4 couple towards more positive values under steady-state conditions in a purely diffusive system. Our model shows that to reach an offset in δ13C between DIC and CH4 in the order of 70‰, as frequently observed in methanogenic zones, a larger fractionation than reported from culture experiments with acetoclastic or autotrophic methanogens would be required. In fact, the observed isotope offset in natural systems would be consistent with the known inorganic equilibrium fractionation factor at in-situ temperature, which may suggest isotope exchange via a microbial pathway, during methanogenesis. Furthermore, the model reproduces strongly negative δ13CCH4 values at the sulphate methane-transition (SMT) as result of a reverse flux of carbon from DIC to CH4 during AOM. Such a reverse AOM has no influence on the δ13CDIC at the SMT as methane is almost completely consumed. Only at high sedimentation rate combined with low porosity, δ13CDIC values significantly more negative than δ13CTOC occur at the SMT

In Search of a Field-Based Relationship Between Benthic Macrofauna and Biogeochemistry in a Modern Brackish Coastal Sea

During several cruises in the southern Baltic Sea conducted in different seasons from 2014 to 2016, sediment cores were collected for the investigation of pore-water biogeochemistry and associated nutrient fluxes across the sediment-water interface. Six stations were positioned along a salinity gradient (ranging from 22 to 8) and covered various sedimentary habitats ranging from mud to sand. Integrated fluxes of nutrients in the supernatant water and sediment oxygen consumption were additionally derived from incubations of intact sediment cores. Subsequently, sediment from the pore-water and incubation cores was sieved for taxonomic identification and estimation of benthic macrofauna density. This combined dataset was used to determine the dominant factors influencing the vertical distribution of geochemical parameters in the pore-waters of the studied habitats and to find similarities and patterns explaining significant variations of solute fluxes across the sediment-water interface. A statistical relationship between the thickness of sulfide-free surface sediments, solute fluxes of sulfide, ammonium, and phosphate as well as oxygen consumption and taxonomic and functional characteristics of macrobenthic communities were tested. Our data and modeling results indicate that bioturbation and bioirrigation alter near-surface pore-water nutrient concentrations toward bottom water values. Besides sediment properties and microbial activity, the biogeochemical fluxes can further be explained by the functional structure of benthic macrofauna. Community bioturbation potential, species richness, and biomass of biodiffusers were the best proxies among the tested set of biotic and abiotic parameters and could explain 63% of multivariate total benthic flux variations. The effects of macrobenthos on ecosystem functioning differ between sediment types, specific locations and seasons. Both, species distribution and nutrient fluxes are temporally dynamic. Those natural patterns, as well as potential anthropogenic and natural disturbances (e.g., fishery, storm events), may cause impacts on field data in a way beyond our present capability of quantitative prediction, and require more detailed seasonal studies. The data presented here adds to our understanding of the complexity of natural ecosystem functioning under anthropogenic pressure

Calcification-driven CO2emissions exceed blue Carbon sequestration in a carbonate seagrass meadow

Long-term Blue Carbon burial in seagrass meadows is complicated by other carbon and alkalinity exchanges that shape net carbon sequestration. We measured a suite of such processes, including denitrification, sulfur, and inorganic carbon cycling, and assessed their impact on air-water CO2 exchange in a typical seagrass meadow underlain by carbonate sediments. Eddy covariance measurements reveal a consistent source of CO2 to the atmosphere at an average rate of 610 ± 990 μmol m-2 hour-1 during our study and 700 ± 660 μmol m-2 hour-1 (6.1 mol m-2 year-1) over an annual cycle. Net alkalinity consumption by ecosystem calcification explains \u3e95% of the observed CO2 emissions, far exceeding organic carbon burial and anaerobic alkalinity generation. We argue that the net carbon sequestration potential of seagrass meadows may be overestimated if calcification-induced CO2 emissions are not accounted for, especially in regions where calcification rates exceed net primary production and burial

Solute Reservoirs Reflect Variability of Early Diagenetic Processes in Temperate Brackish Surface Sediments

Coastal marine sediments are a hotspot of organic matter degradation. Mineralization products of early diagenetic processes accumulate in the pore waters of the sediment, are subject of biological uptake and secondary biogeochemical processes and are released back into the water column via advective and diffusive fluxes across the sediment-water interface. Seven representative sites in the shallow coastal area of the southern Baltic Sea (15–45 m water depth), ranging from permeable sands to fine grained muds, were investigated on a seasonal basis for their key mineralization processes as well as their solid phase and pore water composition to identify the drivers for the variability of early diagenetic processes in the different sediment types. The sandy sediments showed about one order of magnitude lower organic carbon contents compared to the muds, while oxygen uptake rates were similar in both sediment types. Significantly higher oxygen uptake rates were determined in two near-shore muddy sites than in a deeper coastal muddy basin, which is due to higher nutrient loads and the corresponding addition of fresh algal organic matter in the near-shore sites. Pore water concentration profiles in the studied sediments were usually characterized by a typical biogeochemical zonation with oxic, suboxic, and sulfidic zones. An up to 15 cm thick suboxic zone was sustained by downward transport of oxidized material in which dissolved iron and phosphate indicate an intensive reduction of reactive Fe with the release of adsorbed phosphorus. While the geochemical zonation was stable over time in the muds of the studied deeper basin, high variability was observed in the muds of a near-coastal bay probably mainly controlled by sediment mixing activities. The sediments can be characterized by essentially two factors based on their near-surface benthic solute reservoirs: (1) their organic matter mineralization and solute accumulation efficiency and (2) their redox-state. Benthic solute reservoirs in the pore waters of the top decimeter were generally higher in the muddy than in the sandy sediments as the more permeable sands were prone to an intensive exchange between pore water and bottom water. The three studied muddy sites showed great dissimilarities with respect to their predominating redox-sensitive metabolites (dissolved iron, manganese, and sulfide). Surface-near advective transport like irrigation of permeable sands and rearrangement of cohesive muds had a particularly strong influence on early diagenetic processes in the studied sediments and were probably the most important cause for the spatiotemporal variability of their benthic solute reservoirs