Description: 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.

Description: Elemental sulfur is commonly regarded as the product of oxidative sulfur cycling in the sediment. However, reports on the occurrence of elemental sulfur in seepage areas are few and thus its origin and mechanisms controlling its distribution are insufficiently understood. Here, we analyzed the multiple sulfur isotopic compositions for elemental sulfur and pyrite from an iron-dominated gas hydrate-bearing sedimentary environment of the South China Sea to unravel the impact of sulfate-driven anaerobic oxidation of methane (SO4-AOM) on the formation of elemental sulfur. The multiple sulfur isotopes reveal variable ranges for both elemental sulfur and pyrite (δ34S: between −15.7 and +23.3‰ for elemental sulfur and between −35.3 and +34.4‰ for pyrite; Δ33S: between −0.08 and +0.06‰ for elemental sulfur and between −0.03 and +0.15‰ for pyrite). The enrichment of 34S in pyrite throughout the sediment core suggests pronounced SO4-AOM in paleo-sulfate-methane transition zones (SMTZ). In addition, the occurrence of seep carbonates with very negative δ13C values (as low as −57‰, V-PDB) coincides with the inferred paleo-SMTZs and agrees with formerly locally pronounced SO4-AOM. Interestingly, the multiple sulfur isotopic composition of elemental sulfur reveals a different pattern from that of pyrite derived from organoclastic sulfate reduction (i.e., with low δ34S and high Δ33S values for the latter). In comparison to coexisting pyrite, most of the elemental sulfur reveals higher δ34S values (as much as +28.9‰), which is best explained by an enrichment of 34S in the residual pool of dissolved sulfide generated by SO4-AOM. As an intermediate sulfur phase, elemental sulfur can form via sulfide oxidation coupled to iron reduction, but it can only persist in the absence of free sulfide. Therefore, the occurrence of 34S enriched elemental sulfur is likely to represent an oxidative product after hydrogen sulfide had vanished due to vertical displacement of the SMTZ. Our observations suggest that elemental sulfur may serve as a useful recorder for reconstructing the dynamics of sulfur cycling in modern and possibly ancient seepage areas.

Description: The spatial variations in the elemental and stable carbon, nitrogen, and sulphur isotope composition of bladder wrack (Fucus vesiculosus) growing along the shore line of the semi-enclosed urbanized Kiel Fjord (western Baltic Sea) was investigated at more than 60 sites. The analyses of the carbon-nitrogen-sulphur (CNS) stoichiometry and C and N stable isotope signature of F. vesiculosus displayed substantial differences between the north-western and the south-eastern parts of the Kiel Fjord. Different size classes displayed in part differences in C:N and C:S ratios, and the carbon isotope composition, reflecting the impact of the boundary conditions during growth. Whereas the sulphur isotope composition was controlled by the assimilation of seawater sulphate, the carbon isotope composition reflected the difference in the composition of surface waters. The δ15N values of the organic tissue tend to be an integrated monitor of anthropogenic impacts on the fjord. Results are compared to the composition of surface waters.

Description: Seepage of methane (CH4) on land and in the sea may significantly affect Earth's biogeochemical cycles. However processes of CH4 generation and consumption, both abiotic and microbial, are not always clear. We provide new geochemical and isotope data to evaluate if a recently discovered CH4 seepage from the shallow seafloor close to the Island of Elba (Tuscany) and two small islands nearby are derived from abiogenic or biogenic sources and whether carbonate encrusted vents are the result of microbial or abiotic processes. Emission of gas bubbles (predominantly CH4) from unlithified sands was observed at seven spots in an area of 100 m(2) at Pomonte (Island of Elba), with a total rate of 234 ml m(-2) d(-1). The measured carbon isotope values of CH4 of around -18 parts per thousand (VPDB) in combination with the measured delta H-2 value of -120 parts per thousand (VSMOW) and the inverse correlation of delta C-13-value with carbon number of hydrocarbon gases are characteristic for sites of CH4 formation through abiogenic processes, specifically abiogenic formation of CH4 via reduction of CO2 by H-2. The H-2 for methanogenesis likely derives from ophiolitic host rock within the Ligurian accretionary prism. The lack of hydrothermal activity allows CH4 gas to become decoupled from the stagnant aqueous phase. Hence no hyperalkaline fluid is currently released at the vent sites. Within the seep area a decrease in porewater sulphate concentrations by ca. 5 mmol/l relative to seawater and a concomitant increase in sulphide and dissolved inorganic carbon (DIC) indicate substantial activity of sulphate-dependent anaerobic oxidation of methane (AOM). In absence of any other dissimilatory pathway, the delta C-13-values between -17 and -5 parts per thousand in dissolved inorganic carbon and aragonite cements suggest that the inorganic carbon is largely derived from CH4. The formation of seep carbonates is thus microbially induced via anaerobic oxidation of abiotic CH4.

Description: Depth profiles of the stable sulfur isotopic composition of dissolved sulfate in near-surface sediments were measured at five stations of the deep Arabian Sea between 1918 and 4426 m water depth (WAST, WAST-Top, CAST, SAST, NAST), sampled in April 1997. The results clearly indicate that net microbial sulfate reduction took place in the sediments at stations WAST and NAST below about 12 cm depth. Sulfate reduction at WAST was more pronounced compared to station NAST, most likely due to higher organic carbon content in turbiditic sediments. No net sulfate reduction took place within the upper 10 cm of the surface sediments at all stations, and no significant isotopic indication for sulfate reduction was found down to 30 cm bsf at station SAST. Results are in accordance with accumulation of reduced isotopically light sulfur species below about 6 cm bsf at station WAST. It is concluded that the sulfur isotopic composition of remaining sulfate is more sensitive to net sulfate reduction than the [SO4]/[Cl] ratio. The sulfur isotopic composition of a vertical profile for dissolved sulfate through the water column at station WAST was essentially constant (250–4047 m: Full-size image (〈1 K)‰ vs. V-CDT n=8). A similar constancy (20–4565 m water depth Full-size image (〈1 K)‰ vs. V-CDT n=15) was found for the station BIOTRANS in the northeastern Atlantic (47°11′ 19°33W), indicating that the oxygen minimum zone in the Arabian Sea has no influence on the sulfur isotopic composition of dissolved sulfate.

Description: The partitioning of an ionic species between two or more co-existing phases is closely related to chemical speciation, solubility, sorption and solid-solution formation in the geochemical system. The aim of chemical thermodynamic modelling is to find the stable or metastable chemical speciation in such a system; from that, any possible ion partition or distribution coefficient can be retrieved. This chapter aims to highlight some typical features of modelling the equilibrium partitioning of inorganic ionic species between aqueous electrolyte and solid phases, including adsorption and ion exchange on their surfaces. Some guidance is also given on methods and computer codes that can be used in helping us understand and predict ion partitioning in complex scenarios, where several competing solids are involved in a minor element uptake by different mechanisms.

Description: Interstitial water samples from seven ODP sites (Leg 181, Sites 1119–1125) of the southwestern Pacific Ocean have been analyzed for the stable sulfur isotopic composition of dissolved sulfate along with major and minor ions. Sulfate from the interstitial fluids (δ34S values between +20.7 and +60‰ vs. the SO2-based Vienna–Canyon Diablo troilite standard) was enriched in 34S with respect to modern sea water (δ34S≈+20.6‰) indicating that microbial sulfate reduction takes place to different extents at all investigated sites. Microbial sulfate reduction (MSR) was found at all sites, the intensity depending on the availability of organic matter which is controlled by paleo-sedimentation conditions (sedimentation rate, presence of turbidites) and productivity. Microbial net sulfate reduction was additionally confirmed by modeling interstitial water sulfate profiles. Areal net sulfate reduction rates up to 14 mmol m−2 yr−1 have been calculated which were positively related to sedimentation rates. Total reduced inorganic sulfur (TRIS; essentially pyrite) as a product of microbial sulfate reduction was isotopically characterized in squeeze cake samples and gave δ34S values between −51 and +9‰ indicating pyrite formation both close to the sediment–water interface and later diagenetic contributions.

Description: For millennia humans have gravitated towards coastlines for their resource potential and as geopolitical centres for global trade. A basic requirement ensuring water security for coastal communities relies on a delicate balance between the supply and demand of potable water. The interaction between freshwater and saltwater in coastal settings is, therefore, complicated by both natural and human-driven environmental changes at the land-sea interface. In particular, ongoing sea level rise, warming and deoxygenation might exacerbate such perturbations. In this context, an improved understanding of the nature and variability of groundwater fluxes across the land-sea continuum is timely, yet remains out of reach. The flow of terrestrial groundwater across the coastal transition zone as well as the extent of freshened groundwater below the present-day seafloor are receiving increased attention in marine and coastal sciences because they likely represent a significant, yet highly uncertain component of (bio)geochemical budgets, and because of the emerging interest in the potential use of offshore freshened groundwater as a resource. At the same time, “reverse” groundwater flux from offshore to onshore is of prevalent socio-economic interest as terrestrial groundwater resources are continuously pressured by overpumping and seawater intrusion in many coastal regions worldwide. An accurate assessment of the land-ocean connectivity through groundwater and its potential responses to future anthropogenic activities and climate change will require a multidisciplinary approach combining the expertise of geophysicists, hydrogeologists, (bio)geochemists and modellers. Such joint activities will lay the scientific basis for better understanding the role of groundwater in societal-relevant issues such as climate change, pollution and the environmental status of the coastal oceans within the framework of the United Nations Sustainable Development Goals. Here, we present our perspectives on future research directions to better understand land-ocean connectivity through groundwater, including the spatial distributions of the essential hydrogeological parameters, highlighting technical and scientific developments, and briefly discussing its societal relevance in rapidly changing coastal oceans.