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: During Earth’s history, precipitation of calcium carbonate by heterotrophic microbes has substantially contributed to the genesis of copious amounts of carbonate sediment and its subsequent lithification. Previous work identified the microbial sulfur and nitrogen cycle as principal pathways involved in the formation of marine calcium carbonate deposits. While substantial knowledge exists for the importance of the sulfur cycle, specifically sulfate reduction, with regard to carbonate formation, information about carbonate genesis connected to the microbial nitrogen cycle is dissatisfactory. In addition to the established pathways for carbonate mineral formation, also the potential of microbial carbonic anhydrase, a carbonate-relevant, zinc-containing enzyme, is receiving currently increased attention. However, also in this field knowledge is scarce and fragmentary. Here we demonstrate microbial carbonate precipitation as a direct result of the interplay between the microbial nitrogen cycle and a microbially produced enzyme. Using Alcanivorax borkumensis as a model organism, our experiments depict precipitation of a peloidal carbonate matrix within days to weeks, induced by simultaneous ammonification and extracellular carbonic anhydrase activity. The precipitates show similar morphology, mineralogy, δ44/40Ca, and δ88/86Sr to analogs of modern carbonate peloids. The obtained Sr/Ca partition coefficient DSr showed no clear deviation from inorganic carbonate phases, indicating that microbially mediated carbonate precipitation, indeed, follows the principles of physico-chemical precipitation. The observed relative enrichment of the precipitates in zinc might help to constrain zinc variations in natural carbonate archives. Our study demonstrates that ammonification, due to intense microbial organic matter degradation, and carbonic anhydrase may play a substantial role for calcium carbonate precipitation in paleo- and recent shallow marine environments.

Description: Coral epithelia control ion fluxes to the calcification site influencing biomineralization and proxy incorporation. However, data on in vivo characteristics of coral tissue such as permeability, selectivity, and active ion transport are scarce but important for calcification and proxy modeling. To investigate ion permeability and ion fluxes across coral tissues in vivo, we developed an electrophysiological approach for the assessment of active and passive epithelial transport properties. Growing Stylophora pistillata corals in a thin layer over permeable filters allowed ion exchange at the site of skeleton formation for reproducible measurements of electrophysiological properties of coral tissues in a modified Ussing chamber. Compared to former applications, electrical measurements on these coral filter units were dominated by tissue characteristics with minimal influence of skeleton or physical stress. Coral tissues were cation selective. Their overall high electrical resistance characterized them as tight epithelia indicating low paracellular permeability for passive ion diffusion. This includes ions relevant for calcification. A small short-circuit current indicates active charge transport across the entire coral tissue. The present approach is applicable to corals laterally overgrowing substrates. It allows the electrophysiological characterization of coral tissue in vivo in response to environmental conditions. This will improve our knowledge on transepithelial transport relevant for biomineralization in corals.

Description: Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Description: We evaluate the potential of ophiolites as archives of paleoseawater and hydrothermal fluid compositions by analysing the chemical and isotopic composition of abiogenic carbonates, precipitated from fluids within the oceanic crust of the 91 Ma Troodos Ophiolite, Cyprus. Calculated variations in fluid Mg/Ca, Sr/Ca and Sr-87/ Sr-86 with temperature within the upper sections of the ophiolite are similar to those from drilled oceanic crust, and yield literature values for late Cretaceous seawater Mg/Ca, Sr/Ca and Sr-87/ Sr-86. This indicates that carbonates from ophiolites could be used to estimate the composition of ancient seawater at times before the age of the oldest preserved in-situ oceanic crust. Whereas most carbonates recovered from in-situ oceanic crust were precipitated at temperatures 〈 60 degrees C, abiogenic carbonates from the Troodos Ophiolite formed over a temperature range of 7 degrees C to 218 degrees C. These provide unique insights into the chemical and mineralogical processes that transform seawater into a high temperature hydrothermal fluid within the oceanic crust. We use 'hydrothermal variation diagrams' of Mg/Ca, Sr/Ca, Sr-87/ Sr-86 and delta(44)/Ca-40 versus calculated temperature (delta O-18) to trace this fluid evolution within the Troodos oceanic crust. We find that successive fluid-crust-interaction, the precipitation of Mg- and Ca-bearing minerals and the early formation of anhydrite (〉 44 degrees C) gradually transform Cretaceous seawater into a Troodos hydrothermal fluid. Comparison of the Troodos data with a global dataset of abiogenic carbonates from in-situ oceanic crust shows that the chemical pathways of low-temperature fluid evolution are similar for all Cretaceous sites. These different sites represent varied geotectonic settings (midocean ridge vs. suprasubduction zone), with different basement composition (basalt, basaltic andesite/boninite) and situated in different ocean basins (Atlantic, Pacific, Mediterranean [Tethys]). The similarity in the carbonate record indicates that these differences do not significantly influence seafloor weathering and hydrothermal alteration at low temperatures. However, abiogenic carbonates from younger oceanic crust differ from the Cretaceous trends and follow different fluid evolution pathways. This indicates, that temporal variations in the composition of seawater may control the nature and the extent of seafloor weathering and hydrothermal alteration at low temperatures. A thermodynamic model of fluid-crust interaction, in which modern and Cretaceous seawater are heated to 200 degrees C while an average Troodos basaltic andesite is successively added under otherwise identical conditions predicts that fluid evolution and alteration of the oceanic crust were different in the Cretaceous than they are today, and that initial seawater chemistry affects the nature and the extent of seafloor alteration up to moderate fluid temperatures. For example, twice the amount of carbonate formed during alteration of the oceanic crust in the Cretaceous compared to modern times, indicating that the flux of CO2 from the hydrosphere-atmosphere system into the oceanic crust was greater in the Cretaceous than it is nowadays, and that it probably varied throughout geologic time.

Description: Stable isotope records of demosponges from the Caribbean and Coral Sea are described for the purpose of studying the influence of fossil fuel CO2 on the carbon isotopic composition of dissolved inorganic carbon (DIC) in surface water. The slow-growing sponges precipitate calcium carbonate in isotopic equilibrium with ambient sea water and are used to detect changes in δ13CDIC from pre-industrial times (early 19th century) to the present. We observed similar shapes and ranges in δ13C curves measured on Caribbean specimens collected from water depths of 25, 84 and 91 m as well as a specimen collected in shallow waters off New Caledonia. The records reveal a highly significant correlation with atmospheric δ13CCO2. δ13CDIC values for Caribbean and Coral Sea surface waters were calculated using the δ13C sponge records. While δ13C of atmospheric CO2 decreased by about 1.4‰ from the early 19th century to 1990, δ13CDIC of Caribbean and Coral Sea surface waters decreased by 0.9±0.2‰ and 0.7±0.3‰, respectively. No isotopic equilibrium between surface water DIC and atmospheric CO2 was observed, either during the pre-industrial steady state or during the last 100 years. The lower amount of depletion in the surface water δ13CDIC with respect to the atmospheric anthropogenic signal is explained by the dilution of the surface waters by biologically altered subsurface water DIC. The lower δ13C decrease in the Coral Sea points to a stronger influence of the subsurface water source compared to the Caribbean.

Description: The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (δ44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the δ44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of δ44/40Ca ranges from 0.6 to 0.1‰, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and δ44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by δ18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's δ44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean. Highlights ► Corals cultured in aquaria or from natural environment show the same Ca isotopic composition. ► δ44/40Ca of coral skeleton is independent of depositional setting environment. ► Strong influence of vital effects on coral skeleton δ44/40Ca composition and calcification mechanisms

Description: Mytilus edulis were cultured for 3 months under six different seawater pCO(2) levels ranging from 380 to 4000 mu atm. Specimen were taken from Kiel Fjord (Western Baltic Sea, Germany) which is a habitat with high and variable seawater pCO(2) and related shifts in carbonate system speciation (e. g., low pH and low CaCO3 saturation state). Hemolymph (HL) and extrapallial fluid (EPF) samples were analyzed for pH and total dissolved inorganic carbon (C-T) to calculate pCO(2) and [HCO3-]. A second experiment was conducted for 2 months with three different pCO(2) levels (380, 1400 and 4000 mu atm). Boron isotopes (delta B-11) were investigated by LA-MC-ICP-MS (Laser Ablation-Multicollector-Inductively Coupled Plasma-Mass Spectrometry) in shell portions precipitated during experimental treatment time. Additionally, elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF of specimen from the second experiment were measured via ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry). Extracellular pH was not significantly different in HL and EPF but systematically lower than ambient water pH. This is due to high extracellular pCO(2) values, a prerequisite for metabolic CO2 excretion. No accumulation of extracellular [HCO3-] was measured. Elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF increased slightly with pH which is in accordance with increasing growth and calcification rates at higher seawater pH values. Boron isotope ratios were highly variable between different individuals but also within single shells. This corresponds to a high individual variability in fluid B/Ca ratios and may be due to high boron concentrations in the organic parts of the shell. The mean delta B-11 value shows no trend with pH but appears to represent internal pH (EPF) rather than ambient water pH.

Description: Chemical (Sr, Mg) and isotopic (δ18O, 87Sr/86Sr) compositions of calcium carbonate veins (CCV) in the oceanic basement were determined to reconstruct changes in Sr/Ca and Mg/Ca of seawater in the Cenozoic. We examined CCV from 10 basement drill sites in the Atlantic and Pacific, ranging in age between 165 and 2.3 Ma. Six of these sites are from cold ridge flanks in basement 〈46 Ma, which provide direct information about seawater composition. CCV of these young sites were dated, using the Sr isotopic evolution of seawater. For the other sites, temperature-corrections were applied to correct for seawater–basement exchange processes. The combined data show that a period of constant/low Sr/Ca (4.46–6.22 mmol/mol) and Mg/Ca (1.12–2.03 mol/mol) between 165 and 30 Ma was followed by a steady increase in Mg/Ca ratios by a factor of three to modern ocean composition. Mg/Ca–Sr/Ca relations suggest that variations in hydrothermal fluxes and riverine input are likely causes driving the seawater compositional changes. However, additional forcing may be involved in explaining the timing and magnitude of changes. A plausible scenario is intensified carbonate production due to increased alkalinity input to the oceans from silicate weathering, which in turn is a result of subduction-zone recycling of CO2 from pelagic carbonate formed after the Cretaceous slow-down in ocean crust production rate.

Description: Mg/Ca and Sr/Ca ratios were determined on a single species of planktonic foraminiferan, Globigerinoides ruber (white), collected from the Gulf of Eilat and cultured in seawater at five different salinities (32 to 44), five temperatures (18 to 30 °C) and four pH values (7.9 to 8.4). The Mg/Ca-temperature calibration of cultured G. ruber (with an exponential slope of 8 ± 3%/°C) agrees well with previously published calibrations from core-tops and sediment traps. However, the dependence of Mg/Ca on salinity (with an exponential slope of 5 ± 3%/psu) is also significant and should be included in the calibration equation. With this purpose, we calculated a calibration equation for G. ruber dependent on both temperature and salinity within the 95% confidence limits: Mg/Ca(mmol/mol)=exp[0.06(±0.02)*S(psu)+0.08(±0.02)*T(°C)−2.8(±1.0)],R2=0.95 The influence of pH on Mg/Ca ratios is negligible at ambient seawater pH (8.1 to 8.3). However, we observe a dominating pH control on shell Mg/Ca when the pH of seawater is lower than 8.0. Sr/Ca in G. ruber shows a significant positive correlation with average growth rate. Presumably, part of the variability in shell Sr/Ca in the geological record is linked to changes in growth rates of foraminifera as a response to changing environmental conditions.