Fragmentation and dissolution of benthic foraminifera in Kiel Bight, Baltic Sea, Germany

Early diagenetic ultrastructural alterations of benthic foraminifers of the genera Elphidium and Ophthalmina from the shallow water sediments of the Kiel Bight were investigated by scanning electron microscopy. Pure solution patterns were deduced from supplementary experiments.//Several carbonate destroying processes can be specified by ultrastructural patterns of the shell surfaces. Based on these patterns three zones are established, each showing different mechanisms of shell fragmentation: 1) zone of abrasion, 2) zone of disintegration, 3) zone of corrosion. This zonation depends on the water depth and is caused primarily by water agitation and by under saturation of the bottom water with respect to carbonate.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Light-modulated responses of growth and photosynthetic performance to ocean acidification in the model diatom Phaeodactylum tricornutum

Ocean acidification (OA) due to atmospheric CO2 rise is expected to influence marine primary productivity. In order to investigate the interactive effects of OA and light changes on diatoms, we grew Phaeodactylum tricornutum, under ambient (390 ppmv; LC) and elevated CO2 (1000 ppmv; HC) conditions for 80 generations, and measured its physiological performance under different light levels (60 µmol/m**2/s, LL; 200 µmol/m**2/s, ML; 460 µmol/m**2/s, HL) for another 25 generations. The specific growth rate of the HC-grown cells was higher (about 12-18%) than that of the LC-grown ones, with the highest under the ML level. With increasing light levels, the effective photochemical yield of PSII (Fv'/Fm') decreased, but was enhanced by the elevated CO2, especially under the HL level. The cells acclimated to the HC condition showed a higher recovery rate of their photochemical yield of PSII compared to the LC-grown cells. For the HC-grown cells, dissolved inorganic carbon or CO2 levels for half saturation of photosynthesis (K1/2 DIC or K1/2 CO2) increased by 11, 55 and 32%, under the LL, ML and HL levels, reflecting a light dependent down-regulation of carbon concentrating mechanisms (CCMs). The linkage between higher level of the CCMs down-regulation and higher growth rate at ML under OA supports the theory that the saved energy from CCMs down-regulation adds on to enhance the growth of the diatom.

(Table 1) Concentration of PCB and other contaminants in blood plasma of polar bears (Ursus maritimus) from Svalbard

Persistent chemicals accumulate in the arctic environment due to their chemical reactivity and physicochemical properties and polychlorinated biphenyls (PCBs) are the most concentrated pollutant class in polar bears (Ursus maritimus). Metabolism of PCB and polybrominated biphenyl ether (PBDE) flame-retardants alter their toxicological properties and these metabolites are known to interfere with the binding of thyroid hormone (TH) to transthyretin (TTR) in rodents and humans. In polar bear plasma samples no binding of [125I]-T4 to TTR was observed after incubation and PAGE separation. Incubation of the plasma samples with [14C]-4-OH-CB107, a compound with a higher binding affinity to TTR than the endogenous ligand T4 resulted in competitive binding as proven by the appearance of a radio labeled TTR peak in the gel. Plasma incubation with T4 up to 1 mM, a concentration that is not physiologically relevant anymore did not result in any visible competition. These results give evidence that the binding sites on TTR for T4 in wild living polar bears are completely saturated. Such saturation of binding sites can explain observed lowered levels of THs and could lead to contaminant transport into the developing fetus.

Seawater carbonate chemistry and biological processes of oysters Crassostrea virginica during experiments, 2010

Estuarine organisms are exposed to periodic strong fluctuations in seawater pH driven by biological carbon dioxide (CO2) production, which may in the future be further exacerbated by the ocean acidification associated with the global rise in CO2. Calcium carbonate-producing marine species such as mollusks are expected to be vulnerable to acidification of estuarine waters, since elevated CO2 concentration and lower pH lead to a decrease in the degree of saturation of water with respect to calcium carbonate, potentially affecting biomineralization. Our study demonstrates that the increase in CO2 partial pressure (pCO2) in seawater and associated decrease in pH within the environmentally relevant range for estuaries have negative effects on physiology, rates of shell deposition and mechanical properties of the shells of eastern oysters Crassostrea virginica (Gmelin). High CO2 levels (pH ~7.5, pCO2 ~3500 µatm) caused significant increases in juvenile mortality rates and inhibited both shell and soft-body growth compared to the control conditions (pH ~8.2, pCO2 ~380 µatm). Furthermore, elevated CO2 concentrations resulted in higher standard metabolic rates in oyster juveniles, likely due to the higher energy cost of homeostasis. The high CO2 conditions also led to changes in the ultrastructure and mechanical properties of shells, including increased thickness of the calcite laths within the hypostracum and reduced hardness and fracture toughness of the shells, indicating that elevated CO2 levels have negative effects on the biomineralization process. These data strongly suggest that the rise in CO2 can impact physiology and biomineralization in marine calcifiers such as eastern oysters, threatening their survival and potentially leading to profound ecological and economic impacts in estuarine ecosystems.

Effects of light and elevated pCO2 on the growth and photochemical efficiency of Acropora cervicornis

The effects of light and elevated pCO2 on the growth and photochemical efficiency of the critically endangered staghorn coral, Acropora cervicornis, were examined experimentally. Corals were subjected to high and low treatments of CO2 and light in a fully crossed design and monitored using 3D scanning and buoyant weight methodologies. Calcification rates, linear extension, as well as colony surface area and volume of A. cervicornis were highly dependent on light intensity. At pCO2 levels projected to occur by the end of the century from ocean acidification (OA), A. cervicornis exhibited depressed calcification, but no change in linear extension. Photochemical efficiency (F v /F m ) was higher at low light, but unaffected by CO2. Amelioration of OA-depressed calcification under high-light treatments was not observed, and we suggest that the high-light intensity necessary to reach saturation of photosynthesis and calcification in A. cervicornis may limit the effectiveness of this potentially protective mechanism in this species. High CO2 causes depressed skeletal density, but not linear extension, illustrating that the measurement of extension by itself is inadequate to detect CO2 impacts. The skeletal integrity of A. cervicornis will be impaired by OA, which may further reduce the resilience of the already diminished populations of this endangered species.

Effects of seawater pCO2 and temperature on shell growth, shell stability, condition and cellular stress of Western Baltic Sea Mytilus edulis (L.) and Arctica islandica (L.)

Acidification of the World's oceans may directly impact reproduction, performance and shell formation of marine calcifying organisms. In addition, since shell production is costly and stress in general draws on an organism's energy budget, shell growth and stability of bivalves should indirectly be affected by environmental stress. The aim of this study was to investigate whether a combination of warming and acidification leads to increased physiological stress (lipofuscin accumulation and mortality) and affects the performance [shell growth, shell breaking force, condition index (Ci)] of young Mytilus edulis and Arctica islandica from the Baltic Sea. We cultured the bivalves in a fully-crossed 2-factorial experimental setup (seawater (sw) pCO2 levels "low", "medium" and "high" for both species, temperature levels 7.5, 10, 16, 20 and 25 °C for M. edulis and 7.5, 10 and 16 °C for A. islandica) for 13 weeks in summer. Mytilus edulis and A. islandica appeared to tolerate wide ranges of sw temperature and pCO2. Lipofuscin accumulation of M. edulis increased with temperature while the Ci decreased, but shell growth of the mussels only sharply decreased while its mortality increased between 20 and 25 °C. In A. islandica, lipofuscin accumulation increased with temperature, whereas the Ci, shell growth and shell breaking force decreased. The pCO2 treatment had only marginal effects on the measured parameters of both bivalve species. Shell growth of both bivalve species was not impaired by under-saturation of the sea water with respect to aragonite and calcite. Furthermore, independently of water temperatures shell breaking force of both species and shell growth of A. islandica remained unaffected by the applied elevated sw pCO2 for several months. Only at the highest temperature (25 °C), growth arrest of M. edulis was recorded at the high sw pCO2 treatment and the Ci of M. edulis was slightly higher at the medium sw pCO2 treatment than at the low and high sw pCO2 treatments. The only effect of elevated sw pCO2 on A. islandica was an increase in lipofuscin accumulation at the high sw pCO2 treatment compared to the medium sw pCO2 treatment. Our results show that, despite this robustness, growth of both M. edulis and A. islandica can be reduced if sw temperatures remain high for several weeks in summer. As large body size constitutes an escape from crab and sea star predation, this can make bivalves presumably more vulnerable to predation with possible negative consequences on population growth. In M. edulis, but not in A. islandica, this effect is amplified by elevated sw pCO2. We follow that combined effects of elevated sw pCO2 and ocean warming might cause shifts in future Western Baltic Sea community structures and ecosystem services; however, only if predators or other interacting species do not suffer as strong from these stressors.

Seawater acidification by CO2 in a coastal lagoon environment: Effects on life history traits of juvenile mussels Mytilus galloprovincialis

The carbonate chemistry of seawater from the Ria Formosa lagoon was experimentally manipulated, by diffusing pure CO2, to attain two reduced pH levels, by -0.3 and -0.6 pH units, relative to unmanipulated seawater. After 84 days of exposure, no differences were detected in terms of growth (somatic or shell) or mortality of juvenile mussels Mytilus galloprovincialis. The naturally elevated total alkalinity of the seawater (= 3550 µmol/kg) prevented under-saturation of CaCO3, even under pCO2 values exceeding 4000 µatm, attenuating the detrimental effects on the carbonate supply-side. Even so, variations in shell weight showed that net calcification was reduced under elevated CO2 and reduced pH, although the magnitude and significance of this effect varied among size-classes. Most of the loss of shell material probably occurred as post-deposition dissolution in the internal aragonitic nacre layer. Our results show that, even when reared under extreme levels of CO2-induced acidification, juvenile M. galloprovincialis can continue to calcify and grow in this coastal lagoon environment. The complex responses of bivalves to ocean acidification suggest a large degree of interspecific and intraspecific variability in their sensitivity to this type of perturbation. Further research is needed to assess the generality of these patterns and to disentangle the relative contributions of acclimation to local variations in seawater chemistry and genetic adaptation.

Temporal biomass dynamics of an Arctic plankton bloom

Ocean acidification and carbonation, driven by anthropogenic emissions of carbon dioxide (CO2), have been shown to affect a variety of marine organisms and are likely to change ecosystem functioning. High latitudes, especially the Arctic, will be the first to encounter profound changes in carbonate chemistry speciation at a large scale, namely the under-saturation of surface waters with respect to aragonite, a calcium carbonate polymorph produced by several organisms in this region. During a CO2 perturbation study in 2010, in the framework of the EU-funded project EPOCA, the temporal dynamics of a plankton bloom was followed in nine mesocosms, manipulated for CO2 levels ranging initially from about 185 to 1420 ?atm. Dissolved inorganic nutrients were added halfway through the experiment. Autotrophic biomass, as identified by chlorophyll a standing stocks (Chl a), peaked three times in all mesocosms. However, while absolute Chl a concentrations were similar in all mesocosms during the first phase of the experiment, higher autotrophic biomass was measured at high in comparison to low CO2 during the second phase, right after dissolved inorganic nutrient addition. This trend then reversed in the third phase. There were several statistically significant CO2 effects on a variety of parameters measured in certain phases, such as nutrient utilization, standing stocks of particulate organic matter, and phytoplankton species composition. Interestingly, CO2 effects developed slowly but steadily, becoming more and more statistically significant with time. The observed CO2 related shifts in nutrient flow into different phytoplankton groups (mainly diatoms, dinoflagellates, prasinophytes and haptophytes) could have consequences for future organic matter flow to higher trophic levels and export production, with consequences for ecosystem productivity and atmospheric CO2.

In Situ effects of low pH and elevated HCO3 on juvenile massive Porites spp. in Moorea, French Polynesia

Juvenile colonies of massive Porites spp. were exposed to manipulated pH and bicarbonate ([HCO3-]) in situ to test the hypothesis that ocean acidification (OA) does not affect respiration and calcification. Incubations lasted 28 h and exposed corals to ambient temperature and light with ecologically relevant water motion. Three treatments were applied: (1) ambient conditions of pH 8.04 and 1751 µmol HCO3- kg(-1) (Treatment 1), (2) pCO2-induced ocean acidification of pH 7.73 and 2011 µmol HCO3- kg(-1) (Treatment 2), and (3) pCO2 and HCO3--enriched seawater of pH 7.69 and 2730 µmol HCO3- kg(-1) (Treatment 3). The third treatment providing elevated [HCO3-] was used to test for stimulatory effects of dissolved inorganic carbon on calcification under low pH and low saturation of aragonite (Omega arag), but it does not reflect conditions expected to occur under CO2-driven OA. Calcification of juvenile massive Porites spp. was affected by treatments, with an 81% elevation in Treatment 3 versus Treatment 1, but no difference between Treatments 1 and 2; respiration and the metabolic expenditure concurrent with calcification remained unaffected. These findings indicate that juvenile massive Porites spp. are resistant to short exposures to OA in situ, and separately, that they can increase calcification at low pH and low Omega arag if [HCO3-] is elevated. Juvenile Porites spp. may therefore be limited by dissolved inorganic carbon under ambient pCO2 conditions

Data compilation on the biological response to ocean acidification: environmental and experimental context of data sets and related literature

The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

Seawater carbonate chemistry and calcification rate of colonies of Stylophora pistillata, 1998

The carbonate chemistry of seawater is usually not considered to be an important factor influencing calcium-carbonate-precipitation by corals because surface seawater is supersaturated with respect to aragonite. Recent reports, however, suggest that it could play a major role in the evolution and biogeography of recent corals. We investigated the calcification rates of five colonies of the zooxanthellate coral Stylophora pistillata in synthetic seawater using the alkalinity anomaly technique. Changes in aragonite saturation from 98% to 585% were obtained by manipulating the calcium concentration. The results show a nonlinear increase in calcification rate as a function of aragonite saturation level. Calcification increases nearly 3-fold when aragonite saturation increases from 98% to 390%, i.e., close to the typical present saturation state of tropical seawater. There is no further increase of calcification at saturation values above this threshold. Preliminary data suggest that another coral species, Acropora sp., displays a similar behaviour. These experimental results suggest: (1) that the rate of calcification does not change significantly within the range of saturation levels corresponding to the last glacial-interglacial cycle, and (2) that it may decrease significantly in the future as a result of the decrease in the saturation level due to anthropogenic release of CO2 into the atmosphere. Experimental studies that control environmental conditions and seawater composition provide unique opportunities to unravel the response of corals to global environmental changes.

Sedimentological and benthic foraminiferal data pertaining to ODP Holes 208-1262A and 208-1263C

Eocene Thermal Maximum 2 (ETM2) occurred ~1.8 Myr after the Paleocene Eocene Thermal Maximum (PETM) and, like the PETM, was characterized by a negative carbon isotope excursion coupled with warming. We combined benthic foraminiferal and sedimentological records for Southeast Atlantic Sites 1263 (1500 m paleodepth) and 1262 (3600 m paleodepth) to show that benthic foraminiferal diversity and accumulation rates declined more precipitously and severely at the shallower site during peak ETM2. The sites are in close proximity, so differences in surface productivity cannot have caused this differential effect. Instead, on the basis of an analysis of climate modelling experiments, we infer that changes in ocean circulation pattern across ETM2 may have resulted in more pronounced warming at intermediate depths (Site 1263). The effects of more pronounced warming include increased metabolic rates, leading to a decrease in effective food supply and increased deoxygenation, thus potentially explaining the more severe benthic impacts at Site 1263. In response to more severe benthic disturbance, bioturbation may have decreased at Site 1263 as compared to Site 1262, hence differentially affecting the bulk carbonate record. We use a sediment-enabled Earth system model to test whether a reduction in bioturbation and/or the likely reduced carbonate saturation of more poorly ventilated waters can explain the more extreme excursion in bulk d13C and sharper transition in wt% CaCO3 at Site 1263. We find that both enhanced acidification and reduced bioturbation during peak ELMO conditions are needed to account for the observed features. Our combined ecological and modelling analysis illustrates the potential role of ocean circulation changes in amplifying local environmental changes and driving temporary, but drastic, loss of benthic biodiversity and abundance.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.