Calcite saturation and yield and Mg/Ca, Mn/Ca, Al/Ca, Fe/Ca for four species of planktic foraminifera cleaned using Mg-cleaning and Cd-cleaning methods

Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.

Seawater carbonate chemistry in Ischia, Italy, 2008

The atmospheric partial pressure of carbon dioxide (pCO2) will almost certainly be double that of pre-industrial levels by 2100 and will be considerably higher than at any time during the past few million years1. The oceans are a principal sink for anthropogenic CO2 where it is estimated to have caused a 30% increase in the concentration of H+ in ocean surface waters since the early 1900s and may lead to a drop in seawater pH of up to 0.5 units by 2100. Our understanding of how increased ocean acidity may affect marine ecosystems is at present very limited as almost all studies have been in vitro, short-term, rapid perturbation experiments on isolated elements of the ecosystem4, 5. Here we show the effects of acidification on benthic ecosystems at shallow coastal sites where volcanic CO2 vents lower the pH of the water column. Along gradients of normal pH (8.1-8.2) to lowered pH (mean 7.8-7.9, minimum 7.4-7.5), typical rocky shore communities with abundant calcareous organisms shifted to communities lacking scleractinian corals with significant reductions in sea urchin and coralline algal abundance. To our knowledge, this is the first ecosystem-scale validation of predictions that these important groups of organisms are susceptible to elevated amounts of pCO2. Sea-grass production was highest in an area at mean pH 7.6 (1,827 µatm pCO2) where coralline algal biomass was significantly reduced and gastropod shells were dissolving due to periods of carbonate sub-saturation. The species populating the vent sites comprise a suite of organisms that are resilient to naturally high concentrations of pCO2 and indicate that ocean acidification may benefit highly invasive non-native algal species. Our results provide the first in situ insights into how shallow water marine communities might change when susceptible organisms are removed owing to ocean acidification.

Villefranche MedSeA mesocosm experiment 2013: perturbation studies and field studies

A joint mesocosm experiment took place in February/March 2013 in the bay of Villefranche in France as part of the european MedSeA project. Nine mesocosms (52 m**3) were deployed over a 2 weeks period and 6 different levels of pCO2 and 3 control mesocosms (about 450 µatm), were used, in order to cover the range of pCO2 anticipated for the end of the present century. During this experiment, the potential effects of these perturbations on chemistry, planktonic community composition and dynamics including: eucaryotic and prokaryotic species composition, primary production, nutrient and carbon utilization, calcification, diazotrophic nitrogen fixation, organic matter exudation and composition, micro-layer composition and biogas production were studied by a group of about 25 scientists from 8 institutes and 6 countries. This is one of the first mesocosm experiments conducted in oligotrophic waters. A blog dedicated to this experiment can be viewed at: http://medseavillefranche2013.obs-vlfr.fr.

Stareso MedSeA mesocosm experiment: field and perturbation studies 2012

A joint mesocosm experiment took place in June/July 2012 in Corsica (bay of Calvi, Stareso station;http://www.stareso.com/) as part of the european MedSeA project. Nine mesocosms (52 m**3) were deployed over a 20 days period and 6 different levels of pCO2 and 3 control mesocosms (about 450 µatm), were used, in order to cover the range of pCO2 anticipated for the end of the present century. During this experiment, the potential effects of these perturbations on chemistry, planktonic community composition and dynamics including: eucaryotic and prokaryotic species composition, primary production, nutrient and carbon utilization, calcification, diazotrophic nitrogen fixation, organic matter exudation and composition, micro-layer composition and biogas production were studied by a group of about 25 scientists from 8 institutes and 6 countries. This is one of the first mesocosm experiments conducted in oligotrophic waters. A blog dedicated to this experiment can be viewed at: http://medseastareso2012.wordpress.com/.

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.

Potential impact of DOM accumulation on fCO2 and carbonate ion computations in ocean acidification experiments

Culture and mesocosm experiments are often carried out under high initial nutrient concentrations, yielding high biomass concentrations that in turn often lead to a substantial build-up of DOM. In such experiments, DOM can reach concentrations much higher than typically observed in the open ocean. To the extent that DOM includes organic acids and bases, it will contribute to the alkalinity of the seawater contained in the experimental device. Our analysis suggests that whenever substantial amounts of DOM are produced during the experiment, standard computer programmes used to compute CO2 fugacity can underestimate true fCO2 significantly when the computation is based on AT and CT. Unless the effect of DOM-alkalinity can be accounted for, this might lead to significant errors in the interpretation of the system under consideration with respect to the experimentally applied CO2 perturbation. Errors in the inferred fCO2 can misguide the development of parameterisations used in simulations with global carbon cycle models in future CO2-scenarios. Over determination of the CO2-system in experimental ocean acidification studies is proposed to safeguard against possibly large errors in estimated fCO2.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Composition and crystal parameters of carbonate-apatites from animal teeth and bones and from phosphate rocks of the ocean bottom

Samples of recent to Miocene fish and marine mammal bones from the bottom of the Atlantic and Pacific Oceans and Miocene Maikop deposits (Transcaspian region) are studied by X-ray diffraction technique combined with chemical and energy-dispersive analyses. Changes of lattice parameters and chemical composition of bioapatite during fossilization and diagenesis suggest that development of skeletal apatite proceeds from dahllite-type hydroxyapatite to francolite-type carbonate-fluorapatite. It is assumed that jump-type transition from dahllite to francolite during initial fossilization reflects replacement of biogeochemical reactions in living organisms, which are subject to nonlinear laws of nonequilibrium thermodynamics, by physicochemical processes according to the linear equilibrium thermodynamics.

B/Ca ratios in planktonic foraminifera

Boron isotope systematics indicate that boron incorporation into foraminiferal CaCO3 is determined by the partition coefficient, KD = [B/Ca](CaCO3)/[B(OH)4**-/HCO3**-](seawater), and [B(OH)4?/HCO3?](seawater), providing, in principle, a method to estimate seawater pH and PCO2. We have measured B/Ca ratios in Globigerina bulloides and Globorotaliainflata for a series of core tops from the North Atlantic and the Southern Ocean and in Globigerinoides ruber (white) from Ocean Drilling Program (ODP) site 668B on the Sierra Leone Rise in the eastern equatorial Atlantic. B/Ca ratios in these species of planktonic foraminifera seem unaffected by dissolution on the seafloor. KD shows a strong species-specific dependence on calcification temperature, which can be corrected for using the Mg/Ca temperature proxy. A preliminary study of G. inflata from Southern Ocean sediment core CHAT 16K suggests that temperature-corrected B/Ca was ~30% higher during the last glacial. Correspondingly, pH was 0.15 units higher and aqueous PCO2 was 95 ?atm lower at this site at the Last Glacial Maximum. The covariation between reconstructed PCO2 and the atmospheric pCO2 from the Vostok ice core demonstrates the feasibility of using B/Ca in planktonic foraminifera for reconstructing past variations in pH and PCO2.

Signals of resilience to ocean change: high thermal tolerance of early stage Antarctic sea urchins (Sterechinus neumayeri) reared under present-day and future pCO2 and temperature

We tested the hypothesis that development of the Antarctic urchin Sterechinus neumayeri under future ocean conditions of warming and acidification would incur physiological costs, reducing the tolerance of a secondary stressor. The aim of this study is twofold: (1) quantify current austral spring temperature and pH near sea urchin habitat at Cape Evans in McMurdo Sound, Antarctica and (2) spawn S. neumayeri in the laboratory and raise early developmental stages (EDSs) under ambient (-0.7 °C; 400 µatm pCO2) and future (+2.6 °C; 650 and 1,000 µatm pCO2) ocean conditions and expose four EDSs (blastula, gastrula, prism, and 4-arm echinopluteus) to a one hour acute heat stress and assess survivorship. Results of field data from 2011 to 2012 show extremely stable inter-annual pH conditions ranging from 7.99 to 8.08, suggesting that future ocean acidification will drastically alter the pH-seascape for S. neumayeri. In the laboratory, S. neumayeri EDSs appear to be tolerant of temperatures and pCO2 levels above their current habitat conditions. EDSs survived acute heat exposures >20 °C above habitat temperatures of -1.9 °C. No pCO2 effect was observed for EDSs reared at -0.7 °C. When reared at +2.6 °C, small but significant pCO2 effects were observed at the blastula and prism stage, suggesting that multiple stressors are more detrimental than single stressors. While surprisingly tolerant overall, blastulae were the most sensitive stage to ocean warming and acidification. We conclude that S. neumayeri may be unexpectedly physiologically tolerant of future ocean conditions.

Stable isotope record of Globorotalia inflata

We sampled the upper water column for living planktic foraminifera along the SW-African continental margin. The species Globorotalia inflata strongly dominates the foraminiferal assemblages with an overall relative abundance of 70-90%. The shell delta18O and delta13C values of G. inflata were measured and compared to the predicted oxygen isotope equilibrium values (delta18O(eq)) and to the carbon isotope composition of the total dissolved inorganic carbon (delta13C(DIC)) of seawater. The delta18O of G. inflata reflects the general gradient observed in the predicted delta18O(eq) profile, while the delta13C of G. inflata shows almost no variation with depth and the reflection of the delta13C(DIC) in the foraminiferal shell seems to be covered by other effects. We found that offsets between delta18O(shell) and predicted delta18O(eq) in the surface mixed layer do not correlate to changes in seawater [CO3[2-]]. To calculate an isotopic mass balance of depth integrated growth, we used the oxygen isotope composition of G. inflata to estimate the fraction of the total shell mass that is grown within each plankton tow depth interval of the upper 500 m of the water column. This approach allows us to calculate the DELTA delta13C(interval added-DIC); i.e. the isotopic composition of calcite that was grown within a given depth interval. Our results consistently show that the DELTA delta13C(IA-DIC) correlates negatively with in situ measured [CO3[2-]] of the ambient water. Using this approach, we found DELTA delta13C(IA-DIC)/[CO3[2-]] slopes for G. inflata in the large size fraction (250-355 µm) of -0.013 per mil to 0.015 per mil (µmol/kg)**-1 and of -0.013 per mil to 0.017 per mil (µmol/kg)**-1 for the smaller specimens (150-250 µm). These slopes are in the range of those found for other non-symbiotic species, such as Globigerina bulloides, from laboratory culture experiments. Since the DELTA delta13C(IA-DIC)/[CO3[2-]] slopes from our field data are nearly identical to the slopes established from laboratory culture experiments we assume that the influence of other effects, such as temperature, are negligibly small. If we correct the delta13C values of G. inflata for a carbonate ion effect, the delta13C(shell) and delta13C(DIC) are correlated with an average offset of 2.11.

Mg/Ca of planktonic foraminifera from tropical Pacific surface sediments

Mg/Ca in planktonic foraminifers carries two main signals: calcification temperature and postdepositional test dissolution. Shell dissolution thus distorts water temperature reconstructions made with Mg/Ca in foraminifers. This problem could be resolved by quantifying the impact of carbonate dissolution on Mg/Ca with an independent, temperature-insensitive deep-sea calcite dissolution proxy, such as the Globorotalia menardii fragmentation index (MFI). To test the validity of this approach, we measured Mg/Ca in the tests of several planktonic foraminifers and MFI in core tops collected over a wide geographic region of the tropical Pacific and covering a wide range of deep-sea calcite dissolution and seawater temperature. We confirm that Mg/Ca from different species have different susceptibility to temperature and dissolution. Mg/Ca in surface-dwelling Globigerina bulloides is controlled by calcification temperature and is largely unaffected by carbonate dissolution estimated from MFI. In contrast, Mg/Ca in deeper dwelling G. menardii is minimally sensitive to temperature and dominantly affected by dissolution. Mg/Ca in Neogloboquadrina dutertrei and Pulleniatina obliquiloculata are significantly affected by both temperature and dissolution, and MFI can be effectively used to correct temperature estimates from these species for calcite dissolution. Additional variables besides temperature and dissolution appear to control Mg/Ca in Globorotalia tumida, and their identification is a prerequisite for interpreting elemental shell composition in this species. Combining down-core measurements of Mg/Ca in multiple foraminifer species with MFI provides a powerful tool for reconstructing past changes in the upper water column temperature structure in the tropical Pacific.

Coral-algae metabolism and diurnal changes in the CO2-carbonate system of bulk sea water

Precise measurements were conducted in continuous flow seawater mesocosms located in full sunlight that compared metabolic response of coral, coral-macroalgae and macroalgae systems over a diurnal cycle. Irradiance controlled net photosynthesis (Pnet), which in turn drove net calcification (Gnet), and altered pH. Pnet exerted the dominant control on [CO3]2- and aragonite saturation state (Omega arag) over the diel cycle. Dark calcification rate decreased after sunset, reaching zero near midnight followed by an increasing rate that peaked at 03:00 h. Changes in Omega arag and pH lagged behind Gnet throughout the daily cycle by two or more hours. The flux rate Pnet was the primary driver of calcification. Daytime coral metabolism rapidly removes dissolved inorganic carbon (DIC) from the bulk seawater and photosynthesis provides the energy that drives Gnet while increasing the bulk water pH. These relationships result in a correlation between Gnet and Omega arag, with Omega arag as the dependent variable. High rates of H+ efflux continued for several hours following mid-day peak Gnet suggesting that corals have difficulty in shedding waste protons as described by the Proton Flux Hypothesis. DIC flux (uptake) followed Pnet and Gnet and dropped off rapidly following peak Pnet and peak Gnet indicating that corals can cope more effectively with the problem of limited DIC supply compared to the problem of eliminating H+. Over a 24 h period the plot of total alkalinity (AT) versus DIC as well as the plot of Gnet versus Omega arag revealed a circular hysteresis pattern over the diel cycle in the coral and coral-algae mesocosms, but not the macroalgae mesocosm. Presence of macroalgae did not change Gnet of the corals, but altered the relationship between Omega arag and Gnet. Predictive models of how future global changes will effect coral growth that are based on oceanic Omega arag must include the influence of future localized Pnet on Gnet and changes in rate of reef carbonate dissolution. The correlation between Omega arag and Gnet over the diel cycle is simply the response of the CO2-carbonate system to increased pH as photosynthesis shifts the equilibria and increases the [CO3]2- relative to the other DIC components of [HCO3]- and [CO2]. Therefore Omega arag closely tracked pH as an effect of changes in Pnet, which also drove changes in Gnet. Measurements of DIC flux and H+ flux are far more useful than concentrations in describing coral metabolism dynamics. Coral reefs are systems that exist in constant disequilibrium with the water column.