Stable isotope record, opal accumulation rate and geochemistry of middle Miocene sediments of IODP Site 321-U1338

During the middle Miocene, Earth's climate transitioned from a relatively warm phase (Miocene climatic optimum) into a colder mode with re-establishment of permanent ice sheets on Antarctica, thus marking a fundamental step in Cenozoic cooling. Carbon sequestration and atmospheric CO2 drawdown through increased terrestrial and/or marine productivity have been proposed as the main drivers of this fundamental transition. We integrate high-resolution (1-3 k.y.) benthic stable isotope data with XRF-scanner derived biogenic silica and carbonate accumulation estimates in an exceptionally well-preserved sedimentary archive, recovered at Integrated Ocean Drilling Program Site U1338, to reconstruct eastern equatorial Pacific productivity variations and to investigate temporal linkages between high- and low-latitude climate change over the interval 16-13 Ma. Our records show that the climatic optimum (16.8-14.7 Ma) was characterized by high amplitude climate variations, marked by intense perturbations of the carbon cycle. Episodes of peak warmth at (southern hemisphere) insolation maxima coincided with transient shoaling of the carbonate compensation depth and enhanced carbonate dissolution in the deep ocean. A switch to obliquity-paced climate variability after 14.7 Ma concurred with a general improvement in carbonate preservation and the onset of stepwise global cooling, culminating with extensive ice growth over Antarctica at ~13.8 Ma. We find that two massive increases in opal accumulation at ~14.0 and ~13.8 Ma occurred just before and during the final and most prominent cooling step, supporting the hypothesis that enhanced siliceous productivity in the eastern equatorial Pacific contributed to CO2 drawdown.

Seawater carbonate chemistry, POC, PIC, TPC, SPM, N, TEP and growth rate during experiments with coccolithophores Emiliania huxleyi (AC472), Calcidiscus leptoporus (AC370) and Syracosphaera pulchra (AC418) during experiments, 2011

The response of three coccolithophores (Emiliania huxleyi, Calcidiscus leptoporus and Syracosphaera pulchra) to elevated partial pressure (pCO2) of carbon dioxide was investigated in batch cultures. For the first time, we also report on the response of the non calcifying (haploid) life stage of these three species. The growth rate, cell size, inorganic (PIC) and organic carbon (POC) of both life stages were measured at two different pCO2 (400and 760 ppm) and their organic and inorganic carbon production calculated. The two lifestages within the same species generally exhibited a similar response to elevated pCO2, theresponse of the haploid stage being often more pronounced than that of the diploid stage. Thegrowth rate was consistently higher at higher pCO2 but the response of other processes varied among species. The calcification rate of C. leptoporus and of S. pulchra did not change at elevated pCO2 while increased in E. huxleyi. The POC production as well as the cell size of both life stages of S. pulchra and of the haploid stage of E. huxleyi markedly decreased at elevated pCO2. It remained unaltered in the diploid stage of E. huxleyi and C. leptoporus and increased in the haploid stage of the latter. The PIC:POC ratio increased in E. huxleyi and was constant in C. leptoporus and S. pulchra. These results suggest that the non-calcifying stage, is more responsive than the calcifying stage and that the most versatile genera will proliferate in a more acidic ocean rather than all coccolithophores will decline.

Carbon uptake rate calculated for melt pond water samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Melt pond samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Seawater carbonate chemistry, growth rate and processes during experiments with Coccolithus pelagicus and Calcidiscus leptoporus, 2006

Uptake of half of the fossil fuel CO2 into the ocean causes gradual seawater acidification. This has been shown to slow down calcification of major calcifying groups, such as corals, foraminifera, and coccolithophores. Here we show that two of the most productive marine calcifying species, the coccolithophores Coccolithus pelagicus and Calcidiscus leptoporus, do not follow the CO2-related calcification response previously found. In batch culture experiments, particulate inorganic carbon (PIC) of C. leptoporus changes with increasing CO2 concentration in a nonlinear relationship. A PIC optimum curve is obtained, with a maximum value at present-day surface ocean pCO2 levels (?360 ppm CO2). With particulate organic carbon (POC) remaining constant over the range of CO2 concentrations, the PIC/POC ratio also shows an optimum curve. In the C. pelagicus cultures, neither PIC nor POC changes significantly over the CO2 range tested, yielding a stable PIC/POC ratio. Since growth rate in both species did not change with pCO2, POC and PIC production show the same pattern as POC and PIC. The two investigated species respond differently to changes in the seawater carbonate chemistry, highlighting the need to consider species-specific effects when evaluating whole ecosystem responses. Changes of calcification rate (PIC production) were highly correlated to changes in coccolith morphology. Since our experimental results suggest altered coccolith morphology (at least in the case of C. leptoporus) in the geological past, coccoliths originating from sedimentary records of periods with different CO2 levels were analyzed. Analysis of sediment samples was performed on six cores obtained from locations well above the lysocline and covering a range of latitudes throughout the Atlantic Ocean. Scanning electron micrograph analysis of coccolith morphologies did not reveal any evidence for significant numbers of incomplete or malformed coccoliths of C. pelagicus and C. leptoporus in last glacial maximum and Holocene sediments. The discrepancy between experimental and geological results might be explained by adaptation to changing carbonate chemistry.

Seawater carbonate chemistry, survival rate, shell mass growth, shell dissolution and locomotory speed of Limacina retroversa in a laboratory experiment

Anthropogenic carbon dioxide emissions induce ocean acidification, thereby reducing carbonate ion concentration, which may affect the ability of calcifying organisms to build shells. Pteropods, the main planktonic producers of aragonite in the worlds' oceans, may be particularly vulnerable to changes in sea water chemistry. The negative effects are expected to be most severe at high-latitudes, where natural carbonate ion concentrations are low. In this study we investigated the combined effects of ocean acidification and freshening on Limacina retroversa, the dominant pteropod in sub polar areas. Living L. retroversa, collected in Northern Norwegian Sea, were exposed to four different pH values ranging from the pre-industrial level to the forecasted end of century ocean acidification scenario. Since over the past half-century the Norwegian Sea has experienced a progressive freshening with time, each pH level was combined with a salinity gradient in two factorial, randomized experiments investigating shell degradation, swimming behavior and survival. In addition, to investigate shell degradation without any physiologic influence, one perturbation experiments using only shells of dead pteropods was performed. Lower pH reduced shell mass whereas shell dissolution increased with pCO2. Interestingly, shells of dead organisms had a higher degree of dissolution than shells of living individuals. Mortality of Limacina retroversa was strongly affected only when both pH and salinity reduced simultaneously. The combined effects of lower salinity and lower pH also affected negatively the ability of pteropods to swim upwards. Results suggest that the energy cost of maintaining ion balance and avoiding sinking (in low salinity scenario) combined with the extra energy cost necessary to counteract shell dissolution (in high pCO2 scenario), exceed the available energy budget of this organism causing the pteropods to change swimming behavior and begin to collapse. Since L. retroversa play an important role in the transport of carbonates to the deep oceans these findings have significant implications for the mechanisms influencing the inorganic carbon cycle in the sub-polar area.

Seawater carbonate chemistry and length, weight, survival rate, metabolic rate of coral reef fish Amphiprion melanopus in a laboratory experiment

Carbon dioxide concentrations in the surface ocean are increasing owing to rising CO2 concentrations in the atmosphere. Higher CO2 levels are predicted to affect essential physiological processes of many aquatic organisms, leading to widespread impacts on marine diversity and ecosystem function, especially when combined with the effects of global warming. Yet the ability for marine species to adjust to increasing CO2 levels over many generations is an unresolved issue. Here we show that ocean conditions projected for the end of the century (approximately 1,000 µatm CO2 and a temperature rise of 1.5-3.0 °C) cause an increase in metabolic rate and decreases in length, weight, condition and survival of juvenile fish. However, these effects are absent or reversed when parents also experience high CO2 concentrations. Our results show that non-genetic parental effects can dramatically alter the response of marine organisms to increasing CO2 and demonstrate that some species have more capacity to acclimate to ocean acidification than previously thought.

Carbon uptake rate calculated for CTD water samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Seawater samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Carbon uptake rate calculated for sea-ice core samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Melted sea ice samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Seawater carbonate chemistry, cell numbers and growth rate during experiments with dinoflagellates, 2007

The effects of dissolved inorganic carbon (DIC) on the growth of 3 red-tide dinoflagellates (Ceratium lineatum, Heterocapsa triquetra and Prorocentrum minimum) were studied at pH 8.0 and at higher pH levels, depending upon the pH tolerance of the individual species. The higher pH levels chosen for experiments were 8.55 for C. lineatum and 9.2 for the other 2 species. At pH 8.0, which approximates the pH found in the open sea, the maximum growth in all species was maintained until the total DIC concentration was reduced below ~0.4 and 0.2 mM for C. lineatum and the other 2 species, respectively. Growth compensation points (concentration of inorganic carbon needed for maintenance of cells) were reached at ~0.18 and 0.05 mM DIC for C. lineatum and the other 2 species, respectively. At higher pH levels, maximum growth rates were lower compared to growth at pH 8, even at very high DIC concentrations, indicating a direct pH effect on growth. Moreover, the concentration of bio-available inorganic carbon (CO2 + HCO3-) required for maintenance as well as the half-saturation constants were increased considerably at high pH compared to pH 8.0. Experiments with pH-drift were carried out at initial concentrations of 2.4 and 1.2 mM DIC to test whether pH or DIC was the main limiting factor at a natural range of DIC. Independent of the initial DIC concentrations, growth rates were similar in both incubations until pH had increased considerably. The results of this study demonstrated that growth of the 3 species was mainly limited by pH, while inorganic carbon limitation played a minor role only at very high pH levels and low initial DIC concentrations.

Seawater carbonate chemistry, nutrients and growth rate during experiments with coral Astrangia poculata and field observations, 2010

Zooxanthellate colonies of the scleractinian coral Astrangia poculata were grown under combinations of ambient and elevated nutrients (5 µM NO, 0.3 µM PO4, and 2nM Fe) and CO2 (780 ppmv) treatments for a period of 6 months. Coral calcification rates, estimated from buoyant weights, were not significantly affected by moderately elevated nutrients at ambient CO2 and were negatively affected by elevated CO2 at ambient nutrient levels. However, calcification by corals reared under elevated nutrients combined with elevated CO2 was not significantly different from that of corals reared under ambient conditions, suggesting that CO2 enrichment can lead to nutrient limitation in zooxanthellate corals. A conceptual model is proposed to explain how nutrients and CO2 interact to control zooxanthellate coral calcification. Nutrient limited corals are unable to utilize an increase in dissolved inorganic carbon (DIC) as nutrients are already limiting growth, thus the effect of elevated CO2 on saturation state drives the calcification response. Under nutrient replete conditions, corals may have the ability to utilize more DIC, thus the calcification response to CO2 becomes the product of a negative effect on saturation state and a positive effect on gross carbon fixation, depending upon which dominates, the calcification response can be either positive or negative. This may help explain how the range of coral responses found in different studies of ocean acidification can be obtained.