Richard E. Zeebe

An early Cenozoic perspective on greenhouse warming and carbon-cycle dynamics.

Past episodes of greenhouse warming provide insight into the coupling of climate and the carbon cycle and thus may help to predict the consequences of unabated carbon emissions in the future.

Reduced calcification of marine plankton in response to increased atmospheric CO2.

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments. This is important in regulating marine carbon cycling and ocean–atmosphere CO2 exchange. The present rise in atmospheric CO2 levels causes significant changes in surface ocean pH and carbonate chemistry. Such changes have been shown to slow down calcification in corals and coralline macroalgae,, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.

An explanation of the effect of seawater carbonate concentration on foraminiferal oxygen isotopes

Abstract Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ18O of the foraminiferal calcite decreases with increasing CO32− concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H2CO3] + [HCO3−] + [CO32−] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO3 also decreases with increasing pH. The slope of shell δ18O vs. [CO32−] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg−1)−1 (Spero et al., 1997) , whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg−1)−. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed.

Decreasing marine biogenic calcification: A negative feedback on rising atmospheric pCO2

In laboratory experiments with the coccolithophore species Emiliania huxleyi and Gephyrocapsa oceanica, the ratio of particulate inorganic carbon (PIC) to particulate organic carbon (POC) production decreased with increasing CO2 concentration ([CO2]). This was due to both reduced PIC and enhanced POC production at elevated [CO2]. Carbon dioxide concentrations covered a range from a preindustrial level to a value predicted for 2100 according to a “business as usual” anthropogenic CO2 emission scenario. The laboratory results were used to employ a model in which the immediate effect of a decrease in global marine calcification relative to POC production on the potential capacity for oceanic CO2 uptake was simulated. Assuming that overall marine biogenic calcification shows a similar response as obtained for E. huxleyi or G. oceanica in the present study, the model reveals a negative feedback on increasing atmospheric CO2 concentrations owing to a decrease in the PIC/POC ratio.

Carbon Emissions and Acidification

Avoiding environmental damage from ocean acidification requires reductions in carbon dioxide emissions regardless of climate change.

A Cenozoic record of the equatorial Pacific carbonate compensation depth

Atmospheric carbon dioxide concentrations and climate are regulated on geological timescales by the balance between carbon input from volcanic and metamorphic outgassing and its removal by weathering feedbacks; these feedbacks involve the erosion of silicate rocks and organic-carbon-bearing rocks. The integrated effect of these processes is reflected in the calcium carbonate compensation depth, which is the oceanic depth at which calcium carbonate is dissolved. Here we present a carbonate accumulation record that covers the past 53 million years from a depth transect in the equatorial Pacific Ocean. The carbonate compensation depth tracks long-term ocean cooling, deepening from 3.0–3.5 kilometres during the early Cenozoic (approximately 55 million years ago) to 4.6 kilometres at present, consistent with an overall Cenozoic increase in weathering. We find large superimposed fluctuations in carbonate compensation depth during the middle and late Eocene. Using Earth system models, we identify changes in weathering and the mode of organic-carbon delivery as two key processes to explain these large-scale Eocene fluctuations of the carbonate compensation depth.

Making sense of palaeoclimate sensitivity

Many palaeoclimate studies have quantified pre-anthropogenic climate change to calculate climate sensitivity (equilibrium temperature change in response to radiative forcing change), but a lack of consistent methodologies produces a wide range of estimates and hinders comparability of results. Here we present a stricter approach, to improve intercomparison of palaeoclimate sensitivity estimates in a manner compatible with equilibrium projections for future climate change. Over the past 65 million years, this reveals a climate sensitivity (in K W−1 m2) of 0.3–1.9 or 0.6–1.3 at 95% or 68% probability, respectively. The latter implies a warming of 2.2–4.8 K per doubling of atmospheric CO2, which agrees with IPCC estimates.

Seawater pH and isotopic paleotemperatures of Cretaceous oceans

Abstract Stable oxygen isotope ratios ( δ 18 O) of foraminifera are widely used to reconstruct the climatic history of Earth. It is well known that temperature reconstructions based on δ 18 O are complicated by factors such as the unknown isotopic composition of the ocean. In addition, recent experimental and theoretical work has shown that the seawater pH has a marked effect on the δ 18 O of foraminifera. Here I employ this effect to demonstrate that reconstructions based on δ 18 O of foraminifera may underestimate sea surface temperatures in the geological past. Ocean surface temperatures for the mid-Cretaceous are estimated to have been ∼2–3.5°C higher than previously thought.

The influence of symbiont photosynthesis on the boron isotopic composition of foraminifera shells

Culture experiments were carried out with the planktonic foraminifer Orbulina universa under high and low light levels in order to determine the influence of symbiont photosynthetic activity on the boron isotopic composition of shell calcite. Under low light (reduced photosynthetic rates) the boron isotopic composition of the tests is 1.5‰ lower compared to shells grown under high light (elevated photosynthetic rates). In terms of inferred pH, the lower boron isotope values correspond to a reduction in pH of approximately 0.2 units. The boron isotopic composition of Orbulina universa from plankton tows is similar to that of shells grown under low light conditions in the laboratory. These data are consistent with reduced symbiont concentrations in recently secreted shells. In addition to laboratory and field grown O. universa, we present the first data for a symbiont-barren foraminifer, Globigerina bulloides. Data obtained for G. bulloides fall ∼1.4‰ below those of the field grown O. universa. Although the plankton tow results are preliminary, they support the hypothesis that respiration and photosynthesis are the key physiological parameters responsible for species-specific vital effects.

Comparison of two potential strategies of planktonic foraminifera for house building: Mg2+ or H+ removal?

Marine organisms must possess strategies enabling them to initiate calcite precipitation despite the unfavorable conditions for inorganic precipitation in surface seawater. These strategies are poorly understood. Here we compare two potential strategies of marine calcifyers to manipulate seawater chemistry in order to initiate calcite precipitation: Removal of Mg2+ and H+ ions from seawater solutions. An experimental setup was used to monitor the onset of inorganic precipitation on seed crystals as a function of the Mg2+ concentration and pH in artificial seawater. We focused on precipitation rates typical for biogenic calcification in planktonic foraminifera (∼10−3 mol m−2 h−1) and time scales typical for the initiation of calcification in these organisms (minutes to hours). We find that the carbonate ion concentration has to increase by a factor of ∼13 when [Mg2+] increases from 0 to 53 mmol kg−1 in order to maintain a typical biogenic precipitation rate. Model calculations for the energy requirement for various scenarios of Mg2+ and H+ removal including Ca2+ exchange and CO2 diffusion are presented. We conclude that the more cost-effective strategy to initiate calcite precipitation in foraminifera is H+ removal, rather than Mg2+ removal.