Modeling the marine aragonite cycle: changes under rising carbon dioxide and its role in shallow water CaCO3 dissolution

The marine aragonite cycle has been included in the global biogeochemical model PISCES to study the role of aragonite in shallow water CaCO3 dissolution. Aragonite production is parameterized as a function of mesozooplankton biomass and aragonite saturation state of ambient waters. Observation-based estimates of marine carbonate production and dissolution are well reproduced by the model and about 60% of the combined CaCO3 water column dissolution from aragonite and calcite is simulated above 2000 m. In contrast, a calcite-only version yields a much smaller fraction. This suggests that the aragonite cycle should be included in models for a realistic representation of CaCO3 dissolution and alkalinity. For the SRES A2 CO2 scenario, production rates of aragonite are projected to notably decrease after 2050. By the end of this century, global aragonite production is reduced by 29% and total CaCO3 production by 19% relative to pre-industrial. Geographically, the effect from increasing atmospheric CO2, and the subsequent reduction in saturation state, is largest in the subpolar and polar areas where the modeled aragonite production is projected to decrease by 65% until 2100.

Constraints on barium isotope fractionation during aragonite precipitation by corals

We present a barium (Ba) isotope fractionation study of marine biogenic carbonates (aragonitic corals). The major aim is to provide first constraints on the Ba isotope fractionation between modern surface sea water and coral skele- ton. Mediterranean surface sea water was found to be enriched in the heavy Ba isotopes compared to previously reported values for marine open ocean authi- genic and terrestrial minerals. In aquarium experiments with a continuous sup- ply of Mediterranean surface water, the Ba isotopic composition of the bulk sample originating from cultured, aragonitic scleractinian corals (d137/134Ba between +0.16 +/- 0.12permil and +0.41 +/-0.12permil) were isotopically identical or lighter than that of the ambient Mediterranean surface sea water (d137/134Ba = +0.42 +/- 0.07permil, 2SD), which corresponds to an empirical maximum value of Ba isotope fractionation of D137/134Bacoral-seawater = -0.26 +/- 0.14permil at 25°C. This maximum Ba isotope fractionation is close and identical in direction to previous results from inorganic precipitation experiments with aragonite- structured pure BaCO3 (witherite). The variability in measured Ba concentrations of the cultured corals is at odds with a uniform distribution coefficient, DBa/Ca, thus indicating stronger vital effects on isotope than element discrimination. This observation supports the hypothesis that the Ba isotopic compositions of these corals do not result from simple equilibrium between the skeleton and the bulk sea water. Complementary coral samples from natural settings (tropical shallow-water corals from the Bahamas and Florida and cold- water corals from the Norwegian continental shelf) show an even wider range in d137/134Ba values (+0.14 +/- 0.08permil and +0.77 +/- 0.11permil), most probably due to additional spatial and/or temporal sea water heterogeneity, as indicated by recent publications.

Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer

Detection of extraterrestrial life is an ongoing goal in space exploration, and there is a need for advanced instruments and methods for the detection of signatures of life based on chemical and isotopic composition. Here, we present the first investigation of chemical composition of putative microfossils in natural samples using a miniature laser ablation/ionization time-of-flight mass spectrometer (LMS). The studies were conducted with high lateral (similar to 15 mu m) and vertical (similar to 20-200 nm) resolution. The primary aim of the study was to investigate the instrument performance on micrometer-sized samples both in terms of isotope abundance and element composition. The following objectives had to be achieved: (1) Consider the detection and calculation of single stable isotope ratios in natural rock samples with techniques compatible with their employment of space instrumentation for biomarker detection in future planetary missions. (2) Achieve a highly accurate chemical compositional map of rock samples with embedded structures at the micrometer scale in which the rock matrix is easily distinguished from the micrometer structures. Our results indicate that chemical mapping of strongly heterogeneous rock samples can be obtained with a high accuracy, whereas the requirements for isotope ratios need to be improved to reach sufficiently large signal-to-noise ratio (SNR). Key Words: Biogenicity-Biomarkers-Biosignatures-Filaments-Fossilization. Astrobiology 15, 669-682.

Sensitivity of pelagic calcification to ocean acidification

Ocean acidification might reduce the ability of calcifying plankton to produce and maintain their shells of calcite, or of aragonite, the more soluble form of CaCO3. In addition to possibly large biological impacts, reduced CaCO3 production corresponds to a negative feedback on atmospheric CO2. In order to explore the sensitivity of the ocean carbon cycle to increasing concentrations of atmospheric CO2, we use the new biogeochemical Bern3D/PISCES model. The model reproduces the large scale distributions of biogeochemical tracers. With a range of sensitivity studies, we explore the effect of (i) using different parameterizations of CaCO3 production fitted to available laboratory and field experiments, of (ii) letting calcite and aragonite be produced by auto- and heterotrophic plankton groups, and of (iii) using carbon emissions from the range of the most recent IPCC Representative Concentration Pathways (RCP). Under a high-emission scenario, the CaCO3 production of all the model versions decreases from ~1 Pg C yr−1 to between 0.36 and 0.82 Pg C yr−1 by the year 2100. The changes in CaCO3 production and dissolution resulting from ocean acidification provide only a small feedback on atmospheric CO2 of −1 to −11 ppm by the year 2100, despite the wide range of parameterizations, model versions and scenarios included in our study. A potential upper limit of the CO2-calcification/dissolution feedback of −30 ppm by the year 2100 is computed by setting calcification to zero after 2000 in a high 21st century emission scenario. The similarity of feedback estimates yielded by the model version with calcite produced by nanophytoplankton and the one with calcite, respectively aragonite produced by mesozooplankton suggests that expending biogeochemical models to calcifying zooplankton might not be needed to simulate biogeochemical impacts on the marine carbonate cycle. The changes in saturation state confirm previous studies indicating that future anthropogenic CO2 emissions may lead to irreversible changes in ΩA for several centuries. Furthermore, due to the long-term changes in the deep ocean, the ratio of open water CaCO3 dissolution to production stabilizes by the year 2500 at a value that is 30–50% higher than at pre-industrial times when carbon emissions are set to zero after 2100.

Ocean acidification limits temperature-induced poleward expansion of coral habitats around Japan

Using results from four coupled global carbon cycle-climate models combined with in situ observations, we estimate the effects of future global warming and ocean acidification on potential habitats for tropical/subtropical and temperate coral communities in the seas around Japan. The suitability of coral habitats is classified on the basis of the currently observed regional ranges for temperature and saturation states with regard to aragonite (Ωarag). We find that, under the "business as usual" SRES A2 scenario, coral habitats are projected to expand northward by several hundred kilometers by the end of this century. At the same time, coral habitats are projected to become sandwiched between regions where the frequency of coral bleaching will increase, and regions where Ωarag will become too low to support sufficiently high calcification rates. As a result, the habitat suitable for tropical/subtropical corals around Japan may be reduced by half by the 2020s to 2030s, and is projected to disappear by the 2030s to 2040s. The habitat suitable for the temperate coral communities is also projected to decrease, although at a less pronounced rate, due to the higher tolerance of temperate corals for low Ωarag. Our study has two important caveats: first, it does not consider the potential adaptation of the coral communities, which would permit them to colonize habitats that are outside their current range. Second, it also does not consider whether or not coral communities can migrate quickly enough to actually occupy newly emerging habitats. As such, our results serve as a baseline for the assessment of the future evolution of coral habitats, but the consideration of important biological and ecological factors and feedbacks will be required to make more accurate projections.

Imminent ocean acidification in the Arctic projected with the NCAR global coupled carbon cycle-climate model

Ocean acidification from the uptake of anthropogenic carbon is simulated for the industrial period and IPCC SRES emission scenarios A2 and B1 with a global coupled carbon cycle-climate model. Earlier studies identified seawater saturation state with respect to aragonite, a mineral phase of calcium carbonate, as a key variable governing impacts on corals and other shell-forming organisms. Globally in the A2 scenario, water saturated by more than 300%, considered suitable for coral growth, vanishes by 2070 AD (CO2≈630 ppm), and the ocean volume fraction occupied by saturated water decreases from 42% to 25% over this century. The largest simulated pH changes worldwide occur in Arctic surface waters, where hydrogen ion concentration increases by up to 185% (ΔpH=−0.45). Projected climate change amplifies the decrease in Arctic surface mean saturation and pH by more than 20%, mainly due to freshening and increased carbon uptake in response to sea ice retreat. Modeled saturation compares well with observation-based estimates along an Arctic transect and simulated changes have been corrected for remaining model-data differences in this region. Aragonite undersaturation in Arctic surface waters is projected to occur locally within a decade and to become more widespread as atmospheric CO2 continues to grow. The results imply that surface waters in the Arctic Ocean will become corrosive to aragonite, with potentially large implications for the marine ecosystem, if anthropogenic carbon emissions are not reduced and atmospheric CO2 not kept below 450 ppm.

Earth system commitments due to delayed mitigation

As long as global CO₂ emissions continue to increase annually, long-term committed Earth system changes grow much faster than current observations. A novel metric linking this future growth to policy decisions today is the mitigation delay sensitivity (MDS), but MDS estimates for Earth system variables other than peak temperature (ΔT max) are missing. Using an Earth System Model of Intermediate Complexity, we show that the current emission increase rate causes a ΔT max increase roughly 3–7.5 times as fast as observed warming, and a millenial steric sea level rise (SSLR) 7–25 times as fast as observed SSLR, depending on the achievable rate of emission reductions after the peak of emissions. These ranges are only slightly affected by the uncertainty range in equilibrium climate sensitivity, which is included in the above values. The extent of ocean acidification at the end of the century is also strongly dependent on the starting time and rate of emission reductions. The preservable surface ocean area with sufficient aragonite supersaturation for coral reef growth is diminished globally at an MDS of roughly 25%–80% per decade. A near-complete loss of this area becomes unavoidable if mitigation is delayed for a few years to decades. Also with respect to aragonite, 12%–18% of the Southern Ocean surface become undersaturated per decade, if emission reductions are delayed beyond 2015–2040. We conclude that the consequences of delaying global emission reductions are much better captured if the MDS of relevant Earth system variables is communicated in addition to current trends and total projected future changes.