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.

A combined vacuum crushing and sieving (CVCS) system designed to determine noble gas paleotemperatures from stalagmite samples

This paper presents a novel extraction device for water and noble gases from speleothem samples for noble gas paleotemperature determination. The “combined vacuum crushing and sieving (CVCS) system” was designed to reduce the atmospheric noble gas contents from air inclusions in speleothem samples by up to 2 orders of magnitude without adsorbing atmospheric noble gases onto the freshly produced grain surfaces, a process that had often hampered noble gas temperature (NGT) determination in the past. We also present the results from first performance tests of the CVCS system processing stalagmite samples grown at a known temperature. This temperature is reliably reproduced by the NGTs derived from Ar, Kr, and Xe extracted from the samples. The CVCS system is, therefore, suitable for routine determinations of accurate NGTs. In combination with stalagmite dating, these NGTs will allow reconstructing past regional temperature evolutions, and also support the interpretation of the often complex stable isotope records preserved in the stalagmites' calcite.

Stalagmite water content as a proxy for drip water supply in tropical and subtropical areas

In this pilot study water was extracted from samples of two Holocene stalagmites from Socotra Island, Yemen, and one Eemian stalagmite from southern continental Yemen. The amount of water extracted per unit mass of stalagmite rock, termed "water yield" hereafter, serves as a measure of its total water content. Based on direct correlation plots of water yields and δ18Ocalcite and on regime shift analyses, we demonstrate that for the studied stalagmites the water yield records vary systematically with the corresponding oxygen isotopic compositions of the calcite (δ18Ocalcite). Within each stalagmite lower δ18Ocalcite values are accompanied by lower water yields and vice versa. The δ18Ocalcite records of the studied stalagmites have previously been interpreted to predominantly reflect the amount of rainfall in the area; thus, water yields can be linked to drip water supply. Higher, and therefore more continuous drip water supply caused by higher rainfall rates, supports homogeneous deposition of calcite with low porosity and therefore a small fraction of water-filled inclusions, resulting in low water yields of the respective samples. A reduction of drip water supply fosters irregular growth of calcite with higher porosity, leading to an increase of the fraction of water-filled inclusions and thus higher water yields. The results are consistent with the literature on stalagmite growth and supported by optical inspection of thin sections of our samples. We propose that for a stalagmite from a dry tropical or subtropical area, its water yield record represents a novel paleo-climate proxy recording changes in drip water supply, which can in turn be interpreted in terms of associated rainfall rates.

Novel heating/cooling stage designed for fluid inclusion microthermometry of large stalagmite sections

Liquid–vapour homogenisation temperatures of fluid inclusions in stalagmites are used for quantitative temperature reconstructions in paleoclimate research. Specifically for this application, we have developed a novel heating/cooling stage that can be operated with large stalagmite sections of up to 17 × 35 mm2 to simplify and improve the chronological reconstruction of paleotemperature time-series. The stage is designed for use of an oil immersion objective and a high-NA condenser front lens to obtain high-resolution images for bubble radius measurements. The temperature accuracy of the stage is better than ± 0.1 °C with a precision (reproducibility) of ± 0.02 °C.

Glacial–interglacial temperature change in the tropical West Pacific: A comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquide vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O(‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glaciale interglacial cycles (Marine Isotope Stages (MIS) 12 e 9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquide vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion d18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion d18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glaciale interglacial temperature change, indicating temperature shifts of 4-5 C°. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

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.