Exploring foraminiferal Sr/Ca as a new carbonate system proxy

In present day paleoclimate research one of the most pressing challenges is the reconstruction of atmospheric CO2 concentrations. A variety of proxies for several components of the marine inorganic carbon system have been developed in this context (e.g. B isotopes, B/Ca, U/Ca) to allow reconstruction of past seawater pH, HCO3− and CO32− and thereby facilitate estimates of past atmospheric pCO2. Based on culture experiments using the benthic foraminifera Ammonia sp. we describe a positive correlation between Sr/Ca and the carbonate system, namely DIC/bicarbonate ion concentration. Foraminiferal Sr/Ca ratios provide potentially additional constraints on the carbonate system proxy, because the analysis of foraminiferal carbonate Sr/Ca is straightforward and not easily contaminated. Applying our calibration to a published dataset of paleo-Sr/Ca suggests the validity of Sr/Ca as a carbonate system proxy. Furthermore, we explore how our data can be used to advance conceptual understanding of the foraminiferal biomineralization mechanism

Shelled pteropods in peril: Assessing vulnerability in a high CO2 ocean

The impact of anthropogenic ocean acidification (OA) on marine ecosystems is a vital concern facing marine scientists and managers of ocean resources. Euthecosomatous pteropods (holoplanktonic gastropods) represent an excellent sentinel for indicating exposure to anthropogenic OA because of the sensitivity of their aragonite shells to the OA conditions less favorable for calcification. However, an integration of observations, experiments and modelling efforts is needed to make accurate predictions of how these organisms will respond to future changes to their environment. Our understanding of the underlying organismal biology and life history is far from complete and must be improved if we are to comprehend fully the responses of these organisms to the multitude of stressors in their environment beyond OA. This review considers the present state of research and understanding of euthecosomatous pteropod biology and ecology of these organisms and considers promising new laboratory methods, advances in instrumentation (such as molecular, trace elements, stable isotopes, palaeobiology alongside autonomous sampling platforms, CT scanning and high-quality video recording) and novel field-based approaches (i.e. studies of upwelling and CO2 vent regions) that may allow us to improve our predictive capacity of their vulnerability and/or resilience. In addition to playing a critical ecological and biogeochemical role, pteropods can offer a significant value as an early-indicator of anthropogenic OA. This role as a sentinel species should be developed further to consolidate their potential use within marine environmental management policy making

Saturation state of the surface waters of the Greater Caribbean Region (including the Gulf of Mexico) with respect to aragonite

The carbonate chemistry of seawater is changing due to the uptake of increasing atmospheric C02 and is of major scientific concem. The decrease in the aragonite saturation state (Qaragonite) is of special interest, because the ability of some marine organisms (e.g. corals) to form calcium carbonate via biomineralization is suspected to be depending on aragonite saturation in the surrounding seawater. The objective of this thesis was to investigate the aragonite saturation state of two marginal seas, the Gulf of Mexico and the Caribbean Sea. Presented are the results of five cruises that were carried out in the Greater Caribbean Region (including the Gulf of Mexico) in 2008. At least two carbonaterelated analytical parameters were determined on each cruise, which made possible the calculation of the other parameters of the carbonate system, including the aragonite saturation state. All surface waters were supersaturated with respect to Ωaragonite with an average aragonite saturation state of 4.16 (± 0.3) in the Gulf of Mexico and 4.18 (± 0.09) in the Caribbean Sea

A new model for biomineralization and trace-element signatures of Foraminifera tests

The Mg/ Ca ratio of Foraminifera calcium carbonate tests is used as proxy for seawater temperature and widely applied to reconstruct global paleo-climatic changes. However, the mechanisms involved in the carbonate biomineralization process are poorly understood. The current paradigm holds that calcium ions for the test are supplied primarily by endocytosis of seawater. Here, we combine confocal-laser scanning-microscopy observations of a membrane-impermeable fluorescent marker in the extant benthic species Ammonia aomoriensis with dynamic 44Calabeling and NanoSIMS isotopic imaging of its test. We infer that Ca for the test in A. aomoriensis is supplied primarily via trans-membrane transport, but that a small component of passively transported (e.g., by endocytosis) seawater to the site of calcification plays a key role in defining the trace-element composition of the test. Our model accounts for the full range of Mg/ Ca and Sr / Ca observed for benthic Foraminifera tests and predicts the effect of changing seawater Mg/ Ca ratio. This places foram-based paleoclimatology into a strong conceptual framework

pH and calcium change in the microenvironment of a benthic foraminifer (Ammonia sp.) and its size during experiments

Calcareous foraminifera are well known for their CaCO3 shells. Yet, CaCO3 precipitation acidifies the calcifying fluid. Calcification without pH regulation would therefore rapidly create a negative feedback for CaCO3 precipitation. In unicellular organisms, like foraminifera, an effective mechanism to counteract this acidification could be the externalization of H+ from the site of calcification. In this study we show that a benthic symbiont-free foraminifer Ammonia sp. actively decreases pH within its extracellular microenvironment only while precipitating calcite. During chamber formation events the strongest pH decreases occurred in the vicinity of a newly forming chamber (range of gradient about 100 µm) with a recorded minimum of 6.31 (< 10 µm from the shell) and a maximum duration of 7 h. The acidification was actively regulated by the foraminifera and correlated with shell diameters, indicating that the amount of protons removed during calcification is directly related to the volume of calcite precipitated. The here presented findings imply that H+ expulsion as a result of calcification may be a wider strategy for maintaining pH homeostasis in unicellular calcifying organisms