Biogenic Calcium Carbonate Solubilities and Reaction Rates by Lab and Field Saturometry

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The ocean actively exchanges carbon dioxide with the atmosphere and is currently absorbing about a third of the carbon dioxide humans emit through fossil fuel burning. Because carbon dioxide is acidic, ocean pH drops as it takes up carbon dioxide, a process known as "ocean acidification". Ocean acidification negatively affects the health of marine ecosystems by making it harder for organisms to grow their calcium carbonate shells. Yet, the dissolution of these calcium carbonate shells in the deep ocean helps neutralize the carbon dioxide we emit as humans. The extent to which this process takes place is a function of the solubility of marine calcium carbonate. This project will evaluate the temperature and pressure effects on the stability of biologically produced calcium carbonate minerals. The results from this study will allow us to better predict where, how much, and how fast, carbon dioxide will be neutralized and stored in the world's ocean. We will also investigate the ways in which small changes in the chemical composition of calcium carbonate shells - such as the incorporation of magnesium - influence their stability. This project will also conduct micro-computed tomography scans of microorganisms' shells to better visualize them in 3-dimensional detail. We will print these 3-dimensional scans for use as educational tools in the classroom and in the Woods Hole Visitor Center. In addition, professional development workshops for high school teacher on ocean acidification and the importance of marine calcification will be held yearly.The ocean is the ultimate repository for most of anthropogenic carbon dioxide emissions, which in turn is making ocean chemistry less favorable for biogenic carbonate precipitation through the process of ocean acidification. Ocean acidification decreases seawater pH but dissolution of primarily biogenic carbonate minerals has the capacity to buffer this acidification and over thousands of years push whole-ocean pH and atmospheric carbon dioxide to their preindustrial values. Unfortunately, the relationship between seawater chemistry, carbonate mineral solubility, and the kinetics that govern carbonate dissolution and precipitation are not fully understood. Currently, it is clear that relationships based solely on inorganic calcite are insufficient to describe the cycling of biogenic calcites in the ocean. This project will conduct a systematic determination of the solubilities and reaction kinetics of the three most common biogenic carbonates (coccoliths, foraminifera, and pteropods), both in the laboratory and in the field, using spectrophotometric pH saturometry. The saturometer incubates calcium carbonate with seawater in a closed system. During each run, the change in pH within the saturometer traces the progression of calcium carbonate dissolution/precipitation as the system approaches equilibrium. The saturometer therefore has the potential to link mechanistic interpretations of mineral dissolution/precipitation kinetics to measurements of solubility in a single experiment. The spectrophotometric pH method uses well-calibrated indicator dyes, allows solubility and data to be tied to modern pH calibrations and reference materials, and can be used in the laboratory or deployed on a hydrowire at sea. Field experiments will be conducted at multiple depths, elucidating in-situ controls on solubility and kinetics, as well as the sensitivity of biogenic calcite solubility to temperature and pressure. Experiments will be conducted from both sides of equilibrium, allowing for robust determinations of inorganic and biogenic solubilities.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.