Documenting spatial and temporal patterns of ocean acidification and understanding the way marine organisms build carbonate skeletons is critical to assessing their potential vulnerability to present and future stressors. The boron isotopic composition (δ11Bc) of many marine carbonates provides insight into the pH at the site of calcification within biocalcifiers and, by extension, the pH of ambient seawater when the carbonate formed. The modification of seawater carbonate chemistry at the site of calcification by marine calcifiers and the utility of different taxa as paleo-pH proxy archives remains an area of active research. Despite the significance of marine bivalves to ecosystem function, high-resolution paleoclimatic studies, and the shellfish industry, their biocalcification mechanisms, controls on internal pH, and potential for reconstructing records of past seawater pH remain unclear. To address these gaps, a 20.5-week flowthrough tank experiment was conducted in which four species of commercially important bivalves from the northwest Atlantic Ocean were grown in tanks with controlled pHT (pH 7.4 to 8.0) and temperature conditions (6 to 12 °C). A total of 106 shell samples from 99 individuals of adult and juvenile Arctica islandica (ocean quahog), juvenile Mercenaria mercenaria (northern quahog or hard clam), juvenile Mya arenaria (soft-shell clam) and juvenile Placopecten magellanicus (Atlantic sea scallop) were analyzed from this controlled experiment to assess the seawater pH, temperature, and growth rate controls on shell δ11Bc.These four bivalve species, grown under identical, controlled conditions, showed differential responses to the same seawater temperature and pH, likely due to differences in how they regulate the pH of their internal fluids. Juvenile P. magellanicus and juvenile M. mercenaria demonstrated significant relationships (R≥0.60; p-value <0.006) between tank pHT and δ11Bc, suggesting potential utility as proxies for past ambient seawater pH. Conversely, the δ11Bc of juvenile A. islandica and juvenile M. arenaria did not yield a strong relationship with seawater pHT but instead yielded significant relationships with shell growth rate (linear extension), with a positive relationship for M. arenaria and a negative relationship for juvenile A. islandica. The δ11B results from the few (n=9) adult A. islandica shells measured show the most variability across the range of pH and temperatures (range of 16‰) and no significant relationship was found with seawater pH or growth rate. Despite rigorous oxidative cleaning of samples, the data suggest that adult A. islandica shells contain boron-rich organic phases resistant to traditional cleaning techniques. This suggests that the next step in the development of boron-based pH proxies in A. islandica requires additional research into robust cleaning and sampling methods of periostracum and other organics. Despite the need for further investigations to constrain growth rate effects and cleaning techniques in A. islandica and M. arenaria, there is potential for developing paleo-pH proxies from P. magellanicus and M. mercenaria to better understand spatial and temporal patterns of past, present and future ocean acidification.
Thatcher D. L., Stewart J. A., LaVigne M., Williams B., Whitney N. M., Giss M., McMahon T., Jellison B., Guay K., Franklin H. & Wanamaker A. D., in press. Controls on boron isotope ratios in marine bivalve shells: insights from a controlled experiment across pH and temperature gradients. Geochimica et Cosmochimica Acta. Article.
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