Kinetic and metabolic isotope effects in coral skeletal carbon isotopes: A re-evaluation using experimental coral bleaching as a case study

Coral skeletal δ13C can be a paleo-climate proxy for light levels (i.e., cloud cover and seasonality) and for photosynthesis to respiration (P/R) ratios. The usefulness of coral δ13C as a proxy depends on metabolic isotope effects (related to changes in photosynthesis) being the dominant influence on skeletal δ13C. However, it is also influenced by kinetic isotope effects (related to calcification rate) which can overpower metabolic isotope effects and thus compromise the use of coral skeletal δ13C as a proxy. Heikoop et al. (2000) proposed a simple data correction to remove kinetic isotope effects from coral skeletal δ13C, as well as an equation to calculate P/R ratios from coral isotopes. However, despite having been used by other researchers, the data correction has never been directly tested, and isotope-based P/R ratios have never been compared to P/R ratios measured using respirometry. Experimental coral bleaching represents a unique environmental scenario to test this because bleaching produces large physiological responses that influence both metabolic and kinetic isotope effects in corals. Here, we tested the δ13C correction and the P/R calculation using three Pacific and three Caribbean coral species from controlled temperature-induced bleaching experiments where both the stable isotopes and the physiological variables that cause isotopic fractionation (i.e., photosynthesis, respiration, and calcification) were simultaneously measured. We show for the first time that the data correction proposed by Heikoop et al. (2000) does not effectively remove kinetic effects in the coral species studied here, and did not improve the metabolic signal of bleached and non-bleached corals. In addition, isotope-based P/R ratios were in poor agreement with measured P/R ratios, even when the data correction was applied. This suggests that additional factors influence δ13C and δ18O, which are not accounted for by the data correction. We therefore recommend that the data correction not be routinely applied for paleo-climate reconstruction, and that P/R ratios should only be obtained by direct measurement by respirometry.