δ11B, Sr, Mg and B in a modern Porites coral: the relationship between calcification site pH and skeletal chemistry

Sr/Ca, B/Ca, Mg/Ca and delta B-11 were determined at high spatial resolution across similar to 1 year of a modern Hawaiian Porites lobata coral by secondary ion mass spectrometry (SIMS). We observe significant variations in B/Ca, Mg/Ca, Sr/Ca and delta B-11 over short skeletal distances (nominally equivalent to periods of <20 days). This heterogeneity probably reflects variations in the composition of the extracellular calcifying fluid (ECF) from which the skeleton precipitates. Calcification site pH (total scale) was estimated from skeletal delta B-11 and ranged from 8.3 to 8.8 (+/- similar to 0.1) with a mean of similar to 8.6. Sr/Ca and B/Ca heterogeneity is not simply correlated with calcification site pH, as might be expected if Ca-ATPase activity increases the pH and decreases the Sr/Ca and B(OH)(4)(-)/CO32- ratios of the ECF. We produced a simple model of the ECF composition and the skeleton deposited from it, over a range of calcium transport and carbonate scenarios, which can account for these observed geochemical variations. The relationship between the pH and Sr/Ca of the ECF is dependent on the concentration of DIC at the calcification site. At higher DIC concentrations the ECF has a high capacity to buffer the [H+] changes induced by Ca-ATPase pumping. Conversely, at low DIC concentrations, this buffering capacity is reduced and ECF pH changes more rapidly in response to Ca-ATPase pumping. The absence of a simple correlation between ECF pH and skeletal Sr/Ca implies that calcification occurred under a range of DIC concentrations, reflecting variations in the respiration and photosynthesis of the coral and symbiotic zooxanthellate in the overlying coral tissues. Our observations have important implications for the use of coral skeletons as indicators of palaeo-occan pH. (C) 2010 Elsevier Ltd. All rights reserved.