Apparently Seasonal Variations of the Seawater Sr/Ca Ratio Across the Florida Keys Reef Tract

Abstract

AbstractA 4‐year time‐series of surface seawater Sr/Ca ratios was assembled across a section of the Florida Keys Reef Tract, in order to uncover any variability that might explain previously reported anomalies in regional calibrations of the coral aragonite Sr/Ca paleotemperature proxy. Samples were collected semiannually on a grid of 54 sites, from September of 2016 until January of 2020. The 325‐km2 grid extended from the ocean shore to the forereef wall and from the east end of Long Key to the west end of Marathon. A novel ICP‐AES method was used to measure the Sr/Ca ratio, with ratio calibration and normalization against an in‐house seawater reference, yielding a long‐term precision of better than 0.2%. Significant variations (2%–3%) of the seawater Sr/Ca ratio were found. While it was relatively constant offshore, near the coast the ratio alternated seasonally between higher and lower values, generally resulting in seaward Sr/Ca gradients that were markedly negative in summer but reversed in winter. Inshore seawater Sr/Ca ratios ranged from a summer high of 8.83 mmol/mol to a winter low of 8.54 mmol/mol, the difference corresponding to a potential bias of ∼5.5°C in terms of the coral Sr/Ca paleotemperature proxy. This seasonal variation should diminish the slope of empirical Sr/Ca–SST calibration lines, as has indeed been observed in prior studies with local coral species. Open ocean samples obtained from the Atlantic, Indian, and Pacific enlarge the published Sr/Ca data set for surface seawater and show a much smaller variability of 8.646 ± 0.018 mmol/mol (0.2%).