A 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‐km2grid 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%).
A new inductively coupled plasma atomic emission spectrometry (ICP‐AES) method is presented for rapid and routine analysis of Sr/Ca molar ratios in seawater, with a long‐term precision of < 0.2%. It is an adaptation of a method widely employed for the analysis of coral aragonite Sr/Ca ratios in marine paleothermometry studies, which are based on the assumption that the seawater Sr/Ca ratio is constant in space and time. While prior studies have shown variations of up to 1% with depth, smaller variations at the ocean surface are generally accounted for via empirical, species‐specific calibrations of coral Sr/Ca vs. temperature. We found Sr/Ca variations in some coastal waters to be even larger, with distinct periodicity, complicating this approach. Although the high precision necessary for measurements of seawater Sr/Ca has previously relied on advanced mass spectrometry, long analysis times, and expensive isotopic spikes, our method uses more accessible instrumentation and is both time‐ and cost‐saving. The intricate composition of seawater, relative to coral aragonite solutions, requires an intensity ratio calibration technique combined with rigorous normalization to a suitable seawater standard. Key aspects of our method are discussed, including the choice of wavelengths, instrument parameters, accuracy, precision, and matrix effects. Special attention is given to the need for a certified seawater Sr/Ca reference standard, which does not presently exist. Analytical validation is provided by concurrent sharp gradients in Sr/Ca and δ18O, coinciding with the Florida landfall of hurricane Irma, as recorded at near‐daily resolution in a continuous seawater sample collected with an osmotic pump.
more » « less- NSF-PAR ID:
- 10450892
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Limnology and Oceanography: Methods
- Volume:
- 19
- Issue:
- 6
- ISSN:
- 1541-5856
- Page Range / eLocation ID:
- p. 416-430
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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