Search

The coral Li/Mg temperature proxy is revisited through an in-depth trace element analysis of scleractinians collected live from tropical to polar environments. The dataset consists of Li/Ca, Mg/Ca, Sr/Ca and Li/Mg ratios from 64 coral specimens belonging to 8 different taxa, including both reef-building zooxanthellate and cold-water non-zooxanthellate species, from a wide range of water temperature (-1 to 29.5 degrees C), salinity (34.71 to 38.61), and depth (3 to 670m). Our results showed that the reliability of the Li/Mg temperature proxy is strongly limited by the organic matter associated with the coral skeleton, which is most evident within the green bands observed in tropical corals. Organic-rich bands can double the Mg content otherwise present in the skeleton, which may ultimately lead to a temperature overestimation exceeding 15 degrees C. We found that this bias can be overcome by the treatment of coral skeletons with a specific oxidizing cleaning protocol. We also detected the presence of calcite deposits within the aragonite skeleton of some Antarctic living coral specimens, which strongly affects the robustness of the Li/Mg proxy given its temperature sensitivity of similar to 1.5 degrees C/1% calcite. Therefore, to obtain reliable reconstructions a correction needs to be applied when organic matter and/or calcite contamination is present, which requires the scrupulous assessment of the integrity of the aragonite prior to geochemical analyses. Given that some species entrap more organic matter than others, and that some are more prone to calcite contamination, a taxon-related effect is apparent. Here we show that the tropical species Porites spp., Pseudodiploria strigosa and Orbicella annularis, and the cold-water species Madrepora oculata, Caryophyllia antarctica and Flabellum impensum, are all suitable candidates for reconstructing seawater temperatures. The integrated results across a wide temperature range, from extreme cold to tropical shallow waters, yield an overall precision for the Li/Mg-temperature proxy of +/- 1.0 degrees C, as quantified by the standard error of estimates. If calculated from the 95% prediction intervals, the uncertainty of the temperature estimates is +/- 0.9 degrees C at 1 degrees C, +/- 1.5 degrees C at 12 degrees C and +/- 2.6 degrees C at 25 degrees C. However, the uncertainty for the tropical corals (e.g. Porites) can be reduced to +/- 0.6 degrees C if a Li/Mg and Sr/Ca multi-regression approach is applied.

Funding was provided by an Antarctic Bursary awarded to J.A.S., ERC and NERC grants awarded to L.F.R. (278705, NE/S001743/1, NE/R005117/1) and L.F.R. and J.W.B.R. (NE/N003861/1), and a NERC Stable isotope Grant. The Li/Mg, Sr/Ca and oxygen isotopic (δ18O) compositions of many marine biogenic carbonates are sensitive to seawater temperature. Corals, as cosmopolitan marine taxa with carbonate skeletons that can be precisely dated, represent ideal hosts for these geochemical proxies. However, efforts to calibrate and refine temperature proxies in cold-water corals (

International audience; In contrast to Li/Ca and Mg/Ca, Li/Mg is strongly anticorrelated with temperature in aragonites precipitated by the benthic foraminifer Hoeglundina elegans and a wide range of scleractinian coral taxa. We propose a simple conceptual model of biomineralization that explains this pattern and is consistent with available abiotic aragonite partition coefficients. Under this model the organism actively modifies seawater within its calcification pool by raising its [Ca2+], using a pump that strongly discriminates against both Li+ and Mg2+. Rayleigh fractionation during calcification effectively reverses this process, removing Ca2+ while leaving most Li+ and Mg2+ behind in the calcifying fluid. The net effect of these two processes is that Li/Mg in the calcifying fluid remains very close to the seawater value, and temperature-dependent abiotic partition coefficients are expressed in the biogenic aragonite Li/Mg ratio. We further show that coral Sr/Ca is consistent with this model if the Ca2+ pump barely discriminates against Sr2+. In H. elegans the covariation of Sr/Ca and Mg/Ca requires either that the pump more strongly discriminates against Sr2+, or that cation incorporation is affected by aragonite precipitation rate via the mechanism of surface entrapment. In either case Li/Mg is minimally affected by such ‘vital effects’ which plague other elemental ratio paleotemperature proxies.

Caribbean sea surface temperatures (SSTs) have increased at a rate of 0.2°C per decade since 1971, a rate double that of the mean global change. Recent investigations of the coral Siderastrea siderea on the Belize Mesoamerican Barrier Reef System (MBRS) have demonstrated that warming over the last 30 years has had a detrimental impact on calcification. Instrumental temperature records in this region are sparse, making it necessary to reconstruct longer SST records indirectly through geochemical temperature proxies. Here we investigate the skeletal Sr/Ca and Li/Mg ratios of S. siderea from two distinct reef zones (forereef and backreef) of the MBRS. Our field calibrations of S. siderea show that Li/Mg and Sr/Ca ratios are well correlated with temperature, although both ratios are 3 times more sensitive to temperature change in the forereef than in the backreef. These differences suggest that a secondary parameter also influences these SST proxies, highlighting the importance for site- and species-specific SST calibrations. Application of these paleothermometers to downcore samples reveals highly uncertain reconstructed temperatures in backreef coral, but well-matched reconstructed temperatures in forereef coral, both between Sr/Ca-SSTs and Li/Mg-SSTs, and in comparison to the Hadley Centre Sea Ice and Sea Surface Temperature record. Reconstructions generated from a combined Sr/Ca and Li/Mg multiproxy calibration improve the precision of these SST reconstructions. This result confirms that there are circumstances in which both Li/Mg and Sr/Ca are reliable as stand-alone and combined proxies of sea surface temperature. However, the results also highlight that high-precision, site-specific calibrations remain critical for reconstructing accurate SSTs from coral-based elemental proxies.