Case David H.

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David H.
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  • Preprint
    Environmental and biological controls on Mg and Li in deep-sea scleractinian corals
    ( 2010-09-06) Case, David H. ; Robinson, Laura F. ; Auro, Maureen E. ; Gagnon, Alexander C.
    Deep-sea scleractinian corals precipitate aragonite skeletons that provide valuable archives of past ocean conditions. During calcification biological mediation causes variability in trace metal incorporation and isotopic ratios of the aragonite such that signals caused by environmental controls can be overwhelmed. This complicates the interpretation of geochemical proxies used for paleo-reconstructions. In this study we examine the environmental controls on the Mg/Li ratio of 34 individuals from seven genera of deep-sea scleractinian corals: Desmophyllum, Balanophyllia, Caryophyllia, Enallopsammia, Flabellum, Trochocyanthus, and Lophelia. In addition we examine the distributions of Mg and Li in Desmophyllum and Balanophyllia using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Both Mg/Ca and Li/Ca ratios increased by more than a factor of 2 in the center of calcification regions compared to the outer, fibrous regions of the coral skeleton. As a result, replicate ~10 mg subsamples of coral show less variability in the Mg/Li ratio than Mg/Ca. Microscale Mg and Li results are consistent with Rayleigh-type incorporation of trace metals with additional processes dominating composition within centers of calcification. Comparison of Mg/Li to seawater properties near the site of collection shows that the ratio is not controlled by either carbonate ion or salinity. It appears that temperature is the major control on the Mg/Li ratio. For all 34 samples the temperature correlation (R2=0.62) is significantly better than for Mg/Ca (R2=0.06). For corals of the family Caryophyllidae the R2 value increases to 0.82 with the exclusion of one sample that was observed to have an altered, chalky texture. Despite this excellent correlation the scatter in the data suggests that the Mg/Li ratio of deep-sea corals cannot be used to reconstruct temperature to better than approximately ±1.6°C without better temperature control and additional calibration points on modern coral samples.
  • Article
    Interlaboratory study for coral Sr/Ca and other element/Ca ratio measurements
    (John Wiley & Sons, 2013-09-23) Hathorne, Ed C. ; Gagnon, Alexander C. ; Felis, Thomas ; Adkins, Jess F. ; Asami, Ryuji ; Boer, Wim ; Caillon, Nicolas ; Case, David H. ; Cobb, Kim M. ; Douville, Eric ; deMenocal, Peter B. ; Eisenhauer, Anton ; Garbe-Schonberg, Dieter ; Geibert, Walter ; Goldstein, Steven L. ; Hughen, Konrad A. ; Inoue, Mayuri ; Kawahata, Hodaka ; Kolling, Martin ; Cornec, Florence L. ; Linsley, Braddock K. ; McGregor, Helen V. ; Montagna, Paolo ; Nurhati, Intan S. ; Quinn, Terrence M. ; Raddatz, Jacek ; Rebaubier, Helene ; Robinson, Laura F. ; Sadekov, Aleksey ; Sherrell, Robert M. ; Sinclair, Dan ; Tudhope, Alexander W. ; Wei, Gangjian ; Wong, Henri ; Wu, Henry C. ; You, Chen-Feng
    The Sr/Ca ratio of coral aragonite is used to reconstruct past sea surface temperature (SST). Twenty-one laboratories took part in an interlaboratory study of coral Sr/Ca measurements. Results show interlaboratory bias can be significant, and in the extreme case could result in a range in SST estimates of 7°C. However, most of the data fall within a narrower range and the Porites coral reference material JCp-1 is now characterized well enough to have a certified Sr/Ca value of 8.838 mmol/mol with an expanded uncertainty of 0.089 mmol/mol following International Association of Geoanalysts (IAG) guidelines. This uncertainty, at the 95% confidence level, equates to 1.5°C for SST estimates using Porites, so is approaching fitness for purpose. The comparable median within laboratory error is <0.5°C. This difference in uncertainties illustrates the interlaboratory bias component that should be reduced through the use of reference materials like the JCp-1. There are many potential sources contributing to biases in comparative methods but traces of Sr in Ca standards and uncertainties in reference solution composition can account for half of the combined uncertainty. Consensus values that fulfil the requirements to be certified values were also obtained for Mg/Ca in JCp-1 and for Sr/Ca and Mg/Ca ratios in the JCt-1 giant clam reference material. Reference values with variable fitness for purpose have also been obtained for Li/Ca, B/Ca, Ba/Ca, and U/Ca in both reference materials. In future, studies reporting coral element/Ca data should also report the average value obtained for a reference material such as the JCp-1.