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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 7 (2006): Q12004, doi:10.1029/2006GC001354.
    Description: We analyzed Sr/Ca and Mg/Ca ratios in the thecal wall of Lophelia pertusa, a cold-water coral, using SIMS ion microprobe techniques. The wall grows by simultaneous upward extension and outward thickening. Compositional variability displays similar trends along the upward and outward growth axes. Sr/Ca and Mg/Ca ratios oscillate systematically and inversely. The sensitivity of Lophelia Sr/Ca ratios to the annual temperature cycle (−0.18 mmol · mol−1/°C) is twice as strong as that exhibited by tropical reef corals, and four times as strong as the temperature dependence of Sr/Ca ratios of abiogenic aragonites precipitated experimentally from seawater. A comparison of the skeletal composition of Lophelia with results from precipitation calculations carried out using experimentally determined partition coefficients suggests that both temperature-dependent element partitioning and seasonal changes in the mass fraction of aragonite precipitated from the calcifying fluid influence the composition of Lophelia skeleton. Results from calculations that combine these effects reproduce both the exaggerated amplitude of the Sr/Ca and Mg/Ca oscillations and the inverse relationship between Sr/Ca and Mg/Ca ratios.
    Description: This study was supported in part by a WHOI Ocean Life Institute fellowship to ALC, by NSF grant OCE-0527350 to G.A.G. and A.L.C., and by the EU 6FP project HERMES, EC contract GOCE-CT-2005-511234 to T.L.
    Keywords: Coral ; Aragonite ; Vital effects ; Sr/Ca ; Mg/Ca ; Deep-sea
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 19 (2009): Q07005, doi:10.1029/2009GC002411.
    Description: We reared primary polyps (new recruits) of the common Atlantic golf ball coral Favia fragum for 8 days at 25°C in seawater with aragonite saturation states ranging from ambient (Ω = 3.71) to strongly undersaturated (Ω = 0.22). Aragonite was accreted by all corals, even those reared in strongly undersaturated seawater. However, significant delays, in both the initiation of calcification and subsequent growth of the primary corallite, occurred in corals reared in treatment tanks relative to those grown at ambient conditions. In addition, we observed progressive changes in the size, shape, orientation, and composition of the aragonite crystals used to build the skeleton. With increasing acidification, densely packed bundles of fine aragonite needles gave way to a disordered aggregate of highly faceted rhombs. The Sr/Ca ratios of the crystals, measured by SIMS ion microprobe, increased by 13%, and Mg/Ca ratios decreased by 45%. By comparing these variations in elemental ratios with results from Rayleigh fractionation calculations, we show that the observed changes in crystal morphology and composition are consistent with a 〉80% decrease in the amount of aragonite precipitated by the corals from each “batch” of calcifying fluid. This suggests that the saturation state of fluid within the isolated calcifying compartment, while maintained by the coral at levels well above that of the external seawater, decreased systematically and significantly as the saturation state of the external seawater decreased. The inability of the corals in acidified treatments to achieve the levels of calcifying fluid supersaturation that drive rapid crystal growth could reflect a limit in the amount of energy available for the proton pumping required for calcification. If so, then the future impact of ocean acidification on tropical coral ecosystems may depend on the ability of individuals or species to overcome this limitation and achieve the levels of calcifying fluid supersaturation required to ensure rapid growth.
    Description: This study was supported by NSF OCE-0648157 and NSF OCE-0823527 and the Bermuda Institute for Ocean Sciences.
    Keywords: Ocean acidification ; Coral ; Sr/Ca ; Calcification ; Mg/Ca ; Biomineralization
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 32 (2017): 146–160, doi:10.1002/2016PA002976.
    Description: Coral skeletons are valuable archives of past ocean conditions. However, interpretation of coral paleotemperature records is confounded by uncertainties associated with single-element ratio thermometers, including Sr/Ca. A new approach, Sr-U, uses U/Ca to constrain the influence of Rayleigh fractionation on Sr/Ca. Here we build on the initial Pacific Porites Sr-U calibration to include multiple Atlantic and Pacific coral genera from multiple coral reef locations spanning a temperature range of 23.15–30.12°C. Accounting for the wintertime growth cessation of one Bermuda coral, we show that Sr-U is strongly correlated with the average water temperature at each location (r2 = 0.91, P 〈 0.001, n = 19). We applied the multispecies spatial calibration between Sr-U and temperature to reconstruct a 96 year long temperature record at Mona Island, Puerto Rico, using a coral not included in the calibration. Average Sr-U derived temperature for the period 1900–1996 is within 0.12°C of the average instrumental temperature at this site and captures the twentieth century warming trend of 0.06°C per decade. Sr-U also captures the timing of multiyear variability but with higher amplitude than implied by the instrumental data. Mean Sr-U temperatures and patterns of multiyear variability were replicated in a second coral in the same grid box. Conversely, Sr/Ca records from the same two corals were inconsistent with each other and failed to capture absolute sea temperatures, timing of multiyear variability, or the twentieth century warming trend. Our results suggest that coral Sr-U paleothermometry is a promising new tool for reconstruction of past ocean temperatures.
    Description: NSF Graduate Research Fellowships Grant Numbers: NSF-OCE-1338320, NSF-OCE-1031971, NSF-OCE-0926986; WHOI Access to the Sea Grant Numbers: 27500056, 0734826; NSF HRD; UPR Central Administration to EAHD through the Center for Applied Tropical Ecology and Conservation of UPR
    Description: 2017-08-16
    Keywords: Coral ; Temperature ; Paleoceangraphy ; Paleothermometry ; Global warming ; Biomineralization
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 31 (2016): 626–638, doi:10.1002/2015PA002908.
    Description: Coral skeletons archive past climate variability with unrivaled temporal resolution. However, extraction of accurate temperature information from coral skeletons has been limited by “vital effects,” which confound, and sometimes override, the temperature dependence of geochemical proxies. We present a new approach to coral paleothermometry based on results of abiogenic precipitation experiments interpreted within a framework provided by a quantitative model of the coral biomineralization process. DeCarlo et al. (2015a) investigated temperature and carbonate chemistry controls on abiogenic partitioning of Sr/Ca and U/Ca between aragonite and seawater and modeled the sensitivity of skeletal composition to processes occurring at the site of calcification. The model predicts that temperature can be accurately reconstructed from coral skeleton by combining Sr/Ca and U/Ca ratios into a new proxy, which we refer to hereafter as the Sr-U thermometer. Here we test the model predictions with measured Sr/Ca and U/Ca ratios of 14 Porites sp. corals collected from the tropical Pacific Ocean and the Red Sea, with a subset also analyzed using the boron isotope (δ11B) pH proxy. Observed relationships among Sr/Ca, U/Ca, and δ11B agree with model predictions, indicating that the model accounts for the key features of the coral biomineralization process. By calibrating to instrumental temperature records, we show that Sr-U captures 93% of mean annual temperature variability (26–30°C) and has a standard deviation of prediction of 0.5°C, compared to 1°C using Sr/Ca alone. The Sr-U thermometer may offer significantly improved reliability for reconstructing past ocean temperatures from coral skeletons.
    Description: NSF Grant Numbers: OCE-1338320, OCE-1031971, OCE-1220529; NSF Graduate Research Fellowships
    Description: 2016-12-11
    Keywords: Coral ; Paleoclimate ; Sea surface temperature ; Geochemistry ; Biomineralization
    Repository Name: Woods Hole Open Access Server
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  • 5
    Publication Date: 2022-05-26
    Description: Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here for personal use, not for redistribution. The definitive version was published in Chemical Geology 437 (2016): 67-76, doi:10.1016/j.chemgeo.2016.05.007.
    Description: Measurements of B/Ca ratios in marine carbonates have been suggested to record seawater carbonate chemistry, however experimental calibration of such proxies based on inorganic partitioning remains limited. Here we conducted a series of synthetic aragonite precipitation experiments to evaluate the factors influencing the partitioning of B/Ca between aragonite and seawater. Our results indicate that the B/Ca ratio of synthetic aragonites depends primarily on the relative concentrations of borate and carbonate ions in the solution from which the aragonite precipitates; not on bicarbonate concentration as has been previously suggested. The influence of temperature was not significant over the range investigated (20 – 40°C), however, partitioning may be influenced by saturation state (and/or growth rate). Based on our experimental results, we suggest that aragonite B/Ca ratios can be utilized as a proxy of [CO32-]. Boron isotopic composition (δ11B) is an established pH proxy, thus B/Ca and δ11B together allow the full carbonate chemistry of the solution from which the aragonite precipitated to be calculated. To the extent that aragonite precipitation by marine organisms is affected by seawater chemistry, B/Ca may also prove useful in reconstructing seawater chemistry. A simplified boron purification protocol based on amberlite resin and the organic buffer TRIS is also described.
    Description: This work was supported by the Australian Research Council (ARC) Centre of Excellence for Coral Reef Studies. Research conducted at WHOI was supported by NSF grant OCE-1338320. M.H. was supported by an ARC Super Science Fellowship and an NSF International Postdoctoral Fellowship. T.D. was supported by a NSF Graduate Research Fellowship. M.M. was supported by a Western Australian Premiers Fellowship and an ARC Laureate Fellowship.
    Keywords: Boron ; Aragonite ; Coral ; Proxy ; Carbonate
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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