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  • 1
    Publication Date: 2019-01-31
    Description: Abstract High-latitude cold-water coral reefs are particularly vulnerable to climate change due to enhanced CO2 uptake in these regions. To evaluate their physiological functioning and potential application as pH archives, we retrieved both recent and fossil samples of Lophelia pertusa along the Norwegian margin from Oslofjord (59°N), over to Trondheimsfjord, Sula and Lopphavet (70.6°N). Boron isotope analyses (δ11B) were undertaken using solution-based and laser ablation multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS; LA-ICP-MS), and secondary ion mass spectrometry (SIMS). Epi-fluorescence microscopy was employed to provide a rapid pre-screening routine for structure-specific subsampling in the coral skeleton. This integrated approach enabled us to assess heterogeneities within single specimens, as well as to investigate the role of local environmental influences including recent and past variations. All three mass spectrometry methods show substantial differences in the δ11B of the theca wall (TW) and the centres of calcification (COC's). Micro-bulk subsamples milled from the theca wall of modern specimens originating from different habitats but with comparable seawater pH (8–8.16) gave consistent δ11B values averaging 26.7 (±0.2‰, 2σ, n = 4), while COC subsamples systematically deviated towards lower B/Ca (by ~40%) and depleted δ11B values (minimum 22.7 ± 0.3‰, 2σ), implying a difference of at least 4‰ between TW and COC. SIMS and LA-ICP-MS measurements identified much larger internal heterogeneities with maximum variation of ~10‰ between the distinct skeletal structures; minimal SIMS δ11B values of ~17.3 ± 1.2‰ (2σ) were associated with the pure COC material. Our findings may be interpreted in terms of the occurrence of two main, but likely different, biomineralisation mechanisms in L. pertusa, with the COC's generally exhibiting minimal pH up-regulation, potentially supporting the use of bicarbonate in the early stages of biomineralisation. Furthermore, we highlight the potential utility of L. pertusa for palaeo-proxy studies if targeting the compositionally homogenous TW zones devoid of COC admixtures, which appear to provide highly reproducible measurements.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 2
    Publication Date: 2017-06-29
    Description: The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high δ11B compositions ranging from 23.2‰ to 28.7‰. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pHcf), being elevated by ∼0.6–0.8 units (ΔpH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower δ11B composition of 15.5‰, with a corresponding lower ΔpH value of ∼0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pHT and shows an approximate linear correlation with ΔpHDesmo = 6.43 − 0.71pHT (r2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where ΔpHDesmo = 1.09 − 0.14Ωarag (r2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pHcf, and consequently Ωcf, of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+-ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (δ11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium. We also show that the relatively strong up-regulation of pH and consequent elevation of the internal carbonate saturation state (Ωcf ∼8.5 to ∼13) at the site of calcification by cold-water corals, facilitates calcification at or in some cases below the aragonite saturation horizon, providing a greater ability to adapt to the already low and now decreasing carbonate ion concentrations. Although providing greater resilience to the effects of ocean acidification and enhancing rates of calcification with increasing temperature, the process of internal pHcf up-regulation has an associated energetic cost, and therefore growth-rate cost, of ∼10% per 0.1 pH unit decrease in seawater pHT. Furthermore, as the aragonite saturation horizon shoals with rapidly increasing pCO2 and Ωarag < 1, increased dissolution of the exposed skeleton will ultimately limit their survival in the deep oceans.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 3
    Publication Date: 2015-09-22
    Description: We show that the Li/Mg systematics of a large suite of aragonitic coral skeletons, representing a wide range of species inhabiting disparate environments, provides a robust proxy for ambient seawater temperature. The corals encompass both zooxanthellate and azooxanthellate species (Acropora sp., Porites sp., Cladocora caespitosa, Lophelia pertusa, Madrepora oculata and Flabellum impensum) collected from shallow, intermediate, and deep-water habitats, as well as specimens cultured in tanks under temperature-controlled conditions. The Li/Mg ratios observed in corals from these diverse tropical, temperate, and deep-water environments are shown to be highly correlated with temperature, giving an exponential temperature relationship of: Li/Mg (mmol/mol) = 5.41 exp (−0.049 * T) (r2 = 0.975, n = 49). Based on the standard error of the Li/Mg versus temperature correlation, we obtain a typical precision of ±0.9 °C for the wide range of species analysed, similar or better than that of other less robust coral temperature proxies such as Sr/Ca ratios. The robustness and species independent character of the Li/Mg temperature proxy is shown to be the result of the normalization of Li to Mg, effectively eliminating the precipitation efficiency component such that temperature remains as the main controller of coral Li/Mg compositions. This is inferred from analysis of corresponding Li/Ca and Mg/Ca ratios with both ratios showing strong microstructure-related co-variations between the fibrous aragonite and centres of calcification, a characteristic that we attribute to varying physiological controls on growth rate. Furthermore, Li/Ca ratios show an offset between more rapidly growing zooxanthellate and azooxanthellate corals, and hence only an approximately inverse relationship to seawater temperature. Mg/Ca ratios show very strong physiological controls on growth rate but no significant dependence with temperature, except possibly for Acropora sp. and Porites sp. A strong positive correlation is nevertheless found between Li/Ca and Mg/Ca ratios at similar temperatures, indicating that both Li and Mg are subject to control by similar growth mechanisms, specifically the mass fraction of aragonite precipitated during calcification, which is shown to be consistent with a Rayleigh-based elemental fractionation model. The highly coherent array defined by Li/Mg versus temperature is thus largely independent of coral calcification mechanisms, with the strong temperature dependence reflecting the greater sensitivity of the KdLi/Ca partition coefficient relative to KdMg/Ca. Accordingly, Li/Mg ratios exhibit a highly coherent exponential correlation with temperature, thereby providing a more robust tool for reconstructing paleo-seawater temperatures.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 4
    Publication Date: 2019-02-01
    Description: High-latitude cold-water coral (CWC) reefs are particularly susceptible due to enhanced CO2 uptake in these regions. Using precisely dated (U/Th) CWCs (Lophelia pertusa) retrieved during research cruise POS 391 (Lopphavet 70.6°N, Oslofjord 59°N) we applied boron isotopes (δ11B), Ba/Ca, Li/Mg and U/Ca ratios to reconstruct the environmental boundary conditions of CWC reef growth. The sedimentary record from these CWC reefs reveals a lack of corals between ∼ 6.4 and 4.8 ka. The question remains if this phenomenon is related to changes in the carbonate system or other causes. The initial postglacial setting had elevated Ba/Ca ratios, indicative of meltwater fluxes showing a decreasing trend towards cessation at 6.4 ka with a oscillation pattern similar to continental glacier fluctuations. Downcore U/Ca ratios reveal an increasing trend, which is outside the range of modern U/Ca variability in L. pertusa, suggesting changes of seawater pH near 6.4 ka. The reconstructed BWT at Lopphavet reveals a striking similarity to Barent Sea-Surface and sub-Sea-Surface-Temperature records. We infer that meltwater pulses weakened the North Atlantic Current system resulting in southward advances of cold and CO2 rich Arctic waters. A corresponding shift in the δ11B record from ∼ 25.0‰ to ∼ 27.0 ‰ probably implies enhanced pH-up regulation of the CWCs due to the higher pCO2 concentrations of ambient seawater, which hastened Mid-Holocene CWC reef decline on the Norwegian Margin.
    Type: Article , PeerReviewed
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  • 5
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    PANGAEA
    In:  Supplement to: McCulloch, Malcolm T; Trotter, Julie; Montagna, Paolo; Falter, Jim; Dunbar, Robert G; Freiwald, André; Försterra, Günter; López Correa, Matthias; Maier, Cornelia; Rüggeberg, Andres; Taviani, Marco (2012): Resilience of cold-water scleractinian corals to ocean acidification: Boron isotopic systematics of pH and saturation state up-regulation. Geochimica et Cosmochimica Acta, 87, 21-34, https://doi.org/10.1016/j.gca.2012.03.027
    Publication Date: 2019-02-13
    Description: The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2 per mil to 28.7 per mil. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pH(cf)), being elevated by ~0.6-0.8 units (Delta pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5 per mil, with a corresponding lower Delta pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pH(T) and shows an approximate linear correlation with Delta pH(Desmo) = 6.43 - 0.71 pH(T) (r**2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where Delta pH(Desmo) = 1.09 - 0.14 Omega(arag) (r**2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pH(cf), and consequently Omega(cf), of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+ -ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium.
    Type: Dataset
    Format: application/zip, 2 datasets
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  • 6
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    PANGAEA
    In:  Supplement to: Allan, Tony; Robertson, Alastair H F; Sharp, Timothy R; Trotter, Julie (2001): Data report: Whole-rock 87Sr/86Sr composition and apparent strontium isotopic age of limestones from Site 1118, Woodlark rift basin, southwest Pacific (Ocean Drilling Program Leg 180). In: Huchon, P; Taylor, B; Klaus, A (eds.) Proceedings of the Ocean Drilling Program, Scientific Results, College Station, TX (Ocean Drilling Program), 180, 1-5, https://doi.org/10.2973/odp.proc.sr.180.158.2001
    Publication Date: 2019-02-09
    Description: Limestone from Unit VI (857.1-859.15 meters below seafloor) collected at Site 1118 contains a planktonic foraminiferal fauna indicating a latest Miocene to early Pliocene age. Globorotalia tumida is recorded in Sample 180-1118A-68R-4, 46-48 cm, indicating an early Pliocene (N18) age at this level (J. Resig, pers. comm., 2000). Based on their known range in the western Papuan Basin, the presence of (rare) Lepidocyclina and common Amphistegina in some samples suggests that abundant shallow-water bioclastic debris present in these limestones may be reworked from older, possibly middle or early late Miocene sediments. Four samples were selected for whole-rock strontium isotopic analysis to further investigate this possibility. A petrographic examination of samples analyzed was also conducted.
    Type: Dataset
    Format: text/tab-separated-values, 16 data points
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  • 7
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    PANGAEA
    In:  Supplement to: Holcomb, Michael; Venn, Alexander A; Tambutté, Eric; Tambutté, Sylvie; Allemand, D; Trotter, Julie; McCulloch, Malcolm T (2014): Coral calcifying fluid pH dictates response to ocean acidification. Scientific Reports, 4, https://doi.org/10.1038/srep05207
    Publication Date: 2019-02-09
    Description: Ocean acidification driven by rising levels of CO2 impairs calcification, threatening coral reef growth. Predicting how corals respond to CO2 requires a better understanding of how calcification is controlled. Here we show how spatial variations in the pH of the internal calcifying fluid (pHcf) in coral (Stylophora pistillata) colonies correlates with differential sensitivity of calcification to acidification. Coral apexes had the highest pHcf and experienced the smallest changes in pHcf in response to acidification. Lateral growth was associated with lower pHcf and greater changes with acidification. Calcification showed a pattern similar to pHcf, with lateral growth being more strongly affected by acidification than apical. Regulation of pHcf is therefore spatially variable within a coral and critical to determining the sensitivity of calcification to ocean acidification.
    Type: Dataset
    Format: text/tab-separated-values, 2090 data points
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  • 8
  • 9
    Publication Date: 2019-02-09
    Type: Dataset
    Format: text/tab-separated-values, 220 data points
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  • 10
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    PANGAEA
    In:  Supplement to: Trotter, Julie; Montagna, Paolo; McCulloch, Malcolm T; Silenzi, Sergio; Reynaud, Stéphanie; Mortimer, Graham; Martin, Sophie; Ferrier-Pagès, Christine; Gattuso, Jean-Pierre; Rodolfo-Metalpa, Riccardo (2011): Quantifying the pH 'vital effect' in the temperate zooxanthellate coral Cladocora caespitosa: Validation of the boron seawater pH proxy. Earth and Planetary Science Letters, 303, 163-173, https://doi.org/10.1016/j.epsl.2011.01.030
    Publication Date: 2019-02-11
    Description: Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 〉 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.
    Type: Dataset
    Format: text/tab-separated-values, 29568 data points
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