Phosphate defects and apatite inclusions in coral skeletal aragonite revealed by solid-state NMR spectroscopy

Mason, Harris E.; Montagna, Paolo; Kubista, Laura; Taviani, Marco; McCulloch, Malcolm T.; Phillips, Brian L.

doi:10.1016/j.gca.2011.10.002

Cited by 25 publications

(12 citation statements)

References 51 publications

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“…Atomistic studies have shown that there is specific selectivity for the adsorption of HPO 4 2− ions, prevalent at the pH of the solutions of the present work (7.8), for the {10-10} face of aragonite because of stereochemical control [32]. Solid state NMR measurements in corals grown in the presence of orthophosphate have also shown the uptake of phosphate ions present in defects and in apatitic inclusions, which were not found in the present work probably because of the relatively short time of contact between aragonite with the orthophosphate ions [33]. The presence of orthophosphate adsorbed onto the growing aragonite crystals was identified.…”

Section: Influence Of the Presence Of Low Concentrations Of Orthophoscontrasting

confidence: 49%

Crystal growth of aragonite in the presence of phosphate

Tadier

Rokidi

Rey

et al. 2017

Journal of Crystal Growth

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The crystal growth of aragonite was investigated at pH 7.8, 37°C and constant solution supersaturation from aragonite-seeded supersaturated solutions. The effect of the presence of orthophosphate ions in the supersaturated solution on the kinetics of crystallization of aragonite was investigated over the range of orthophosphate concentrations of 0.25 µM-1 mM. In the presence of orthophosphate in the range of 0.25 µM-8 µM, the crystal growth rate of aragonite decreased with increasing phosphate concentration. At orthophosphate concentration levels exceeding 2 µM, induction times were measured and were found to increase with orthophosphate concentration. At orthophosphate concentration levels > 8 µM, the crystal growth of aragonite was inhibited, suggesting the blockage of the active growth sites by the adsorption of orthophosphate ions. Adsorption was confirmed by the investigation of orthophosphate uptake on aragonite, which was: i) found to depend on the equilibrium concentration of orthophosphate in aqueous solutions saturated with respect to aragonite; ii) not influenced by the ionic strength of the electrolyte up to 0.15 M NaCl, showing that electrostatic interactions between orthophosphate and CaCO 3 did not play a significant role in this concentration range. Adsorption data of orthophosphate on the aragonite crystals gave satisfactory fit to the Langmuir adsorption model and was confirmed by XPS analysis.

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Section: Influence Of the Presence Of Low Concentrations Of Orthophoscontrasting

confidence: 49%

Crystal growth of aragonite in the presence of phosphate

Tadier

Rokidi

Rey

et al. 2017

Journal of Crystal Growth

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“…Sinclair, 2005;Meibom et al, 2006;Mason et al, 2011), an alternative approach is to focus on proxies for which vital effects are minimal.…”

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confidence: 99%

Li/Mg systematics in scleractinian corals: Calibration of the thermometer

Montagna

McCulloch

Douville

et al. 2014

Geochimica et Cosmochimica Acta

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122

151

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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 (À0.049 * T) (r 2 = 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 ⇑ Corresponding author at: Istituto di Scienze Marine (ISMAR), Consiglio Nazionale delle Ricerche, Via Gobetti 101, 40129 Bologna, Italy. Tel.: +39 051 6398913.E-mail address: paolo.montagna@bo.ismar.cnr.it (P. Montagna). 1Published in which should be cited to refer to this work.http://doc.rero.ch 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 K dLi/Ca partition coefficient relative to K d Mg/Ca . Accordingly, Li/Mg ratios exhibit a highly coherent exponential correlation with temperature, thereby providing a more robust tool for reconstructing paleo-seawat...

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“…S11 caption, fitting methods in Text S4). The CP kinetics can be described using the classical biexponential equation (Text S4), in which intensity increases at short contact times with a time constant T PH and then decreases at longer times with a time constant T 1ρ,H . , T PH relates to the spatial proximity of P to H, and T 1ρ,H to the relaxation of the 1 H nuclei . For a system with two 1/2 nucleus (in this case 31 P and 1 H), the heteronuclear dipolar–dipolar interaction is inversely proportional to the internuclear distance and the longer internuclear distance is related to longer T PH and lower CP efficiency .…”

Section: Results and Discussionmentioning

confidence: 99%

“…31,32 T PH relates to the spatial proximity of P to H, and T 1ρ,H to the relaxation of the 1 H nuclei. 32 For a system with two 1/2 nucleus (in this case 31 P and 1 H), the heteronuclear dipolar−dipolar interaction is inversely proportional to the internuclear distance and the longer internuclear distance is related to longer T PH and lower CP efficiency. 33 The mobility of the proton sources (e.g., water molecules, surface P−OH and Al−OH groups) also affects the CP efficiency.…”

Section: Environmental Science and Technologymentioning

confidence: 99%

Polyphosphate Adsorption and Hydrolysis on Aluminum Oxides

Wan

Huang

Diaz

et al. 2019

Environ. Sci. Technol.

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The geochemical behaviors of phosphate-containing species at mineral−water interfaces are of fundamental importance for controlling phosphorus mobility, fate, and bioavailability. This study investigates the sorption and hydrolysis of polyphosphate (a group of important long-chained phosphate molecules) on aluminum oxides in the presence of divalent metal cations (Ca 2+ , Cu 2+ , Mg 2+ , Mn 2+ , and Zn 2+ ) at pH 6−8. γ-Al 2 O 3 with three particle sizes (5, 35, and 70 nm) was used as an analogue of natural aluminum oxides to investigate the particle size effect. All metal cations enhanced polyphosphate hydrolysis at different levels, with Ca 2+ showing the most significant enhancement, and the difference in the enhancement might be due to the intrinsic affinity of metal cations to polyphosphate. In the presence of Ca 2+ , the hydrolysis rate decreased with increasing mineral particle size. Solid-state 31 P nuclear magnetic resonance spectroscopy (NMR) revealed the main surface P species to be amorphous calcium phosphate precipitates, phosphate groups in polyphosphate that formed direct bonds with the mineral surface as inner-sphere complexes, and phosphate groups in polyphosphate that were not directly bonded to the mineral surfaces. Our results reveal the critical roles of mineral−water interface processes and divalent metal cations on controlling polyphosphate speciation and transformation and phosphorus cycling.

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Phosphate defects and apatite inclusions in coral skeletal aragonite revealed by solid-state NMR spectroscopy

Cited by 25 publications

References 51 publications

Crystal growth of aragonite in the presence of phosphate

Crystal growth of aragonite in the presence of phosphate

Li/Mg systematics in scleractinian corals: Calibration of the thermometer

Polyphosphate Adsorption and Hydrolysis on Aluminum Oxides

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