Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa

Cusack, Maggie; Dauphin, Yannicke; Cuif, Jean‐Pierre; Salomé, Murielle; Freer, A. A.; Yin, Huabing

doi:10.1016/j.chemgeo.2008.05.007

Cited by 55 publications

(48 citation statements)

References 57 publications

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“…In sedimentary carbonates, sulfate contents have been used as an indicator of diagenetic change (Land and Hoops, 1973). Furthermore, sulfate is one of the most common anions present in biomaterials like corals (Tokuyama et al, 1972) and brachiopod shells (Cusack et al, 2008). The sulfate content of biogenic calcites can be higher than 20000 ppm.…”

Section: Introductionmentioning

confidence: 99%

The role of sulfate groups in controlling CaCO3 polymorphism

Fernández-Dı́az¹,

Fernández-González²,

Prieto³

2010

Geochimica et Cosmochimica Acta

132

100

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The nucleation and growth of CaCO 3 phases from aqueous solutions with SO 4 2À :CO 3 2À ratios from 0 to 1.62 and a pH of $10.9 were studied experimentally in batch reactors at 25°C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO 4 2À :CO 3 2À ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO 4 2À:CO 3 2À 6 1. For SO 4 2À :CO 3 2À > 1, vaterite persisted as a major phase for a longer time (>250 h for SO 4 2À :CO 3 2À = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.

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Section: Introductionmentioning

confidence: 99%

The role of sulfate groups in controlling CaCO3 polymorphism

Fernández-Dı́az¹,

Fernández-González²,

Prieto³

2010

Geochimica et Cosmochimica Acta

132

100

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“…On the other hand, higher sulphur concentrations may indicate a greater content of organic material in the calcareous lattice (Lorens & Bender, 1980;Vander Putten et al, 2000). In calcitic shells of brachiopods, Cusack et al (2008) found sulphur in a form of sulphate and sulphur-containing amino acids (proteins), whereas Gorzelak et al (2013) recorded that in crinoids calcite sulphur was associated with sulphated polysaccharides. In addition, Gorzelak et al (2013) observed that high Mg concentrations in the skeleton were correlated with the distribution of sulphates, and this pattern agrees with our results (Fig.…”

Section: Discussionmentioning

confidence: 99%

Trace element accumulation in the shell of the Arctic cirriped Balanus balanus

et al. 2018

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Barnacles are widespread and abundant inhabitants of rock surfaces in the intertidal zone, providing considerable contributions to the formation of carbonate sediments. The main goal of this study was to test two hypotheses: (1) the chemical composition of the Balanus balanus shell is mostly controlled biologically, and environmental factors have only minor influences, and (2) the chemical composition of B. balanus shells does not vary with size. To test these hypotheses, samples were collected in two fjords from two depths. This study revealed site-related differences in shell chemistry, although no variability in shell chemical compositions was detected between the depths and among the size categories. Barnacle shell plates had different accumulation patterns for different trace elements (Mg, S, Sr), with the operculum as the most distinctive shell plate. As those plates are precipitated under the same environmental conditions, the different accumulation patterns may indicate biological control of element uptake in cirripedes. We suggest that the specific chemical composition of the operculum may be related to the required mechanical properties of this shell part, and thus, it is likely that this organism regulates accumulation patterns within its shell, because such regulation increases its adaptive properties. Our results supported both presented hypotheses.

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“…Sulfur and magnesium K-edge X-ray absorption near edge structure (XANES) has also been applied to the characterization of the chemical environment (e.g., Pingitore et al, 1995;Morra et al, 1997;Finch and Allison, 2008;Foster et al, 2008;Cusack et al, 2008;Yoshimura et al, 2013a). XAS can be used in combination with X-ray fluorescence with a focused X-ray beam (i.e., micro-X-ray fluorescence; µ-XRF) to determine the speciation-specific spatial element distribution in biogenic carbonates and to generate time series of trace-element profiles in biogenic CaCO 3 with high lateral resolution.…”

Section: T Yoshimura Et Al: Fluctuations Of Sulfate S-bearing Aminmentioning

confidence: 99%

“…The chemical environment of sulfur has been studied in biogenic carbonates (Cuif et al, 2003Cusack et al, 2008;Dauphin et al, 2008), and the sulfate concentration in biogenic carbonates has been proposed as an indicator of skeletal organic materials (Lorens and Bender, 1980;Cuif et al, 2003;Takesue et al, 2008), but inorganic sulfate is also present in CaCO 3 (e.g., Kitano et al, 1975;Takano, 1985;Kralj et al, 2004;Kontrec et al, 2004). Because of the complexity of organic compounds associated with CaCO 3 biomineralization processes (e.g., Cusack and Freer, 2008), both organic and inorganic sulfur potentially contribute to the total sulfur concentration of shell carbonates.…”

Section: T Yoshimura Et Al: Fluctuations Of Sulfate S-bearing Aminmentioning

confidence: 99%

“…The characteristic variations of element profiles in biogenic calcium carbonates are widely used for identifying differences in biological and physicochemical processes associated with element partitioning (Henderson, 2002;Corrège, 2006;Cusack and Freer, 2008). Long-lived bivalves such as reef-dwelling giant clams are geologically important producers of biominerals that provide long-term records (up to ∼ 100 years) of environmental conditions in tropical and subtropical oceans (e.g., Watanabe et al, 2004;Aubert et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

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Fluctuations of sulfate, S-bearing amino acids and magnesium in a giant clam shell

et al. 2014

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Abstract. We used micro-X-ray fluorescence combined with X-ray photoabsorption spectroscopy to investigate speciation-specific sulfur profiles in the inner shell layer of a giant clam (Hippopus hippopus). The sulfate, S-bearing amino acids, and total sulfur profiles indicated that inorganic sulfate was the dominant component in the shell of this bivalve. Sulfur profiles in the inner shell layer showed clear annual fluctuations that varied by more than one order of magnitude, from < 50 to 1420 ppm, and sulfate and total sulfur maxima became higher with age, whereas no ontogenetic trend was noticeable in the profile of S-bearing amino acids. A change in the carbonate ion concentration in the calcifying fluid would suggest that an ontogenetic increase in the relative activity of sulfate ions to carbonate ions in the calcifying fluid affects sulfate concentrations in the shells. These results suggest that trace sulfur profiles in the shell of the giant clam may reflect both cyclic shell growth related to environmental factors such as insolation and temperature and ontogenetic changes of the calcifying fluid chemistry mediated by physiological processes. The observed S profile implies a clear change in calcifying fluid chemistry towards less alkaline condition with age. Magnesium fluctuations suggested that Mg was incorporated into the shells at high growth rates during warm seasons. The spectrum of Mg K-edge X-ray absorption near edge structure (XANES) and comparison of Mg and S-bearing amino acids profiles indicated that a pronounced effect of the organic fraction or disordered phases were observed in aragonitic shell of H. hippopus rather than regulated substitution into the aragonite crystal lattice.

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Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa

Cited by 55 publications

References 57 publications

The role of sulfate groups in controlling CaCO3 polymorphism

The role of sulfate groups in controlling CaCO3 polymorphism

Trace element accumulation in the shell of the Arctic cirriped Balanus balanus

Fluctuations of sulfate, S-bearing amino acids and magnesium in a giant clam shell

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