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  1. ABSTRACT

    Carbonate concretions collected from the Dominican Republic present a valuable opportunity to evaluate the internal isotopic variations within concretions that have never been exposed to deep burial or structural deformation. Here, three concretions from the Neogene (Late Miocene–Early Pliocene) Cibao Basin are investigated, utilizing a multi‐isotope (δ13C, δ18O, δ34SCASand ∆47values) high‐resolution approach, to constrain the microenvironmental conditions associated with multiple stages of concretion growth. Isotopic variability and potential disequilibrium effects, which can influence geological interpretations utilizing concretions, are also considered. The petrographic characteristics and geochemical profiles indicate internal differences relating to concretion growth mechanisms and environmental changes, driven by sea‐level fluctuations. The δ34S values of carbonate‐associated sulphate indicate a closed system environment; however, the overall values are influenced by sulphide oxidation within the sediments, resulting in a complex signal. The ∆47‐derived temperatures of the concretions range between 29 to 55°C, indicating significantly warmer temperatures than are measured from the host sediments, which average 24°C. This indicates that carbonate concretion ∆47values are in disequilibrium with their environments of formation, likely related to ion diffusion in the pore fluids or isotopic fractionation associated with microbial processes. Here geochemical variations within concretions are utilized to assess the environmental conditions and microbial interactions after sediment deposition. However, for future studies, caution should be taken when using concretions for making environmental assessments as the signals can be influenced by a multitude of processes, even prior to diagenetic alteration.

     
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  3. Rationale

    Information on the temperature of formation or alteration of carbonate minerals can be obtained by measuring the abundance of the isotopologues 47 and 48 (Δ47and Δ48values) of CO2released during acid dissolution. The combination of these two proxies can potentially provide a greater insight into the temperature of formation, particularly if the carbonate minerals form by non‐equilibrium processes.

    Methods

    We have precipitated calcium carbonates at seven temperatures between 5 and 65°C and measured their δ48values using a Thermo‐253 plus isotope ratio mass spectrometer. The values were transformed to Δ48values in the conventional manner and then converted to the carbon dioxide equilibrium scale.

    Results

    Using the Δ48values, we have established an empirical calibration between temperature and Δ48values:urn:x-wiley:09514198:media:rcm9147:rcm9147-math-0001

    Conclusions

    The calibration line produced allows the determination of the temperature of natural carbonates using the Δ48values and agrees with the measurements of the Δ47and Δ48values of some carbonates assumed to have formed under equilibrium conditions.

     
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