Influence of Mg²⁺, Fe²⁺ and Zn²⁺ Cations on ¹³C-¹⁸O Bonds in Precipitated Aragonite, Calcite and Dolomite: An ab Initio Study

Jie Yuan

Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Science, Beijing, China.

DOI: 10.4236/ojg.2015.55023                

Abstract

The influence of metal cations on ¹³C-¹⁸O bonds in carbonates is still under debate. This paper used ab initio method to investigate this kind of influence of Mg²⁺, Fe²⁺ and Zn²⁺ cations on ¹³C-¹⁸O bonds in precipitated aragonite, calcite and dolomite. The polynomials of Δ₄₇ and reduced partition function ratios (RPFRs) for ^13/12C, ^14/12C and ^18/16O of these minerals were given within temperatures ranging from 260 to 1500 K. We found that these cations significantly decreased the Δ₄₇ values at the level of 10^-3 - 10^-2 per mil, comparing with pure crystals; and that if the Δ₄₇ values were used to reconstruct the temperatures Ts, the deviation of T was about 7.2°C for, for instance, zinc-enriched aragonite, as discussed in our paper. It was suggested that due to such influence, researchers would better use a proper thermometer according to the main impurity metal cations in carbonates. We also found that according to the probability theory, the theoretical value of the influence of phosphoric acid on Δ₄₇ of CO₂ degassed from different carbonates was zero.

Keywords

Metal Cation, ¹³C-¹⁸O Bond, Δ47, Phosphoric Acid, ab Initio Calculation

Conflicts of Interest

The authors declare no conflicts of interest.

References

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[46]	Watson, E.B. (1996) Surface Enrichment and Trace-Element Uptake during Crystal Growth. Geochimica et Cosmochimica Acta, 60, 5013-5020. http://dx.doi.org/10.1016/S0016-7037(96)00299-2
[47]	Watson, E.B. (2004) A Conceptual Model for Near-Surface Kinetic Controls on the Trace-Element and Stable Isotope Composition of Abiogenic Calcite Crystals. Geochimica et Cosmochimica Acta, 68, 1473-1488. http://dx.doi.org/10.1016/j.gca.2003.10.003
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[49]	DePaolo, D.J. (2011) Surface Kinetic Model for Isotopic and Trace Element Fractionation during Precipitation of Calcite from Aqueous Solutions. Geochimica et Cosmochimica Acta, 75, 1039-1056. http://dx.doi.org/10.1016/j.gca.2010.11.020
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[53]	Petersson, G.A. and Allaham, M.A. (1991) A Complete Basis Set Model Chemistry. II. Open-Shell Systems and the Total Energies of the First-Row Atoms. Journal of Chemical Physics, 94, 6081-6090. http://dx.doi.org/10.1063/1.460447
[54]	Petersson, G.A., Bennett, A., Tensfeldt, T.G., Allaham, M.A., Shirley, W.A. and Mantzaris, J. (1988) A Complete Basis Set Model Chemistry. I. The Total Energies of Closed-Shell Atoms and Hydrides of the First-Row Elements. Journal of Chemical Physics, 89, 2193-2218. http://dx.doi.org/10.1063/1.455064
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[56]	Bigeleisen, J. and Mayer, M.G. (1947) Calculation of Equilibrium Constants for Isotopic Exchange Reactions. Journal of Chemical Physics, 15, 261-267. http://dx.doi.org/10.1063/1.1746492
[57]	Jarosch, D. and Heger, G. (1986) Neutron Diffraction Refinement of the Crystal-Structure of Aragonite. Tschermaks mineralogische und petrographische Mitteilungen, 35, 127-131. http://dx.doi.org/10.1007/BF01140844
[58]	Maslen, E.N., Streltsov, V.A. and Streltsova, N.R. (1993) X-Ray Study of the Electron-Density in Calcite, CaCo3. Acta Crystallographica Section B-Structural Science, 49, 636-641. http://dx.doi.org/10.1107/S0108768193002575
[59]	Steinfink, H. and Sans, F.J. (1959) Refinement of the Crystal Structure of Dolomite. American Mineralogist, 44, 679-682.
[60]	Yuan, J. (2014) Reduced Partition Function Ratio in the Frequency Complex Plane: A Mathematical Approach. Open Journal of Geology, 4, 654-664. http://dx.doi.org/10.4236/ojg.2014.412049
[61]	Yuan, J. and Liu, Y. (2012) Quantum-Mechanical Equilibrium Isotopic Fractionation Correction to Radiocarbon Dating: A Theory Study. Journal of Radioanalytical and Nuclear Chemistry, 292, 335-338. http://dx.doi.org/10.1007/s10967-011-1563-3
[62]	Grauel, A.L., Schmid, T.W., Hu, B., Bergami, C., Capotondi, L., Zhou, L.P., et al. (2013) Calibration and Application of the “Clumped Isotope” Thermometer to Foraminifera for High-Resolution Climate Reconstructions. Geochimica et Cosmochimica Acta, 108, 125-140. http://dx.doi.org/10.1016/j.gca.2012.12.049
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[64]	Swart, P.K., Burns, S.J. and Leder, J.J. (1991) Fractionation of the Stable Isotopes of Oxygen and Carbon in Carbon-Dioxide during the Reaction of Calcite with Phosphoric-Acid as a Function of Temperature and Technique. Chemical Geology, 86, 89-96.
[65]	Cao, X. and Liu, Y. (2012) Theoretical Estimation of the Equilibrium Distribution of Clumped Isotopes in Nature. Geochimica et Cosmochimica Acta, 77, 292-303. http://dx.doi.org/10.1016/j.gca.2011.11.021
[66]	Wang, J., Qian, Z., Qian, W., Zhuang, Y., He, Y. and Pan, C. (1999) Probability Statistics (Engineering Mathematics). Tongji University, Shanghai, 240-247. (In Chinese)
[67]	Cui, L.L. and Wang, X. (2014) Determination of Clumped Isotopes in Carbonate Using Isotope Ratio Mass Spectrometer: Effects of Extraction Potential and Long-Term Stability. International Journal of Mass Spectrometry, 372, 46-50. http://dx.doi.org/10.1016/j.ijms.2014.08.006
[68]	Levine, I.N. (1995) Physical Chemistry. 4th Edition, McGraw-Hill, Inc., New York.