Abstract
Magnesian calcites are important components of sediments and biominerals. Although Raman spectra of calcite, dolomite, and magnesite are well known, those of magnesian calcites deserve further investigation. Nineteen syntheses of magnesian calcites covering the range 0–50 mol% MgCO3 have been carried out at high pressure and temperature (1–1.5 GPa, 1000–1100 ℃). The crystalline run products have been characterized by μ-Raman spectroscopy.
For all lattice and internal modes (L, T, ν1, ν4, 2ν2) but ν3, wavenumbers align closer to the calcite– dolomite line than the calcite–magnesite line. The compositional dependence is strong and regression curves with high correlation coefficients have been determined. Full-width at half maximum (FWHM) plot along parabolas that depart from the calcite–dolomite or calcite–magnesite lines. The limited data dispersion of both shifts and FWHM allow using Raman spectral properties of magnesian calcites to determine the Mg content of abiotic calcites.
A comparison with Raman data from the literature obtained on synthetic magnesian amorphous calcium carbonate (Mg ACC) shows that the wavenumber position of the ACC ν1 mode is systematically shifted toward lower values, and that their FWHM are higher than those of their crystalline counterparts. The FWHM parameters of crystalline and amorphous materials do not overlap, which allows a clear-cut distinction between crystalline and amorphous materials.
In synthetic magnesian calcites, the shift and FWHM of Raman bands as a function of magnesium can be interpreted in terms of changes of metal-O bond lengths resulting from the replacement of calcium by magnesium. The facts that the wavenumber of magnesian calcites are close to the calcite–dolomite line (not calcite-magnesite), that the FWHM of the T, L, and ν4 modes reach a maximum around 30 ±5 mol% MgCO3, and that a peak specific to dolomite at 880 cm–1 is observed in high-magnesian calcites indicate that dolomite-like ordering is present above ~10 mol% MgCO3. Mg atom clustering in cation layers combined with ordering in successive cation basal layers may account for the progressive ordering observed in synthetic magnesian calcites.
Acknowledgments
This work has been supported by the Centre National de la Recherche Scientifique (CNRS), by Institut National des Sciences de l’Univers (INSU) through grant INTERRVIE 2013, by the Agence National pour la Recherche (ANR) through ANR CoRo 2011–2015, by the Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), and by the European Union COST action TD0903. This work has been partly carried out within the framework of the ICoME2 Labex (ANR-11-LABX-0053) and the A*MIDEX projects (ANR-11-IDEX-0001-02) cofunded by the French program “Investissements d’Avenir,” which is managed by the ANR, the French National Research Agency. Observations were made on a FESEM financed by the European Fund for Regional Development (EFRD). We thank F. Bedu and I. Ozerov for their assistance on this instrument and B. Devouard for providing the OCN calcite. We thank J.L. Devidal and N. Bolfan-Casanova (LMV, Clermond-Fd) for their assistance with electron microprobe and a-Raman, respectively. D.V. benefited from a financial support by E.M. Stolper for a three month stay at Caltech in 2014, where and when most of the μRaman analyses were made. Reviews by R.L. Frost and an anonymous reviewer as well as editorial handling by R. Stalder and K. Putirka are gratefully acknowledged. This is contribution ANR CoRo number 09.
References cited
Addadi, L., Raz, S., and Weiner, S. (2003) Taking advantage of disorder: Amorphous calcium carbonate and its roles in biomineralization. Advanced Materials, 15(12), 959–970.10.1002/adma.200300381Search in Google Scholar
Alia, J.M., de Mera, Y.D., Edwards, H.G.M., Martin, P.G., and Andres, S.L. (1997) FT-Raman and infrared spectroscopic study of aragonite-strontianite (CaxSr1–xCO3) solid solution. Spectrochimica Acta Part a-Molecular and Bio-molecular Spectroscopy, 53(13), 2347–2362.10.1016/S1386-1425(97)00175-3Search in Google Scholar
Bathurst, R. (1975) Carbonate Sediments and Their Diagenesis. Elsevier, Amsterdam.Search in Google Scholar
Beniash, E., Aizenberg, J., Addadi, L., and Weiner, S. (1997) Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth. Proceedings of the Royal Society B-Biological Sciences, 264, 461–465.10.1098/rspb.1997.0066Search in Google Scholar
Benzerara, K., Menguy, N., Lopez-Garcia, P., Yoon, T.H., Kazmierczak, J., Tyliszczak, T., Guyot, F., and Brown, G.E. (2006) Nanoscale detection of organic signatures in carbonate microbialites. Proceedings of the National Academy of Sciences, 103, 9440–9445.10.1073/pnas.0603255103Search in Google Scholar
Bhagavantam, S., and Venkatarayudu, T. (1939) Raman effect in relation to crystal structure. Proceedings of the Indian Academy of Sciences, Section A, 9, 224–258.10.1007/BF03046465Search in Google Scholar
Bischoff, W.D., Bishop, F.C., and Mackenzie, F.T. (1983) Biogenically produced magnesian calcite inhomogeneities in chemical and physical-properties comparison with synthetic phases. American Mineralogist, 68, 1183–1188.Search in Google Scholar
Bischoff, W.D., Sharma, S.K., and Mackenzie, F.T. (1985) Carbonate ion disorder in synthetic and biogenic magnesian calcites—A Raman spectral study. American Mineralogist, 70, 581–589.Search in Google Scholar
Boulard, E., Menguy, N., Auzende, A., Benzerara, K., Bureau, H., Antonangeli, D., Corgne, A., Morard, G., Siebert, J., and Perrillat, J.-P. (2012) Experimental investigation of the stability of Fe-rich carbonates in the lower mantle. Journal of Geophysical Research: Solid Earth (1978–2012), 117(B2).10.1029/2011JB008733Search in Google Scholar
Byrnes, A.P., and Wyllie, P.J. (1981) Subsolidus and melting relations for the join CaCO3-MgCO3 at 10 kbar. Geochimica et Cosmochimica Acta, 45(3), 321–328.10.1016/0016-7037(81)90242-8Search in Google Scholar
Cabannes, J., and Aynard, R. (1942) Étude expérimentale et théorique sur le spectre Raman de l’eau de cristallisation dans le gypse. Le Journal de Physique et Le Radium, 3(8), 137–145.10.1051/jphysrad:0194200308013700Search in Google Scholar
Chave, K.E. (1954a) Aspects of the biogeochemistry of magnesium 1. Calcareous marine organisms. The Journal of Geology, 266–283.10.1086/626162Search in Google Scholar
——— (1954b) Aspects of the biogeochemistry of magnesium 2. Calcareous sediments and rocks. The Journal of Geology, 587–599.10.1086/626208Search in Google Scholar
Couture, L. (1947) Etude des spectres de vibration de monocristaux ioniques. Annales de physique, 2, 5–94.10.1051/anphys/194711020005Search in Google Scholar
Deelman, J. (2003) Low-temperature formation of dolomite and magnesite. Compact disc publications v2.3. (http://www.jcdeelman.demon.nl/dolomite/bookprospectus.html), Accessed: 2015-06.Search in Google Scholar
Doriguetto, A.C., Boschi, T.M., Pizani, P.S., Mascarenhas, Y.P., and Ellena, J. (2004) The effect of the cation substitution on the structural and vibrational properties of Cs2NaGaxSc1-xF6 solid solution. Journal of Chemical Physics, 121(7), 3184–3190.10.1063/1.1773772Search in Google Scholar
Dresselhaus, M., Dresselhaus, G., and Hofmann, M. (2008) Raman spectroscopy as a probe of graphene and carbon nanotubes. Philosophical Transactions of the Royal Society of London A: Mathematical, Physical and Engineering Sciences, 366, 231–236.10.1098/rsta.2007.2155Search in Google Scholar
Falini, G., Fermani, S., Gazzano, M., and Ripamonti, A. (1998) Structure and morphology of synthetic magnesium calcite. Journal of Materials Chemistry, 8(4), 1061–1065.10.1039/a707893eSearch in Google Scholar
Finch, A.A., and Allison, N. (2007) Coordination of Sr and Mg in calcite and aragonite. Mineralogical Magazine, 71(5), 539–552.10.1180/minmag.2007.071.5.539Search in Google Scholar
Goldsmith, J.R., and Heard, H.C. (1961) Subsolidus phase relations in the system. The Journal of Geology, 45–74.10.1086/626715Search in Google Scholar
Goldsmith, J., Graf, D., and Heard, H. (1961) Lattice constants of the calcium-magnesium carbonates. American Mineralogist, 46, 453–457.Search in Google Scholar
Irving, A.J., and Wyllie, P.J. (1975) Subsolidus and melting relationships for calcite, magnesite and the join CaCO3-MgCO3 36 kb. Geochimica et Cosmochimica Acta, 39(1), 35–53.10.1016/0016-7037(75)90183-0Search in Google Scholar
Kastler, A., and Rousset, A. (1941) L’effet Raman et le pivotement des molécules dans les cristaux. Théorie générale et vérification expérimentale dans le cas du naphtalène. Le Journal de Physique et Le Radium, 2(2), 49–57.10.1051/jphysrad:019410020204900Search in Google Scholar
Krishnamurti, D. (1956) Raman spectrum of magnesite. Proceedings of the Indian Academy of Sciences-Section A, 43, 210–212.10.1007/BF03052736Search in Google Scholar
Krishnan, R. (1945) Raman spectra of the second order in crystals Part I: Calcite. Proceedings of the Indian Academy of Sciences, Section A, 22, 182–193.10.1007/BF03170928Search in Google Scholar
Land, L.S. (1967) Diagenesis of skeletal carbonates. Journal of Sedimentary Petrology, 37, 914–930.Search in Google Scholar
Lekgoathi, M.D.S., and Kock, L.D. (2016) Effect of short and long range order on crystal structure interpretation: Raman and powder X-ray diffraction of LiPF6. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 153, 651–654.10.1016/j.saa.2015.09.025Search in Google Scholar PubMed
Long, X., Nasse, M.J., Ma, Y., and Qi, L. (2012) From synthetic to biogenic Mg-containing calcites: a comparative study using FTIR microspectroscopy. Physical Chemistry Chemical Physics, 14(7), 2255–2263.10.1039/c2cp22453dSearch in Google Scholar PubMed
Mackenzie, F.T., Bischoff, W.D., Bishop, F.C., Loijens, M., Schoonmaker, J., and Wollast, R. (1983) Magnesian calcites; low-temperature occurrence, solubility and solid-solution behavior. Reviews in Mineralogy and Geochemistry, 11, 97–144.10.1515/9781501508134-008Search in Google Scholar
Michel, F.M., MacDonald, J., Feng, J., Phillips, B.L., Ehm, L., Tarabrella, C., Parise, J.B., and Reeder, R.J. (2008) Structural characteristics of synthetic amorphous calcium carbonate. Chemistry of Materials, 20(14), 4720–4728.10.1021/cm800324vSearch in Google Scholar
Morse, J.W., Arvidson, R.S., and Lüttge, A. (2007) Calcium carbonate formation and dissolution. Chemical Reviews, 107(2), 342–381.10.1021/cr050358jSearch in Google Scholar PubMed
Navrotsky, A., and Capobianco, C. (1987) Enthalpies of formation of dolomite and magnesian calcites. American Mineralogist, 72, 782–787.Search in Google Scholar
Politi, Y., Arad, T., Klein, E., Weiner, S., and Addadi, L. (2004) Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase. Science, 306, 1161–1164.10.1126/science.1102289Search in Google Scholar PubMed
Politi, Y., Levi-Kalisman, Y., Raz, S., Wilt, F., Addadi, L., Weiner, S., and Sagi, I. (2006) Structural characterization of the transient amorphous calcium carbonate precursor phase in sea urchin embryos. Advanced Functional Materials, 16(10), 1289–1298.10.1002/adfm.200600134Search in Google Scholar
Politi, Y., Batchelor, D.R., Zaslansky, P., Chmelka, B.F., Weaver, J.C., Sagi, I., Weiner, S., and Addadi, L. (2010) Role of magnesium ion in the stabilization of biogenic amorphous calcium carbonate: A structure-function investigation. Chemistry of Materials, 22(1), 161–166.10.1021/cm902674hSearch in Google Scholar
Railsback, L.B. (1999) Patterns in the compositions, properties, and geochemistry of carbonate minerals. Carbonates and Evaporites, 14(1), 1–20.10.1007/BF03176144Search in Google Scholar
Roisnel, T., and Rodríquez-Carvajal, J. (2001) WinPLOTR: a windows tool for powder diffraction pattern analysis. Materials Science Forum, 378, 118–123.10.4028/www.scientific.net/MSF.378-381.118Search in Google Scholar
Rutt, H., and Nicola, J. (1974) Raman spectra of carbonates of calcite structure. Journal of Physics C: Solid State Physics, 7, 4522.10.1088/0022-3719/7/24/015Search in Google Scholar
Schauble, E.A., Ghosh, P., and Eiler, J.M. (2006) Preferential formation of 13C–18O bonds in carbonate minerals, estimated using first-principles lattice dynamics. Geochimica et Cosmochimica Acta, 70, 2510–2529.10.1016/j.gca.2006.02.011Search in Google Scholar
Tao, J.H., Zhou, D.M., Zhang, Z.S., Xu, X.R., and Tang, R.K. (2009) Magnesium-aspartate-based crystallization switch inspired from shell molt of crustacean. Proceedings of the National Academy of Sciences, 106, 22096–22101.10.1073/pnas.0909040106Search in Google Scholar PubMed PubMed Central
Valenzano, L., Noel, Y., Orlando, R., Zicovich-Wilson, C.M., Ferrero, M., and Dovesi, R. (2007) Ab initio vibrational spectra and dielectric properties of carbonates: magnesite, calcite and dolomite. Theoretical Chemistry Accounts, 117(5-6), 991–1000.10.1007/s00214-006-0213-2Search in Google Scholar
Vielzeuf, D., Baronnet, A., Perchuk, A.L., Laporte, D., and Baker, M.B. (2007) Calcium diffusivity in alumino-silicate garnets: an experimental and ATEM study. Contributions to Mineralogy and Petrology, 154(2), 153–170.10.1007/s00410-007-0184-xSearch in Google Scholar
Wang, D.B., Wallace, A.F., De Yoreo, J.J., and Dove, P.M. (2009) Carboxylated molecules regulate magnesium content of amorphous calcium carbonates during calcification. Proceedings of the National Academy of Sciences, 106, 21511–21516.10.1073/pnas.0906741106Search in Google Scholar PubMed PubMed Central
Wang, D.B., Hamm, L.M., Bodnar, R.J., and Dove, P.M. (2012) Raman spectroscopic characterization of the magnesium content in amorphous calcium carbonates. Journal of Raman Spectroscopy, 43(4), 543–548.10.1002/jrs.3057Search in Google Scholar
Weiner, S., Sagi, I., and Addadi, L. (2005) Choosing the crystallization path less traveled. Science, 309, 1027–1028.10.1126/science.1114920Search in Google Scholar PubMed
Weiss, I.M., Tuross, N., Addadi, L., and Weiner, S. (2002) Mollusc larval shell formation: Amorphous calcium carbonate is a precursor phase for aragonite. Journal of Experimental Zoology, 293(5), 478–491.10.1002/jez.90004Search in Google Scholar PubMed
White, W.B. (1974a) The carbonate minerals. In E.V.C. Farmer, Ed., The Infrared Spectra of Minerals, Mineralogical Society Monograph 4, p. 227–284. Mineralogical Society, London.10.1180/mono-4.12Search in Google Scholar
——— (1974b) Order-disorder effects. In E.V.C. Farmer, Ed., The Infrared Spectra of Minerals, Mineralogical Society Monograph, 4 p. 87–110. Mineralogical Society, London.10.1180/mono-4.6Search in Google Scholar
Zolotoyabko, E., Caspi, E.N., Fieramosca, J.S., Von Dreele, R.B., Marin, F., Mor, G., Addadi, L., Weiner, S., and Politi, Y. (2010) Differences between bond lengths in biogenic and geological calcite. Crystal Growth & Design, 10(3), 1207–1214.10.1021/cg901195tSearch in Google Scholar
© 2016 by Walter de Gruyter Berlin/Boston
