Molybdenum and sulfur incorporation as oxyanion substitutional impurities in calcium carbonate minerals: a computational investigation

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Midgley, S. D., Taylor, J. O., Fleitmann, D. and Grau-Crespo, R. ORCID: https://orcid.org/0000-0001-8845-1719 (2020) Molybdenum and sulfur incorporation as oxyanion substitutional impurities in calcium carbonate minerals: a computational investigation. Chemical Geology, 553. 119796. ISSN 0009-2541 doi: 10.1016/j.chemgeo.2020.119796

Abstract/Summary

Marked increases in sulfur and molybdenum concentration in stalagmites have been proposed as possible evidence of volcanic activity in the past. Thus, speleothems have great potential to deliver long and continuous records of volcanic activity. However, little is known about the chemical nature of these impurities in the calcium carbonate (CaCO3) phases forming stalagmites, which hinders the rationalization of the incorporation mechanisms. While sulfur is known to incorporate as a sulfate anion in CaCO3 polymorphs, the nature and stability of molybdenum incorporation in these minerals has not been investigated yet. Here, we present a computer simulation study, based on density functional theory, comparing the thermodynamics of incorporation of sulfur and molybdenum as tetrahedral oxyanions [XO4]2- (X=S, Mo) in anion sites of CaCO3 polymorphs (calcite, aragonite, vaterite, monohydrocalcite and ikaite). Among the different polymorphs, vaterite incorporates [XO4]2- ions most favourably, which reflects the relatively low density of this carbonate phase. We show that molybdate anions are very unstable (more so than sulfate anions) in the bulk of all three anhydrous carbonate phases, with respect to the formation of naturally occurring competing phases. Most of the Mo impurities found in typical calcite/aragonite stalagmites is therefore likely to concentrate at surface/interface regions such as grain boundaries. Using the calcite (10.4) surface as a model, we show that the energies of substitution are indeed much lower at the surface than at the bulk. Our results suggest that factors affecting the crystallinity of CaCO3 in stalagmites, and therefore the specific surface area, will have a significant effect on the concentration of incorporated molybdenum, which should be a key consideration when interpreting data from Mo-based speleothem archives.

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Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/92282
Identification Number/DOI	10.1016/j.chemgeo.2020.119796
Refereed	Yes
Divisions	Science > School of Archaeology, Geography and Environmental Science > Department of Archaeology Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry Interdisciplinary centres and themes > Centre for Past Climate Change
Uncontrolled Keywords	calcium carbonate; sulfate; molybdate; calcite; aragonite; vaterite; monohydrocalcite; ikaite
Publisher	Elsevier
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Date Deposited:	19 Aug 2020 08:37	Date item deposited into CentAUR
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References

Affolter, S., Häuselmann, A., Fleitmann, D., Edwards, R.L., Cheng, H. and Leuenberger, M. (2019) Central Europe temperature constrained by speleothem fluid inclusion water isotopes over the past 14,000 years. Sci Adv 5, eaav3809. Arroyo-de Dompablo, M.E., Fernández-González, M.A. and Fernández-Díaz, L. (2015) Computational investigation of the influence of tetrahedral oxoanions (sulfate, selenate and chromate) on the stability of calcium carbonate polymorphs. RSC Adv. 5, 59845-59852. Badertscher, S., Borsato, A., Frisia, S., Cheng, H., Edwards, R.L., Tüysüz, O. and Fleitmann, D. (2014) Speleothems as sensitive recorders of volcanic eruptions – the Bronze Age Minoan eruption recorded in a stalagmite from Turkey. Earth and Planetary Science Letters 392, 58-66. Balan, E., Blanchard, M., Pinilla, C. and Lazzeri, M. (2014) First-principles modeling of sulfate incorporation and 34S/32S isotopic fractionation in different calcium carbonates. Chemical Geology 374-375, 84-91. Blöchl, P.E. (1994) Projector augmented-wave method. Physical Review B 50, 17953-17979. Böke, H., Göktürk, E.H., Caner-Saltık, E.N. and Demirci, Ş. (1999) Effect of airborne particle on SO2–calcite reaction. Applied Surface Science 140, 70-82. Busenberg, E. and Plummer, L.N. (1985) Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites. Geochimica et Cosmochimica Acta 49, 713-725. De Choudens-Sanchez, V. and Gonzalez, L.A. (2009) Calcite and Aragonite Precipitation Under Controlled Instantaneous Supersaturation: Elucidating the Role of CaCO3 Saturation State and Mg/Ca Ratio on Calcium Carbonate Polymorphism. Journal of Sedimentary Research 79, 363-376. de Leeuw, N.H. and Parker, S.C. (1998) Surface Structure and Morphology of Calcium Carbonate Polymorphs Calcite, Aragonite, and Vaterite: An Atomistic Approach. The Journal of Physical Chemistry B 102, 2914-2922. De Villiers, J.P.R. (1971) Crystal Structures of Aragonite, Strontianite, and Witherite. American Mineralogist 56, 758-767. Dorale, J.A., Edwards, R.L., Calvin-Alexander Jr, E., Shen, C.C., Richards, D.A. and Cheng, H. (2004) Studies of Cave Sediments. Springer US, Boston, MA. Fairchild, I.J. and Treble, P.C. (2009) Trace elements in speleothems as recorders of environmental change. Quaternary Science Reviews 28, 449-468. Fernández-Díaz, L., Fernández-González, Á. and Prieto, M. (2010) The role of sulfate groups in controlling CaCO3 polymorphism. Geochimica et Cosmochimica Acta 74, 6064-6076. Field, L.P., Milodowski, A.E., Shaw, R.P., Stevens, L.A., Hall, M.R., Kilpatrick, A., Gunn, J., Kemp, S.J. and Ellis, M.A. (2018) Unusual morphologies and the occurrence of pseudomorphs after ikaite (CaCO3·6H2O) in fast growing, hyperalkaline speleothems. Mineralogical Magazine 81, 565-589. Finch, A.A., Shaw, P.A., Weedon, G.P. and Holmgren, K. (2001) Trace element variation in speleothem aragonite: potential for palaeoenvironmental reconstruction. Earth and Planetary Science Letters 186, 255-267. Fischbeck, R. and Müller, G. (1971) Monohydrocalcite, hydromagnesite, nesquehonite, dolomite, aragonite, and calcite in speleothems of the Fränkische Schweiz, Western Germany. Contributions to Mineralogy and Petrology 33, 87-92. Fleitmann, D., Cheng, H., Badertscher, S., Edwards, R.L., Mudelsee, M., Göktürk, O.M., Fankhauser, A., Pickering, R., Raible, C.C., Matter, A., Kramers, J. and Tüysüz, O. (2009) Timing and climatic impact of Greenland interstadials recorded in stalagmites from northern Turkey. Geophysical Research Letters 36. Given, R.K. and Wilkinson, B.H. (1985) Kinetic Control of Morphology, Composition, and Mineralogy of Abiotic Sedimentary Carbonates. SEPM Journal of Sedimentary Research Vol. 55, 109-119. Hartland, A., Fairchild, I.J., Lead, J.R., Borsato, A., Baker, A., Frisia, S. and Baalousha, M. (2012) From soil to cave: Transport of trace metals by natural organic matter in karst dripwaters. Chemical Geology 304-305, 68-82. Hesse, K.F., Küppers, H. and Suess, E. (1983) Refinement of the structure of Ikaite, CaCO3 - 6H2O, Zeitschrift für Kristallographie - Crystalline Materials, p. 227. Kampschulte, A., Bruckschen, P. and Strauss, H. (2001) The sulphur isotopic composition of trace sulfates in Carboniferous brachiopods: implications for coeval seawater, correlation with other geochemical cycles and isotope stratigraphy. Chemical Geology 175, 149-173. Kresse, G. and Furthmüller, J. (1996a) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science 6, 15-50. Kresse, G. and Furthmüller, J. (1996b) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B 54, 11169-11186. Kresse, G. and Joubert, D. (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B 59, 1758-1775. Lacelle, D., Lauriol, B. and Clark, I.D. (2009) Formation of seasonal ice bodies and associated cryogenic carbonates in caverne de l'ours, Québec, Canada: Kinetic isotope effects and pseudo-biogenic crystal structures. Journal of Cave and Karst Studies 71, 48-62. Lowe, D.J. (2011) Tephrochronology and its application: A review. Quaternary Geochronology 6, 107-153. Malaga-Starzec, K., Panas, I. and Lindqvist, O. (2004) Model study of initial adsorption of SO2 on calcite and dolomite. Applied Surface Science 222, 82-88. Markgraf, S. and Reeder, R. (1985) High-temperature structure refinements of calcite and magnesite. Am. Mineral. 70, 590-600. Marshall, D., Ghaleb, B., Countess, R. and Gabities, J. (2009) Preliminary paleoclimate reconstruction based on a 12,500 year old speleothem from Vancouver Island, Canada: stable isotopes and U-Th disequilibrium dating. Quaternary Science Reviews 28, 2507-2513. McCarroll, D. and Loader, N.J. (2004) Stable isotopes in tree rings. Quaternary Science Reviews 23, 771-801. Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized Gradient Approximation Made Simple. Physical Review Letters 77, 3865-3868. Railsback, L.B., Brook, G.A., Chen, J., Kalin, R. and Fleisher, C.J. (1994) Environmental Controls on the Petrology of a Late Holocene Speleothem from Botswana with Annual Layers of Aragonite and Calcite. SEPM Journal of Sedimentary Research Vol. 64A, 147-155. Raiteri, P., Gale, J.D., Quigley, D. and Rodger, P.M. (2010) Derivation of an Accurate Force-Field for Simulating the Growth of Calcium Carbonate from Aqueous Solution: A New Model for the Calcite−Water Interface. The Journal of Physical Chemistry C 114, 5997-6010. Robock, A. (2000) Volcanic eruptions and climate. Reviews of Geophysics 38, 191-219. Rohl, A.L., Wright, K. and Gale, J.D. (2003) Evidence from surface phonons for the (2 × 1) reconstruction of the (101̅4) surface of calcite from computer simulation. American Mineralogist 88, 921-925. Ruiz-Hernandez, S.E., Grau-Crespo, R., Ruiz-Salvador, A.R. and De Leeuw, N.H. (2010) Thermochemistry of strontium incorporation in aragonite from atomistic simulations. Geochimica et Cosmochimica Acta 74, 1320-1328. Severi, M., Udisti, R., Becagli, S., Stenni, B. and Traversi, R. (2012) Volcanic synchronisation of the EPICA-DC and TALDICE ice cores for the last 42 kyr BP. Climate of the Past 8, 509-517. Sigl, M., McConnell, J.R., Layman, L., Maselli, O., McGwire, K., Pasteris, D., Dahl-Jensen, D., Steffensen, J.P., Vinther, B., Edwards, R., Mulvaney, R. and Kipfstuhl, S. (2013) A new bipolar ice core record of volcanism from WAIS Divide and NEEM and implications for climate forcing of the last 2000 years. Journal of Geophysical Research: Atmospheres 118, 1151-1169. St Pierre, E., Zhao, J.-X. and Reed, E. (2009) Expanding the utility of Uranium-series dating of speleothems for archaeological and palaeontological applications. Journal of Archaeological Science 36, 1416-1423. Stoffers, P. and Fischbeck, R. (1974) Monohydrocalcite in the sediments of Lake Kivu (East Africa). Sedimentology 21, 163-170. Swainson, I.P. (2008) The structure of monohydrocalcite and the phase composition of the beachrock deposits of Lake Butler and Lake Fellmongery, South Australia. American Mineralogist 93, 1014-1018. Ünal-İmer, E., Shulmeister, J., Zhao, J.-X., Tonguç Uysal, I., Feng, Y.-X., Duc Nguyen, A. and Yüce, G. (2015) An 80 kyr-long continuous speleothem record from Dim Cave, SW Turkey with paleoclimatic implications for the Eastern Mediterranean. Scientific reports 5, 13560-13560. Vavouraki, A.I., Putnis, C.V., Putnis, A. and Koutsoukos, P.G. (2008) An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate. Chemical Geology 253, 243-251. Voelker, A.H.L. (2002) Global distribution of centennial-scale records for Marine Isotope Stage (MIS) 3: a database. Quaternary Science Reviews 21, 1185-1212. Wang, J. and Becker, U. (2009) Structure and carbonate orientation of vaterite (CaCO3). American Mineralogist 94, 380-386. Wang, Q., Grau-Crespo, R. and de Leeuw, N.H. (2011) Mixing Thermodynamics of the Calcite-Structured (Mn,Ca)CO3 Solid Solution: A Computer Simulation Study. The Journal of Physical Chemistry B 115, 13854-13861. Yalcin, K., Wake, C.P., Kreutz, K.J., Germani, M.S. and Whitlow, S.I. (2007) Ice core paleovolcanic records from the St. Elias Mountains, Yukon, Canada. Journal of Geophysical Research 112, D08102-D08102. Zielinski, G.A. (2000) Use of paleo-records in determining variability within the volcanism–climate system. Quaternary Science Reviews 19, 417-438. Zielinski, G.A., Mayewski, P.A., Meeker, L.D., Whitlow, S., Twickler, M.S., Morrison, M., Meese, D.A., Gow, A.J. and Alley, R.B. (1994) Record of Volcanism Since 7000 B.C. from the GISP2 Greenland Ice Core and Implications for the Volcano-Climate System. Science 264, 948-952.

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