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Spontaneous movement of ions through calcite at standard temperature and pressure


At the resolution limits of traditional geochemical techniques, there is little evidence to challenge the common assumptions that, under the Earth's ambient surface conditions, dry calcite is static and that the bulk mineral behaves as a closed system. Solid-state diffusion has been recognized at elevated temperatures1,2,3, but ithas always been assumed that diffusion in carbonate minerals is negligible under standard conditions4,5. There is, however, some evidence to the contrary. More than 30 years ago, the 45Ca diffusion coefficient was estimated to be 8 × 10−20 cm2 (ref. 6) and, more recently, we have demonstrated movement of adsorbed Cd2+ and Zn2+ into bulk calcite at rates of tens of nanometres over weeks to months (refs 7, 8). Here we present evidence thatmonovalent ions, Na+, K+ and Cl, originating from fluid inclusions, accumulate in crystallites on the surface of calcite. This process is spontaneous at the Earth's surface conditions, in air. The results show that calcite under standard conditions does not always behave as a closed system, which is a critical assumption in the use of isotope ratios, trace-element distribution and fluid-inclusion composition for interpretations of palaeoclimate, geochronology or petrogenesis. Moreover, calcite's uptake capacity for contaminants in environmental systems is probably higher than current models predict, because surface sites are constantly renewed by ionic mobility.

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Figure 1: Atomic force microscopy images, taken in air, of calcite surfaces.
Figure 2: Positive time-of-flight secondary ion mass spectrometry maps for Ca and K from the same aged surface shown in Fig. 1e.
Figure 3: TOF-SIMS maps of relative elemental intensity from fresh (top row) and aged (bottom row) calcite surfaces.
Figure 4: An optical microscope view through a calcite cleavage flake 1.5 mm thick.

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  1. Wada, H. Microscale isotopic zoning in calcite and graphite crystals in marble. Nature 331, 61–63 (1988).

    Article  ADS  CAS  Google Scholar 

  2. Farver, J. R. Oxygen self-diffusion in calcite: Dependence on temperature and water fugacity. Earth Planet. Sci. Lett. 121, 575–587 (1994).

    Article  ADS  CAS  Google Scholar 

  3. Cherniak, D. J. An experimental study of strontium and lead diffusion in calcite, and implications for carbonate diagenesis and metamorphism. Geochim. Cosmochim. Acta 61, 4173–4179 (1997).

    Article  ADS  CAS  Google Scholar 

  4. Lahann, R. W. & Siebert, R. M. Akinetic model for distribution coefficients and application to Mg-calcites. Geochim. Cosmochim. Acta 46, 2229–2237 (1982).

    Article  ADS  CAS  Google Scholar 

  5. Davis, J. A., Fuller, C. C. & Cook, A. D. Amodel for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation. Geochim. Cosmochim. Acta 51, 1477–1490 (1987).

    Article  ADS  CAS  Google Scholar 

  6. Lahav, N. & Bolt, G. H. Self-diffusion of 45Ca into certain carbonates. Soil Sci. 97, 293–299 (1964).

    Article  ADS  CAS  Google Scholar 

  7. Stipp, S. L., Hochella, M. F. J, Parks, G. A. & Leckie, J. O. Cd2+ uptake by calcite, solid-state diffusion, and the formation of solid-solution: Interface processes observed with near-surface sensitive techniques (XPS, LEED, and AES). Geochim. Cosmochim. Acta 56, 1941–1954 (1992).

    Article  ADS  CAS  Google Scholar 

  8. Stipp, S. L. S. Understanding interface processes and their role in the mobility of contaminants in the geosphere: The use of surface sensitive techniques. Eclogae Geol. Helv. 87, 335–355 (1994).

    Google Scholar 

  9. Reeder, R. Carbonates: Mineralogy and Chemistry. (Reviews in Mineralogy Vol. 11, Mineralogical Society of America, Washington DC, 1983).

    Book  Google Scholar 

  10. Plummer, L. N. & Busenberg, E. The solubilities of calcite, aragonite, and vaterite in CO2-H2O solutions between 0° and 90 °C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O. Geochim. Cosmochim. Acta 46, 1011–1040 (1982).

    Article  ADS  CAS  Google Scholar 

  11. Eggleston, C. M. in Scanning Probe Microscopy of Clay Minerals (eds Nagy, K. L. & Blum, A. E.) 1–90 (Vol. 7, Workshop Lectures, Clay Mineral. Soc., Boulder, CO, 1994).

    Google Scholar 

  12. Stipp, S. L. S., Gutmannsbauer, W. & Lehmann, T. The dynamic nature of calcite surfaces in air. Am. Mineral. 81, 1–8 (1996).

    Article  ADS  CAS  Google Scholar 

  13. Chiarello, R. P., Wogelius, R. A. & Sturchio, N. C. In-situ synchrotron X-ray reflectivity measurements at the calcite-water interface. Geochim. Cosmochim. Acta 57, 4103–4110 (1993).

    Article  ADS  CAS  Google Scholar 

  14. Benninghoven, A., Hagenhoff, B. & Neihus, E. Surface MS-probing of real-world samples. Anal. Chem. 65, 630A–640A (1993).

    Article  Google Scholar 

  15. Stipp, S. L. S., Kulik, A. J., Franzreb, K., Benoit, W. & Mathieu, H. J. Acombination of SFM and TOF-SIMS imaging for observing local inhomogenieties in morphology and composition. Surf. Interface Anal. 25, 959–965 (1997).

    Article  CAS  Google Scholar 

  16. Roedder, E. Fluid Inclusions. (Reviews in Mineralogy Vol 12, Mineralogical Society of America, Washington DC, 1984).

    Book  Google Scholar 

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We thank W. Benoit, H.-R. Pfeifer and J.-C. Védy for support during the early stages of the work; J. Rønsbo and E. Makovicky for discussions; U. Hoffmann for help with collection of Fig. 1f; P.Shi, D. Léonard and Y. Chevolot for instrument support; and B. Svane Nielsen, R. Bromley, B. Buchardt, H.J.Hansen, R. Yund and G. Jenkin for comments. This work is dedicated to George A. Parks. Partial funding was provided by the Danish Research Council.

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Correspondence to S. L. S. Stipp.

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Stipp, S., Konnerup-Madsen, J., Franzreb, K. et al. Spontaneous movement of ions through calcite at standard temperature and pressure. Nature 396, 356–359 (1998).

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