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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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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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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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