Diffusion of tetravalent cations in zircon

Diffusion rates for the three tetravalent cations U, Th and Hf have been measured in synthetic zircon. Diffusant sources included oxide powders and ground pre-synthesized silicates. Rutherford backscattering spectrometry (RES) was used to measure depth profiles. Over the temperature range 1400-1650 degrees C, the following Arrhenius relations were obtained (diffusion coefficients in m(2)sec(-1)): log D-Th = (1.936 +/- 0.9820) + (-792 +/- 34 kJ mol(-1)/2.303 RT) logD(U) = (0.212 +/- 2.440) + (-726 +/- 83 kJ mol(-1)/2.303 RT) logD(Hf) = (3.206 +/- 1.592) + (-812 +/- 54 kJ mol(-1)/2.303 RT) The data show a systematic increase in diffusivity with decreasing ionic radius (i.e., faster diffusion rates for Hf than for U or Th), a trend also observed in our earlier study of rare earth diffusion in zircon. Diffusive fractionation may be a factor in the Lu-Hf system given the much slower diffusion rates of tetravalent cations when compared with the trivalent rare earths. The very slow diffusion rates measured for these tetravalent cations suggest that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores.