Precise age determinations and petrogenetic studies using the KCa method

High precision mass spectrometric determination of calcium isotope ratios allows the ⁴⁰K → ⁴⁰Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ is used to monitor enrichments in ⁴⁰Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low $\text{K}\text{Ca}$ (～0.01) that it has retained “primordial” ${}^{40}\text{Ca}{}^{42}\text{Ca}\text{= 151.016}$ ± 0.011 (normalized to ${}^{42}\text{Ca}{}^{44}\text{Ca}\text{= 0.31221}$), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ ratios can be conveniently expressed relative to this value as ?_Ca in units of 10^?4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λ_K = 0.5543 b.y.^?1, $\text{λ}{}_{\mathrm{\beta ?}}\text{λ}{}_{\mathrm{<mtext>K</mtext>}}\text{= 0.8952}$, ⁴⁰K = 0.01167%). The initial ${}^{40}\text{Ca}{}^{42}\text{Ca}$ of 151.024 ± 0.016 (?_Ca = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of ⁴⁰K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.