Ion microprobe survey of the grain-scale oxygen isotope geochemistry of minerals in metamorphic rocks

Abstract

The oxygen isotope compositions of calcite, diopside, dolomite, forsterite, garnet, K-feldspar, kyanite, plagioclase, quartz, and wollastonite were analyzed in suites of contact and regional metamorphic rocks using an ion microprobe. Spatial resolution was ∼10μm. Precision, measured as the standard deviation of working standards averaged over the entire project, was 0.13–0.18‰ for three carbonate standards and 0.11–0.12‰ for two silicate standards. A total of 1176 analyses (excluding standards) were made of 73 minerals in 23 samples. Both intercrystalline and intracrystalline variability in δ18O is greater in contact than in regional metamorphic rocks. Of 27 minerals analyzed in contact metamorphosed rocks, 70% exhibit statistically significant grain-to-grain variability in δ18O over areas ⩽1.41cm2 with the largest range in silicates and carbonates in a single sample of 7.4‰ (forsterite) and 10.6‰ (dolomite). Of 88 grains analyzed in two or more places in contact metamorphosed rocks, 32% exhibit statistically significant intracrystalline variability in δ18O with the largest range in a single silicate and carbonate grain of 3.1‰ (forsterite) and 10.1‰ (dolomite). In contrast, 44% of 45 minerals in regional metamorphic rocks exhibit significant grain-to-grain variability in δ18O over areas ⩽1.17cm2 with the largest range in silicates and carbonates in a single sample of only 1.1‰ (plagioclase) and 0.9‰ (calcite). Only 6% of 144 grains analyzed in two or more places in regional metamorphic rocks exhibit significant intracrystalline variability in δ18O with the largest range in a single silicate and carbonate grain of only 1.5‰ (diopside) and 0.7‰ (calcite). The difference in intercrystalline and intracrystalline variability in δ18O between contact and region metamorphic rocks is explained by the longer duration and slower reaction rates of regional metamorphism rather than to differences in temperature. There is no significant difference in intercrystalline and intracrystalline variability in δ18O in regional metamorphic rocks among samples from the biotite, garnet, and kyanite zones. Calcite inclusions in forsterite, and calcite and quartz inclusions in garnet either have δ18O that is statistically indistinguishable from δ18O of the same mineral occurring as nearby matrix grains or have statistically significant lower δ18O. No reversed isotope fractionations were measured between coexisting mineral pairs. Minerals in individual samples, however, exhibit a wide range in the degree to which they attained and preserve oxygen isotope fractionations consistent with metamorphic temperatures recorded by mineral equilibria. Processes that account for grain-scale departures from isotope exchange equilibrium include: (a) overstepping of prograde mineral reactions, (b) growth zoning in low-diffusivity minerals, (c) interaction of rocks with fluids at the peak of metamorphism and/or during cooling, (d) retrograde mineral reactions, and (e) closed-system isotope exchange between coexisting minerals during cooling. This study provides new information about (1) the degree to which a variety of textural changes experienced by rocks during metamorphism are associated with changes in δ18O, (2) oxygen isotope homogenization at the outcrop scale among contrasting lithologies, (3) changes in δ18O with increasing grade of regional metamorphism, and (4) time scales of metamorphic process.