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 ∼10 μm. 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 δ 18 O 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 δ 18 O over areas ⩽1.41 cm 2 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 δ 18 O 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 δ 18 O over areas ⩽1.17 cm 2 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 δ 18 O 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 δ 18 O 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 δ 18 O 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 δ 18 O that is statistically indistinguishable from δ 18 O of the same mineral occurring as nearby matrix grains or have statistically significant lower δ 18 O. 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 δ 18 O, (2) oxygen isotope homogenization at the outcrop scale among contrasting lithologies, (3) changes in δ 18 O with increasing grade of regional metamorphism, and (4) time scales of metamorphic process.