Oxygen isotope variations of garnets and clinopyroxenes in a layered diamondiferous calcsilicate rock from Kokchetav Massif,Kazakhstan: a window into the geochemical nature of deeply subducted UHPM rocks

Calcsilicate and garnet-pyroxene rocks with dolomite and Mg-calcite matrices occur with UHPM diamondiferous biotite gneisses and schists of the Kokchetav Massif. The calcsilicates are characterized by high diamond grade, K-bearing diopside, and very high Mg-garnets (Mg# > 77) with variable Ca contents (Ca# = 42.5–80). A rare calcsilicate sample with alternating layers of different bulk compositions was selected for oxygen isotope and electron probe microanalysis of garnets and pyroxenes. A grain of fresh garnet with a brownish-yellow luminescent inner domain (Mg# 94) and a non-luminescent outer part (Mg# 88) was selected for in situ analysis of δ¹⁸O by ion microprobe (10 μm spot). The profile demonstrates a δ¹⁸O gradient of 1.5‰/200 μm, from 11.3 (rim) to 12.8‰ (core) VSMOW. Additional 2 mg samples of hand-picked garnet and clinopyroxene fragments from different parts of the same sample (selected by color and chemical differences) were analyzed for δ¹⁸O by laser fluorination, yielding even larger differences in δ¹⁸O: 6.3–10.6‰ in garnets and 6.1–8.1 in clinopyroxenes. The zonation in δ¹⁸O among grains of the same mineral in different lithologies may in part reflect initial heterogeneities of the finely layered sedimentary precursors. The δ¹⁸O values for the garnets are among the highest observed for UHP-origin (both for crustal or mantle rocks), confirming a sedimentary origin for these carbonate-bearing rocks, and ruling out a primitive mantle-derived protolith. Oxygen diffusion in garnet at peak metamorphism temperature (1,000°C) was arrested by rapid cooling.