Oxygen-Carbon and Strontium Isotope Evidence for the Origin and Evolution of CO2-rich Volatiles from Oligocene to Miocene Mantle Magmas, Southwestern Colorado and Northwestern New Mexico

Oligocene to Miocene, alkaline mafic to ultramafic, rocks that are exposed in the Navajo volcanic field and dikes on the northern San Juan basin (NVSJ) contain calcite in vugs, veins, and breccias. Oxygen-carbon and Sr isotope signatures of bulk carbonate samples from these rocks were used to test hypotheses on the history of volatiles related to this pulse of mantle magmatism. Elevated fluorine in rocks, and fluorite-calcite breccias in some outcrops, indicate that magmatic volatiles were released by NVSJ melts. Oxygen and carbon isotope data for carbonate samples record a complex paragenetic history. δ13C values are mostly -8‰ to -4‰ with a mean value of -5.3 ± 2.0‰, similar to δ13C for primary mantle-derived carbonate. A subset of δ18O values are +5‰ to +10‰ which are within the accepted range of δ18O values for magmatic carbonate in carbonatite and kimberlite. A majority of δ18O values, however, range from +10‰ to +24‰ revealing that low-δ18O magmatic volatiles were overprinted by processes that caused enrichment of ¹⁸O at some stage during melt generation and emplacement. A subset of 87Sr/86Sr_i data from carbonate samples are nearly identical to 87Sr/86Sr_i for related rocks, hinting that the melts and volatiles came from the same source. Generally, NVSJ calcite samples have higher 87Sr/86Sr_i ratios than those of rocks, reflecting different melt-volatile sources or crustal contamination from Paleozoic limestone. Field and petrologic evidence does not lend convincing support for crustal contamination. Limestone fragments comprise less than 1% of xenoliths in NVSJ rocks. Also, rock samples do not show elevated CaO, MgO, FeO, Ba or Sr with increasing δ18O calcite which is expected for contamination of magmas with limestone. We propose that CO₂-H₂O-F volatiles in NVSJ magmas came from distinct melt-volatile sources, similar to the interpretation of Nowell (1993). Our assertion is that CO₂-rich volatiles that exsolved from low δ18O mafic melts interacted with volatiles and melts from carbonate-bearing metasomatized lithospheric mantle. This is consistent with the subtle increase of 87Sr/86Sr_{i rock} and fluorine over the +6‰ to +24‰ range of δ18O_calcite values recorded in minette samples. This hypothesis is supported by other studies that document +21‰ to +25‰ δ18O for carbonate in mantle xenoliths from Pliocene alkaline basalts in the region. Incipient to extensive alteration of olivine and phlogopite phenocrysts in NVSJ rocks reveals that deuteric isotopic exchange with H₂O-CO₂ magmatic fluids was a plausible factor for some of the variation in δ18O of calcite samples. In addition, melt contamination with limestone cannot be ruled out, but it requires nearly complete digestion of xenoliths in feeder dikes that had relatively low volumes of magma and cooled quickly. Overall, the isotope data combined with field and petrologic results are not consistent with models that invoke groundwater as the main source of volatiles in NVSJ magmas.