Iron and sulfur isotopic compositions of carbonatite-related REE deposits in the Mianning–Dechang REE belt, China: Implications for fluid evolution

Abstract

Carbonatite-related rare earth element (REE) deposits are the most significant source of REEs worldwide. The processes of REE precipitation, enrichment, and mineralization remain controversial. The Cenozoic Mianning–Dechang (MD) REE belt, located in Sichuan Province, southwestern China, comprises one giant (Maoniuping), one large (Dalucao), and two small–medium (Muluozhai and Lizhuang) deposits. These deposits provide a continuous record of fluid evolution, and thus are ideal for investigating the processes of REE mineralization in carbonatite-related REE deposits. Given that sulfate (i.e., barite and celestite) and sulfide (i.e., pyrite and galena) minerals crystallized and precipitated in the pegmatitic to hydrothermal stages, respectively, the REE minerals formed later than the sulfate minerals. However, the formation sequence of the sulfide minerals and bastnäsite is unclear, although both pyrite and bastnäsite formed in the late hydrothermal stage. We used S isotope data for sulfate and sulfide minerals and Fe isotope data for pyrite to investigate the composition and evolution of ore-forming fluids during the magmatic–hydrothermal stages. The sulfate minerals have positive δ34SCDT values (+3.2‰ to +8.3‰), and the sulfide minerals have negative δ34SCDT values (−13.5‰ to − 5.6‰) in the four REE deposits. In the Maoniuping deposit, δ34SCDT values for barite from the pegmatitic stage (+4.7‰ to +5.7‰) are higher than for barite from the hydrothermal stage (+4.1‰ to +4.5‰), which indicate that hydrothermal activity led to relative enrichment in isotopically light S. The δ34SCDT values for barite (+3.2‰ to +5.5‰) are lower than for celestite (+6.2‰ to +7.2‰) from the pegmatitic stage in the Dalucao deposit. The δ34SCDT values for galena (−13.5‰) are also lower than for pyrite (−13.5‰ to −7.2‰) from the hydrothermal stage in the Guangtoushan section. In general, δ34SCDT values change from positive to negative values (+8.3‰ to −16.4‰) as the fluids evolved from the pegmatitic to hydrothermal stages, which can be attributed to a decrease in oxygen fugacity (fO2) and addition of sediment containing isotopically light S. Iron isotopic compositions of pyrite from the hydrothermal stage show significant variations (δ56FeIRMM-014 = −0.03‰ to +0.65‰ for the Maoniuping deposit; −0.14‰ to 0.00‰ for the Dalucao deposit; +0.05‰ to +0.35‰ for the Lizhuang deposit), and are higher than those for the carbonatites (δ56Fe IRMM-014 = −0.47‰ to −0.17‰). These data indicate there are two sources of Fe in the MD REE belt, which are the carbonatite–nordmarkite magma and 56Fe-rich sediment. Paleozoic–Mesozoic volcanic–sedimentary and Mesozoic clastic and carbonate rocks are exposed in the MD REE belt. In general, the S–Fe isotope data, along with geological and petrographic observations, indicate that the REE minerals formed later than the sulfate minerals, and the S–Fe were derived from both carbonatite magma and sediment containing isotopically light S and heavy Fe.