Isotopes of carbon and oxygen of siderite and their genetic indications for the Late Permian critical-metal tuffaceous deposits (Nb-Zr-REY-Ga) from Yunnan, southwestern China

This paper describes numerous siderite occurrences from Nb-Zr-REY-Ga-enriched beds of tuffaceous mudstone from the Yujingshan borehole, eastern Yunnan, southwestern China. The mineral phases in the samples were identified and characterized through macroscopic observation, XRD (X-ray diffraction) analysis, optical microscopy, and FE-SEM (field emission-scanning electron microscopy). The results show that the siderite occurs in the drill core from depths of 664.07 to 729.21 m, where its content varies from 15.1 to 65.7%, 31.3% on average. Modes of occurrence of authigenic siderite include irregular banded or massive aggregates, discrete fine particles, oolitic aggregates, and double or multi-ring ellipsoid-shaped or rhombohedral aggregates. The mineralogical association with quartz, anatase, ilmenite, chromite, and zircon with sharp-edged outlines, high-temperature cracks and/or corroded embayments, and REE-bearing minerals and geochemical characteristics such as Al2O3/TiO2 between 3 and 8, less commonly 8–23.77, indicate that abundant siderite was produced by hydrothermal alteration of airborne volcaniclastic materials. The δ13CPDB, δ18OPDB, and δ18OSMOW values of siderite in the argillized tuff range from −12.56 to −1.32‰, −8.98 to −5.88‰, and 21.60 to 24.80‰, respectively. In the δ13CPDB-δ18OSMOW diagram, plots of the studied siderite are distributed between the fields of marine carbonate rocks, sedimentary organic matter, and carbonates of hydrothermal ores. Some siderite from the upper part of the studied borehole is isotopically close to REY carbonates from the Abramovka lignite deposit, Far Eastern Russia, which precipitated from evolved basinal waters mixed with CO2 from a mantle source. In summary, this indicates a hybrid origin for the studied siderite including carbonate dissolution, dehydroxylation of sedimentary organic matter, and hydrothermal activity. Furthermore, the paleosalinity (Z) and paleotemperature (T) of the ore-forming fluids were calculated based on the age-corrected stable carbon and oxygen isotopic data in the samples. The Z values range from 96.65 to 121.5‰, suggesting the formation of siderite under brackish-water conditions. The T values vary from 19.47 to 47.12 °C, with some sharp fluctuations that may be due to ash falls and/or hydrothermal injections. Overall, our data support the model for critical-metal Nb(Ta)-Zr(Hf)-REY-Ga enrichment in tuffaceous deposits of southwest China including a combination of volcanic activity and terrestrial organic-rich sedimentation under warm and humid conditions, followed by low-temperature alteration evolved from acidic leaching, which is responsible for the Nb-Zr-REY-Ga enrichment, and, subsequently, formation of authigenic siderite with associated quartz, sulfide minerals, and phosphate minerals under reducing neutral/weakly alkaline conditions.