Stable isotope, chemical, and mineral compositions of the Middle Proterozoic Lijiaying Mn deposit, Shaanxi Province, China

The Lijiaying Mn deposit, located about 250 km southwest of Xian, is a high-quality ore characterized by low P and Fe contents and a mean Mn content of about 23%. The ore deposit occurs in shallow-water marine sedimentary rocks of probable Middle Proterozoic age. Carbonate minerals in the ore deposit include kutnahorite, calcite, Mn calcite, and Mg calcite. Carbon (−0.4 to −4.0‰) and oxygen (−3.7 to −12.9‰) isotopes show that, with a few exceptions, those carbonate minerals are not pristine low-temperature marine precipitates. All samples are depleted in rare earth elements (REEs) relative to shale and have negative Eu and positive Ce anomalies on chondrite-normalized plots. The Fe/Mn ratios of representative ore samples range from about 0.034 to <0.008 and P/Mn from 0.0023 to <0.001. Based on mineralogical data, the low ends of those ranges of ratios are probably close to ratios for the pure Mn minerals. Manganese contents have a strong positive correlation with Ce anomaly values and a moderate correlation with total REE contents. Compositional data indicate that kutnahorite is a metamorphic mineral and that most calcites formed as low-temperature marine carbonates that were subsequently metamorphosed. The braunite ore precursor mineral was probably a Mn oxyhydroxide, similar to those that formed on the deep ocean-floor during the Cenozoic. Because the Lijiaying precursor mineral formed in a shallow-water marine environment, the atmospheric oxygen content during the Middle Proterozoic may have been lower than it has been during the Cenozoic.