Trace and rare earth element geochemistry of phosphate nodules from the lower Cambrian black shale sequence in the Mufu Mountain of Nanjing, Jiangsu province, China

Phosphate nodules are abundant in the lowermost section of the Lower Cambrian black shale sequence along a NE-trend belt in the Yangtze Platform, south China. In this study, we examined the Neoproterozoic-Cambrian Mufu Mountain section near Nanjing of Jiangsu province, and conducted a detailed trace and rare earth element (REE) study on the phosphate nodules. We employed a step-leaching acid dissolution protocol of 1 M HAc and 1 M HCl, respectively, to separate carbonate from phosphate mineral contributions in the nodules. Both the HAc-leached and HCl-leached fractions of the phosphate nodules show similar symmetrical variations in trace and REE concentrations and ratios. The total REEs and a number of redox-sensitive trace metals such as V, Cr, Mo, Ni abundances show a systematic increase from the core to rim, whereas the U and Mn abundances decrease from the core to rim in most of the nodules. Similar trends are also observed for the Rb/Sr, U/Th, Co/Ni, and V/Ni ratios, but these trends in the HAc-leached fractions are less pronounced than the HCl-leached fractions. All of the HCl-leached fractions for the nodule cores show seawater-like shale-normalized REE patterns, but the rims of the nodules display slightly MREE-enriched and HREE-depleted patterns. We suggest that the phosphate nodules may have formed in a basinal setting beneath a stratified water column during Early Cambrian, and the compositional variations of REEs and redox-sensitive trace elements from the core to rim may record a changing redox condition and fluid mixing during different stages of nodule growth. The cores of the nodules preserve more pronounced negative Ce anomalies and progressively HREE-enriched patterns, which may retain primary Early Cambrian seawater chemistry, whereas the nodule rims record chemistry consistent with changed redox conditions and/or influences from pore fluids such as generated from degradation of organic matter.