Trace and rare earth element geochemistry of the black and grey shales of the Calabar Flank, Southeastern Nigeria: constraints on the depositional environment and the degree of metal enrichment

This study focuses on the trace and rare earth elements (REE) geochemistry of the Nkporo and Ekenkpon Shales of the Calabar Flank. The main aim is to infer their depositional environment and the degree of their metal enrichment. The shale samples were analyzed using inductively coupled plasma mass spectrometry. The results indicated that the mean concentrations of K, Na, and Fe in Nkporo and Ekenkpon Shales are 1.45, 0.4, and 4.17 wt%, and 1.11, 0.44, and 5.42 wt%; respectively. The Nkporo Shale is enriched with the following trace elements; P > Mn > Sr > Ba > Zn > Ce > Rb > Zr > V>Cr > Ni and depleted in the following trace elements; Ta > Ge > Sb > Bi > Cd > Ag > Te > In > Hg. While the Ekenkpon Shale is enriched with the following trace elements; P > Mn > Ba > Sr > V>Ce > Zr > Rb > Cr > Zn > Ni and depleted in; Sb > Ge > Bi > Ag > Ce > Te > In > Hg. The concentration of redox-sensitive elements such as V, Ni, Mo, U, Cu, Cr, Re, Cd, Sb, Ti, Mn, and their ratio V/Mo and U/Mo in the black and grey shale samples show different patterns. The REE obtained from the Nkporo and Ekenkpon Shales were PAAS normalized. The Nkporo Shale showed a slightly flat light rare-earth element (LREE), middle rare-earth element (MREE), and heavy rare earth element (HREE) pattern enrichment. Ce/Ce* ranges from 0.95 to 1.09 in Nkporo Shale and 0.67 to 1.40 in Ekenkpon Shale. The Ekenkpon Shale showed a slight LREE, MREE enrichment, and depleted HREE patterns. The Mn contents and U/Mo ratio in Nkporo and Ekenkpon Shales suggests a poor oxygen transitional environment. The V/Mo and V/(V + Ni) ratios indicated that the Nkporo shales were deposited in an anoxic to suboxic conditions and Ekenkpon shales were also deposited under an anoxic to suboxic conditions. The V/Ni ratio indicated that the organic matter in the Nkporo shale is terrigenous while that of the Ekenkpon shales are both terrigenous and marine in origin.