Petrochemistry and Environmental Geochemistry of Shale and Coal from the Daedong Supergroup, Chungnam Coal Field, Korea

충남탄전, 대동누층군의 셰일과 탄질암에 관한 암석화학 및 환경지구화학적 특성

Characteristics of sedimentary rocks and enrichment of toxic elements in shale and coal from the Chungnam coal field were investigated based upon geochemistry of major, trace and rare earth elements. Shale and coal of the area are interbedded along the Traissic to the Jurassic Daedong Supergroup, which can be subdivided into grey shale, black shale and coal. The coal had been mined, however all the mines are abandonded due to the economic problems. The shale and coal are characterized by relatively low contents of $SiO_2$, and $Al_2O_3$ and high levels of loss-on-ignition (LOI), CaO and $Na_2O$ in comparison with the North American Shale Composite (NASC). Light rare earth elements (La, Ce, Yb and Lu) are highly enriched with the coal. Ratios of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in shale and coal range from 30.0 to 351.8 and from 4.2 to 106.8, which have partly negative correlations against $SiO_2/Al_2O_3$ (1.24 to 6.06), respectively. Those are suggested that controls of mineral compositions in shale and coal can be due to substitution and migration of those elements by diagenesis and metamorphism. Shale and coal of the area may be deposited in terrestrial basin deduced from high C/S (39 to 895) and variable composition of organic carbon (0.39 to 18.40 wt.%) and low contents of reduced sulfur (0.01 to 0.05 wt.%). These shale and coal were originated from the high grade metamorphic and/or igneous rocks, and the rare earth elements of those rocks are slightly influenced with diagenesis and metamorphism on the basis of $Al_2O_3$ versus La, La against Ce, Zr versus Yb, the ratios of La/Ce (0.38 to 0.85) and Th/U (3.6 to 14.6). Characteristics of trace and rare earth elements as Co/Th (0.07 to 0.86), La/Sc (0.31 to 11.05), Se/Th (0.28 to 1.06), V/Ni (1.14 to 3.97), Cr/V (1.4 to 28.3), Ni/Co (2.12 to 8.00) and Zr/Hf (22.6~45.1) in the shale and coal argue for inefficient mixing of the simple source lithologies during sedimentation. These rocks also show much variation in $La_N/Yb_N$ (1.36 to 21.68), Th/Yb (3.5 to 20.0) and La/Th (0.31 to 7.89), and their origin is explained by derivation from a mixture of mainly acidic igneous and metamorphic rocks. Average concentrations in the shale and coal are As=7.2 and 7.5, Ba=913 and 974, Cr=500 and 145, Cu=20 and 26, Ni=38 and 35, Pb=30 and 36, and Zn=77 and 92 ppm, respectively, which are similar to those in the NASC. Average enrichment indices for major elements in the shale (0.79) and coal (0.77) are lower than those in the NASC. In addition, average enrichment index for rare earth elements in coal (2.39) is enriched rather than the shale (1.55). On the basis of the NASC, concentrations of minor and/or environmental toxic elements in the shale and coal were depleted of all the elements examined, excepting Cr, Pb, Rb and Th. Average enrichment indices of trace and/or potentially toxic elements (As, Cr, Cu, Ni, Pb, U and Zn) are 1.23 to 1.24 for shale and 1.06 to 1.22 for coal, respectively.