• Economic and Environmental Geology
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• v.30 no.5
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• pp.417-431
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• 1997

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.

• Economic and Environmental Geology
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• v.8 no.3
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• pp.117-124
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• 1975

Wet chemical analysis (for $MnO_2$, MnO, and $H_2O$(+)) and electron microprobe analysis (for $Fe_2O_3$ and PbO) give $MnO_2$ 74.91, MnO 11.33, $Fe_2O_3$ (total Fe) 4.19, PbO 0.03, $H_2O$ (+) 9.46, sum 99.92%. 'Available oxygen determined by oxalate titration method is allotted to $MnO_2$ from total Mn, and the remaining Mn is calculated as MnO. Traces of Ba, Ca, Mg, K, Cu, Zn, and Al were found. Li and Na were not found. The existence of (OH) is verified from the infrared absorption spectra. The analysis corresponds to the formula $Mn^{4+}{_{4.85}}(Mn^{2+}{_{0.90}}Fe^{3+}{_{0.30}})_{1.20}O_{8.09}(OH)_{5.91}$, on the basis of O=14, 'or ideally $Mn^{4+}{_{5-x}}(Mn^{2+},Fe^{3+})_{1+x}O_{8}(OH)_{6}$ ($x{\approx}0.2$). X-ray single crystal study could not be made because of the distortion of single crystals. But the x-ray powder pattern is satisfactorily indexed by an orthorhombic cell with a 9.324, b 14.05, c $7.956{\AA}$., Z=4. The indexed powder diffraction lines are 9.34(s) (100), 7.09(s) (020), 4.62(m) (200, 121), 4.17(m) (130), 3.547(s) (112), 3.212(vw) (041), 3.101(s) (300), 2.597(w) (013), 2.469(m) (331), 2.214(vw)(420), 2.098(vw) (260), 2.014 (vw) (402), 1.863(w) (500), 1.664(w) (314), 1.554(vw) (600), 1.525(m) (601), 1.405(m) (0.10.0). DTA curve shows the endothermic peaks at $250-370^{\circ}C$ and $955^{\circ}C$. The former is due to the dehydration: and oxidation forming$(Mn,\;Fe)_2O_3$(cubic, a $9.417{\AA}$), and the latter is interpreted as the formation of a hausmannite-type oxide (tetragonal, a 5.76, c $9.51{\AA}$) from $(Mn,\;Fe)_2O_3$. Infrared absorption spectral curve shows Mn-O stretching vibrations at $515cm^{-1}$ and $545cm^{-1}$, O-H bending vibration at $1025cm^{-1}$ and O-H stretching vibration at $3225cm^{-1}$. Opaque. Reflectance 13-15%. Bireflectance distinct in air and strong in oil. Reflection pleochroism changes from whitish to light grey. Between crossed nicols, color changes from yellowish brown with bluish tint to grey in air and yellowish brown to grey through bluish brown in oil. No internal reflections. Etching reactions: HCl(conc.) and $H_2SO_4+H_2O_2$-grey tarnish; $SnCl_2$(sat.)-dark color; $HNO_3$(conc.)-grey color; $H_2O_2$-tarnish with effervescence. It is black in color. Luster dull. Cleavage one direction perfect. Streak brownish black to dark brown. H. (Mohs) 2-3, very fragile. Specific gravity 3.59(obs.), 3.57(calc.). It occurs as radiating groups of flakes, flower-like aggregates, colloform bands, dendritic or arborescent masses composed of fine grains in the cementation zone of the supergene manganese oxide deposits of the Janggun mine, Bonghwa-gun, southeastern Korea. Associated minerals are calcite, nsutite, todorokite, and some undetermined manganese dioxide minerals. The name is for the mine, the first locality. The mineral and name were approved before publication by the Commission on New Minerals and Mineral Names, I.M.A.