Chemical analysis and geochemical associations in Devonian black shale core samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee

Core samples from Devonian shales from five localities in the Appalachian Basin have been analyzed for major, minor, and trace constituents. The contents of major elements are rather similar; however, the minor constituents, organic C, S, PO4, and CO3, show variations by a factor of 10. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As, and Mn show variations that can be related graphically and statistically to the minor constituents. Down-hole plots show the relationships most clearly. Mn is associated with CO3 content, the other trace elements are strongly Controlled by organic C. Amounts of organic C are generally in the range of 3-6 percent, and S is in the range of 2-5 percent. Trace-element amounts show the following general ranges (ppm, parts per million)- Co, 20-40; Cu,40-70; U, 10-40; As, 20-40, V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, whereas the organic C and sulfide S created an environment for preservation or immobilization of trace elements. Closely spaced samples showing an abrupt transition in color from black to gray and gray to black shale show similar effects of trace-element changes, that is, black shale contains enhanced amounts of organic C and trace elements. Ratios of trace elements to organic C or sulfide S were relatively constant even though deposition rates varied from 10 to 300 meters in 5 million years.