PALEOPRODUCTIVITY AND GEOCHEMICAL PROXIES: INDICATORS OF WATER-COLUMN CONDITIONS, FRASNIAN-FAMENNIAN BOUNDARY, NEW ALBANY SHALE, INDIANA
In addition to high concentrations of major elements Al, Na, Mn, and Ti, Frasnian green-gray shales are enriched in trace metals: Nb, Ru, Th, Ba, and La. Si and K values are slightly more elevated than those in the overlying Famennian shales whereas Corg, P, Ni, and C/N values are much lower. Oxic bottom-water conditions are indicated by low trace-element redox indicators (Mo, Ni+Co, V/Cr). Acritarchs, considered remains of normal marine phytoplankton, dominate the samples.
Trace-metal and major elemental data confirm major shifts in watercolumn conditions across the boundary. Famennian shales contain significant amounts of Corg, P, and N, and have elevated C/N ratios. The shales are enriched in trace metals: U, Mo, Cu, Ni, Pb, V, and Zn. High Mo contents and V/Cr and V/(V + Ni) redox proxies imply dysoxic-anoxic conditions during sediment accumulation. Green algae (notably Tasmanites) predominated surface waters. Sporadic Zn and low La concentrations as well as rare spores and wood, and the small size of black phytoclasts (<20 µm) indicate a distal, basinal setting during the Famennian.
Changes in C/N, δ13C, and Corg values across the boundary suggest metal enrichment may be dependent upon OM type as well as water-column conditions. This is directly related to a significant shift from acritarch- to prasinophyte-sourced OM. Biogeochemical proxies and palynological data signify a direct influence by phytoplankton on nutrient and elemental distributions, as well as a direct response by phytoplankton to changing paleoceanographic chemistry during times of black shale formation in the Upper Devonian Illinois Basin.