Trace metal records of regional paleoenvironmental variability in Pennsylvanian (Upper Carboniferous) black shales

Abstract

Regional geochemical differences within a laterally continuous, cyclic Pennsylvanian (Upper Carboniferous) shale in midcontinent North America are interpreted in light of models of glacioeustatic forcing and new views on water-column paleoredox stability and trace-metal behavior in black shale environments. Specifically, we characterize differences in transition metal (Fe, Mn, Mo, V, Ni, Zn, Pb and U) concentrations in black shales of the Hushpuckney Shale Member of the Swope Limestone in Iowa and equivalent black shale beds of the Coffeyville Formation in Oklahoma. Although C–S–Fe systematics and uniform 34S-depleted isotope ratios of pyrite indicate pervasive euxinic deposition (anoxic and sulfidic bottom waters) for these shales, regional variations can be inferred for the efficiency of Mo scavenging and for the rates of siliciclastic sedimentation as expressed in spatially varying Fe/Al ratios. Black shales in Iowa show Mo enrichment roughly five times greater than that observed in coeval euxinic shales in Oklahoma. By contrast, Fe/Al ratios in Oklahoma shales are as much as five times greater than the continental ratio of 0.5 observed in the over- and underlying oxic facies and in the coeval black shales in Iowa. Recent work in modern marine settings has shown that enrichments in Fe commonly result from scavenging in a euxinic water column during syngenetic pyrite formation. In contrast to Fe, the concentrations of other transition metals (Mo, V, Ni, Pb, Zn, U) are typically more enriched in the black shales in Iowa relative to Oklahoma. The transition metal trends in these Paleozoic shales are reasonably interpreted in terms of early fixation in organic-rich sediments due to euxinic water-column conditions. However, regional variations in (1) rates of siliciclastic input, (2) organic reservoirs, including relative inputs of terrestrial versus marine organic matter, and (3) additional inputs of metals to bottom waters from contemporaneous hydrothermal vents are additional key controls that lead to geographic variation in the extent of metal enrichments preserved in ancient organic-rich sediments.