Calibration of redox thresholds in black shale: Insight from a stratified Mississippian basin with warm saline bottom waters

Abstract

Depositional models for black shale formation rely on a detailed understanding of redox conditions and how they relate to basin development. Here, we calibrate multiple redox proxies (Fe speciation, U and Mo systematics, and pyrite framboid distributions) in the Bowland Shale, a major hydrocarbon unit in the Mississippian basin of northern England, and develop a depositional model for black shale deposition in basins adjacent to extensive carbonate platforms. The transition from deep ramp carbonates to basinal mudrocks initially occurred under oxic conditions before anoxic conditions began to expand from basin-center locations. By the end of Bowland Shale deposition, ∼10 m.y. later, black shale deposition extended from the basin, where platform-edge carbonates were deposited, into shallow-water settings. By this stage, euxinic conditions were widespread throughout the Bowland Shale. The prolonged persistence of euxinia during younger Bowland Shale deposition, and the sharp transition to fully oxygenated facies at the basin margin, suggest there was a well-developed water-column pycnocline. Black shale development in silled basins is traditionally interpreted to form beneath a halocline with a positive water balance caused by freshwater run-off (estuarine circulation). This model is not considered appropriate in this case. Bowland Shale deposition was terminated by the onset of turbidite deposition supplied by a major deltaic system; but for most of its history, the basin was surrounded by carbonate platforms that are unlikely to have experienced brackish conditions. The encroachment of the clastic system saw the rapid improvement of basinal oxygenation in the uppermost Bowland Shale, and even minor turbidite sandstones within the black shales coincided with a weakening in the intensity of euxinia, which suggests that fresher, sediment-laden waters flushed out and oxygenated the basin. We therefore suggest a warm saline bottom-water model for black shale deposition, with basinal waters generated on the adjacent carbonate platforms due to evaporation. Such a scenario is likely more broadly applicable to basinal black shales that developed adjacent to shallow-water carbonate successions.