Linking Redox Processes and Black Shale Resource Potential
2019
Black shales, such as the Mississippian (~330 Ma) Bowland Shale Formation, are targets for unconventional hydrocarbon exploration in the UK and in equivalents across Europe. Despite this interest, global decarbonisation, by definition, will either require; (1) complete replacement of natural gas with renewables and nuclear power generation, or; (2) moderate to limited natural gas use globally or locally, for example as a ‘bridge fuel’, as a source for hydrogen via steam reformation, or coupled to carbon capture and storage (CCS) technology. Any of these scenarios will increase the demand for transition metals such as V, Co and Ni, key elements used for energy storage and as catalysts in steam reformation. Black shales in general can host ore-grade enrichments in these metals, although the exact resource potential of UK Mississippian black shales remains unresolved.
We integrate comprehensive sedimentological and geochemical data from three sections through the Bowland Shale in the Craven Basin (Lancashire, UK) to explore the links between controls on hydrocarbon and metal prospectivity. The Bowland Shale at these sites is a highly heterogeneous and complex ~120 m thick succession comprising carbonate-rich, siliceous and siliciclastic, argillaceous mudstones. These sedimentary facies developed in response to a combination of high-frequency (~111 kyr) sea level changes, fault activity at the basin margins and linkage with the nearby prograding Pendle delta system.
Palaeoredox proxies such as Fe-speciation, redox-sensitive trace elements and S isotope analysis from extracted pyrite (δ34Spy) demonstrate intervals associated with metal enrichment were deposited under anoxic and at least intermittently euxinic (sulphidic) bottom water conditions. Trace element enrichment ‘V scores’ (sum of V+Mo+Se+Ni+Zn in ppm) indicate the greatest enrichments in these key transition metals and non-metals are associated with deposition under strongly sulphidic conditions during marine transgressions. V scores in these intervals are often >400 ppm and sometimes >1000 ppm. These bulk enrichments are comparable to stratiform low-grade ores such as the Upper Mudstone Member of the Devonian Popovich Formation (Nevada, USA). Hosts for these metals likely include solid sulphides such as pyrite, organic matter and possibly phosphates or carbonates.
Critically, a process of switching between ferruginous and euxinic conditions in anoxic porewaters, termed ‘redox oscillation’, is recognised by a distinctive redox-sensitive trace element enrichment pattern, particularly competition between V and Ni metalation. Redox oscillation operated during periods of reduced sea level, where an increased supply of reactive Fe to the basin promoted development of intermittently ferruginous conditions in bottom waters and early diagenetic porewaters. Therefore the distribution of many redox-sensitive elements through the Bowland Shale is predictable. If these elements can be efficiently extracted from the mineral or organic hosts, UK Mississippian black shales may represent a significant resource. This work also improves understanding of the potential for co-extraction of metals during hydraulic fracturing, or during remediation of waste water. Future work will seek to understand which minerals or organic compounds host these redox-sensitive trace elements.
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