Controls on amorphous organic matter type and sulphurization in a Mississippian black shale

Emmings, Joseph F.; Hennissen, Jan A.I.; Stephenson, Michael H.; Poulton, Simon W.; Vane, Christopher H.; Davies, Sarah J.; Leng, Melanie J.; Lamb, Angela; Moss-Hayes, Vicky

Abstract

Paleoredox proxies (Fe speciation, trace element and δ34Spy) integrated with sedimentological and palynological observations link the distribution and type of particulate organic matter (OM) preserved to hydrocarbon source rock potential. In the Mississippian Bowland Shale Formation (Lancashire, UK), particulate OM is dominated by “heterogeneous” amorphous OM (AOM), primarily “sharp-edged, pellet-like” (AOMpel) and “heterogeneous, granular” (AOMgr) types. AOMpel is abundant in muds deposited under anoxic and moderately to highly sulphidic conditions and most likely represents the fecal minipellets of zooplankton and/or pellets of macro-zooplankters. We recognize two intervals, “A” and “B,” which exhibit Sorg/TOC > 0.04, suggesting a bulk Type II-S kerogen composition. The Interval A palynofacies is typified by pyritized AOMpel (AOMpyr) particles that contain high-relief organic spheres surrounding individual pyrite framboids, within each AOMpyr particle. These textures are interpreted as sulphurized OM local to pyrite framboids (Sorg-PF). Sorg-PF is rarely observed in Interval B, and absent in all other samples. Redox oscillation between ferruginous and euxinic conditions during early diagenesis of Interval A likely promoted S cycling in microenvironments surrounding pyrite framboids, which generated reactive S species and reactive OM required for sulphurization. Early diagenetic redox oscillation processes were apparently triggered by relative sea level fall, associated with an increased supply of FeHR from adjacent shelves into the basin. Interval B represents deposition during the late stages of basin infill and transition from anoxic to (sub)oxic bottom waters, where AOMpel is replaced by AOMgr as the dominant type of AOM. A large particle diameter at the limit of the mesh size (500 μm), sheet-like, fragmented character, and presence of candidate organic sheaths suggests AOMgr at least partially represent fragments of benthic microbial mats, probably as sulphide-oxidizers. A ternary plot of AOMpel + AOMpyr versus AOMgr versus spores + phytoclasts links the observed palynofacies to bottom and pore water redox conditions, water column productivity and proximity to fluvial (deltaic) supply of spores and phytoclasts. These variables were moderated by changing basin accommodation, driven primarily by eustatic sea level fluctuation. A sequence-stratigraphic control on AOM type and sulphurization is important for understanding the link between source rock heterogeneity and the timing of hydrocarbon generation and expulsion from this source rock.

• Journal Article Type: Article
• Acceptance Date: Apr 2, 2019
• Online Publication Date: Apr 5, 2019
• Publication Date: 2019-09
• Deposit Date: Jun 13, 2019
• Publicly Available Date: Jun 13, 2019
• Journal: Review of Palaeobotany and Palynology
• Print ISSN: 0034-6667
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 268
• Pages: 1-18
• DOI: https://doi.org/10.1016/j.revpalbo.2019.04.004
• Keywords: Palaeontology; Ecology, Evolution, Behavior and Systematics
• Public URL: https://nottingham-repository.worktribe.com/output/2184702
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S0034666718302859
• Additional Information: This article is maintained by: Elsevier; Article Title: Controls on amorphous organic matter type and sulphurization in a Mississippian black shale; Journal Title: Review of Palaeobotany and Palynology; CrossRef DOI link to publisher maintained version: https://doi.org/10.1016/j.revpalbo.2019.04.004; Content Type: article; Copyright: © 2019 UKRI, as represented by its component body, the British Geological Survey/ The University of Leicester. Published by Elsevier B.V.