Elsevier

Organic Geochemistry

Volume 98, August 2016, Pages 38-53
Organic Geochemistry

Lipid biomarker stratigraphic records through the Late Devonian Frasnian/Famennian boundary: Comparison of high- and low-latitude epicontinental marine settings

https://doi.org/10.1016/j.orggeochem.2016.05.007Get rights and content

Highlights

  • Biomarker records of Upper Kellwasser event at two paleolatitudes were compiled.

  • High C28/C29 sterane ratios suggest abundant prasinophytes at high paleolatitudes.

  • Very low abundances of Chlorobi-derived carotenoids were detected.

  • C/N/P relationships suggest chronic N-limitation despite high algal contributions.

Abstract

The pervasiveness of black shale preservation in association with Late Devonian biological crises suggests marine anoxia played a major role in driving ecological perturbations. However, Devonian black shale deposition is still mechanistically poorly understood. We have compiled detailed biomarker lipid chemostratigraphic records for 83 different rock samples using molecular constituents of bitumens of Upper Kellwasser equivalent black shales from two foreland basins: from the low paleolatitude Appalachian Basin (New York State) and from the high paleolatitude Madre de Dios Basin (Bolivia), in order to better understand local environmental conditions and organic source inputs during this depositional event. Despite strong indications from stable nitrogen isotopic signatures for fixed nitrogen nutrient limitation, the biomarker assemblages with consistently low-moderate hopane/sterane ratios (< 0.8) indicate that algae were major marine primary producers in both basins throughout the Frasnian/Famennian (F/F) stratigraphic coverage. Consistently higher C28/C29 sterane ratios at higher paleolatitude in the more nutrient-replete Madre de Dios Basin suggest prasinophyte microalgae flourished in this setting in accordance with palynological evidence for high contributions of Tasmanites cysts in these strata. All samples contain only very low absolute amounts of aryl isoprenoids (with 2,3,6-trimethyl substitution) and other aromatic carotenoids, up to several orders of magnitude lower than concentrations reported from other Phanerozoic euxinic basins. These data are consistent with local marine paleo-redox models for both basins lacking a persistently shallow sulfidic aquatic zone and demonstrate that temporally persistent or spatially pervasive photic zone euxinia is not necessarily associated with all black shale sequences in the Late Devonian.

Introduction

Organic-rich sedimentary rocks are prolific hydrocarbon (oil and gas) sources and, since their occurrences commonly correlate with mass extinction events throughout the Phanerozoic, the geochemical and fossil records preserved in these strata are of central interest to many paleoenvironmental studies (most recently, Lenniger et al., 2014, Rivera et al., 2015, Van Helmond et al., 2015). The details of the processes of black shale accumulation, however, are poorly understood and under continual debate (Tyson and Pearson, 1991, Harris, 2005, Tyson, 2005).

The Late Devonian is particularly known for its global abundance of organic-rich sedimentary facies that are associated with biotic events of varying magnitudes (House, 2002). Reconstructing these depositional environments is of particular value and interest to black shale research: unique continental configurations, with much of the continental masses concentrated near the equator (Golonka et al., 1994), coupled with high sea level stands and active orogenesis (notably the Acadian and Antler orogenies of Laurentia; Averbuch et al., 2005), created the ideal conditions for massive epeiric seaways, the loci for organic carbon burial. These global black shale depositional events characteristically occur in association with elevated extinction rates in marine fauna. The bio-event at the Frasnian/Famennian (F/F) stage boundary, the Kellwasser Event (Buggisch, 1991, House, 2002), which correlates with the deposition of the Upper Kellwasser bituminous limestone in Europe and organic rich facies globally, has been recognized as a mass extinction event (Raup and Sepkoski, 1982, McGhee, 1996, Bambach et al., 2004). Furthermore, research on the patterns of extinction, origination, and marine ecological selectivity coincident with black shale deposition in the Late Devonian suggest that the environmental processes driving diversity loss may have differed fundamentally from those mechanisms forcing mass extinction events in the Late Ordovician, Late Permian and Late Cretaceous, because the resultant ecosystem restructuring was distinct in its taxonomic impact and ecological fingerprint (Droser et al., 2000, Bambach, 2006, Alroy, 2008).

Because black shale facies are widely characterized as dysoxic or anoxic, studies of Devonian rocks have traditionally invoked spatially pervasive and temporally persistent marine anoxia as the likely mechanism for these biological perturbations (Joachimski and Buggisch, 1993, Becker and House, 1994, Joachimski et al., 2001, Levman and Von Bitter, 2002, Bond et al., 2004). There is a growing body of literature, however, suggesting a wider range of possible preservation and/or depositional conditions for black shales beyond the traditional interpretation of requiring a persistently anoxic water-column (Arthur and Sageman, 1994, Murphy et al., 2000a, Boyer and Droser, 2011, Boyer et al., 2011, Rivera et al., 2015). To better understand the range of environments in which black shales can be deposited and to reconstruct the settings for Devonian ecological perturbations, this study examines the microbial ecology and, to a lesser extent, the marine redox chemistry of two Late Devonian basins preserving Frasnian/Famennian black shale.

This study focuses on characterization of the lipid biomarker assemblages in bitumens for a large suite of oil window-mature Late Devonian rocks traversing the Upper Kellwasser Event of the Frasnian/Famennian extinction, from both high and low paleolatitude marine settings. Lipid biomarkers can yield valuable information pertaining to the origins of source organisms (particularly the assemblages of microbial aquatic primary producers which generally account for a high proportion of the biomarker signals in marine paleoenvironments), the thermal maturity of the host organic matter, and the paleoenvironmental conditions (redox, salinity, etc.) in the water column. Hopane/sterane ratios provide a broad but informative measure of bacterial/eukaryotic source inputs which can be compared with a large dataset for source rocks and oils of different geological ages, while sterane carbon number patterns reveal important insights about the major groups of marine algae functioning as important primary producers during Devonian time. Redox sensitive biomarkers, like pristane/phytane ratios and the aromatic carotenoid pigment molecule derived from lipids of green sulfur bacteria, isorenieratane, provide molecular evidence for the occurrence and persistence of anoxia and photic zone euxinia in the Late Devonian basins.

We also measured elemental ratios, including C, N and P, and stable carbon and nitrogen isotopic signatures to gauge important information about local redox conditions and nutrient cycling since microorganisms are the primary mediators of biogeochemical processes, and the relative abundances of eukaryotes and prokaryotes may drive disruptions to ecosystem functions linked to extinction events. For example, nitrogen cycling will differ significantly in an environment dominated by diazotrophic prokaryotes rather than algae, with important implications for primary production, trophic web dynamics and organic matter preservation. These data, in concert with the lipid biomarker stratigraphic record, illuminate the similarities and differences between the low-latitude Appalachian Basin and the high-latitude Madre de Dios Basin during the deposition of the Upper Kellwasser black shale at the Frasnian/Famennian boundary and highlight the marine ecological signatures characteristic of this turnover event.

Section snippets

Geological and sedimentological setting

This study characterizes depositional conditions of black shale deposits from the low-latitude Appalachian Basin of Laurentian (present-day New York State) and the high-latitude Madre de Dios Basin of Gondwana (present-day Bolivia). During the Late Devonian, the Appalachian Basin was situated in the sub-tropics (approximately 30 °S latitude), while the Madre de Dios Basin was at approximately 60 °S latitude (Scotese and McKerrow, 1990; Fig. 1), making a comparison between these two basins useful

Thermal maturity parameters

For a total of 18 Madre de Dios samples and the 65 Appalachian Basin samples, abundant rock bitumen extract (12–109 mg of total bitumen from 5–15 g of rock powder) was generated and a full complement of linear, branched and polycyclic hydrocarbon biomarkers, such as hopanes and steranes and their methylated homologs, was detected using MRM–GC–MS with high signal/noise ratios. Hopane and sterane maturity ratios are consistent with a mid-oil window stage of thermal maturity (Fig. 2); while most of

Conclusions

Detailed lipid biomarker stratigraphic records compiled for the Upper Kellwasser intervals for two different foreland epicontinental basins, from a low and high paleolatitude, indicated a stable marine microbial community, characterized by abundant eukaryotic phytoplankton, as indicated by low hopane/sterane ratios (consistently < 0.75). Consistently higher C28/C29 sterane ratios in the Madre de Dios Basin (average of 0.52), coupled with palynological evidence for abundant Tasmanites and

Acknowledgments

This work was funded principally by a National Science Foundation Earth Sciences Program grants to GDL (NSF-EAR 1348988) and DLB (NSF-EAR 1348981). GDL also thanks the Agouron Institute for grant support. EEH acknowledges graduate student support from the NSF GRFP, AAPG, SEPM, the Gulf Coast Section of SEPM, and the Paleontological Society. The authors are indebted to Sarah de la Rue for providing Pando X-1 core samples for geochemical analysis.

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