Enhanced paleo-wildfire occurrences caused by marine organic carbon burial during the Late Devonian Frasnian–Famennian mass extinction

<p>The Frasnian–Famennian (F–F) boundary is characterized by worldwide depositions of organic-rich strata, a series of marine anoxia events and one of the biggest five mass extinction events of the Phanerozoic. Due to the enhanced burial of organic matter, a coeval positive carbon isotope (δ<sup>13</sup>C) excursion occurred around the F–F boundary, raising questions about carbon cycle feedbacks during the mass extinction. In this study, we test the hypothesis that enhanced burial organic carbon during the F–F mass extinction led to the rise of paleo-wildfire occurrences. Here, we reconstructed paleo-wildfire changes across the F–F boundary via analyzing fossil charcoal (inertinites) and pyrogenic polycyclic aromatic hydrocarbons (PAHs) from an Upper Devonian Chattanooga Shale in the southern Appalachian Basin. Our data show low abundances of inertinites and pyrogenic PAHs before the F–F transition and an increasing trend during the F–F transition, followed by a sustained enhancement through the entire Famennian interval. The changes in paleo-wildfire proxies suggest a rise of wildfires starting from the F–F transition. Furthermore, we quantified the amount of organic carbon burial required to drive the observed δ<sup>13</sup>C excursion using a forward box model. The modeling results show an increased carbon burial rate after the onset of the F–F transition and peaking during its termination. The comparison of the carbon burial rate and wildfire proxies indicates that widespread organic carbon burial during the F–F transition might cause elevated atmospheric oxygen levels and hence increased occurrences of wildfires. In addition, chemical index alteration index and plant biomarkers suggest a drying climate initiated during the F–F transition, implying that the enhanced carbon burial probably result in the climate change and amplify the wildfire occurrences.</p>

Biomarker evidence of algal-microbial community changes linked to redox and salinity variation, Upper Devonian Chattanooga Shale (Tennessee, USA)

Late Devonian marine systems were characterized by major environmental perturbations and associated biotic community changes linked to climate change and widespread oceanic anoxia. Here, we provide high-resolution lipid biomarker chemostratigraphic records from the Upper Devonian Chattanooga Shale (Tennessee, USA) to investigate algal-microbial community changes in the southern Illinois Basin that were related to contemporaneous shifts in marine redox (as proxied by trace metals, Fe-species, and Corg/P) and salinity conditions (as proxied by B/Ga, Sr/Ba, and S/total organic carbon). The Frasnian was characterized by dominantly bacterial lipids (high hopane/sterane), near-marine salinity, and a shift from oxic to increasingly reducing conditions in response to increasing organic carbon sinking fluxes. Aryl isoprenoids and aryl isoprenoid ratios reveal that the O2-H2S chemocline was unstable and intermittently shallow (i.e., within the photic zone). The Frasnian-Famennian boundary was marked by a shift in microalgal community composition toward green algal (e.g., prasinophyte) dominance (lower C27 and higher C28 and C29 steranes), a sharp reduction in watermass salinity, and a stable O2-H2S chemocline below the photic zone, conditions that persisted until nearly the end of the Famennian. We infer that changing watermass conditions, especially a sharp reduction in salinity to possibly low-brackish conditions (<10 psu), were the primary cause of concurrent changes in the microalgal community, reflecting tolerance of low-salinity conditions by green algae. Transient spikes in moretane/hopane (M/H) ratios may record enhanced terrestrial weathering at the Frasnian-Famennian and Devonian–Carboniferous boundaries, triggered by coeval glacio-eustatic falls and increased inputs of soil organic matter. High M/H and pristane/phytane, in combination with low chemical index of alteration and K/Al, record a decrease in chemical weathering intensity during the Famennian that may have been due to contemporaneous climatic cooling, and a concurrent reduction in silt content may reflect stabilization of land surfaces by vascular plants and resulting reduced sediment yields. This study demonstrates the effectiveness of combining organic and inorganic geochemical proxies (including novel paleosalinity indices) for determination of environmental controls on the composition and productivity of plankton communities in paleomarine systems.

Supplemental Material: Biomarker evidence of algal-microbial community changes linked to redox and salinity variation, Upper Devonian Chattanooga Shale (Tennessee, USA)

Table S1: original data of all proxies in this paper and concentration of each element and compound; Figure S2: Mass chromatograms of selected sample showing the distribution of (a) n-alkanes, (b) C27-C29 steranes and diasteranes (m/z 217), (c) Terpane m/z 191 fingerprint, (d) aryl isoprenoids (m/z 133 or 134).

Supplemental Material: Biomarker evidence of algal-microbial community changes linked to redox and salinity variation, Upper Devonian Chattanooga Shale (Tennessee, USA)

Table S1: original data of all proxies in this paper and concentration of each element and compound; Figure S2: Mass chromatograms of selected sample showing the distribution of (a) n-alkanes, (b) C27-C29 steranes and diasteranes (m/z 217), (c) Terpane m/z 191 fingerprint, (d) aryl isoprenoids (m/z 133 or 134).

Erratum to “A Perspective on Stratigraphic, Vertically-Upward “Displacements or Dislocations” of Conodont-Elements: An Example From the Upper Devonian, Pre-Lithified, Black Shales of the Chattanooga Shale Formation In Tennessee, USA” ...

Even though the author already incorporated the citation of Sinninghe-Damste & Schouten (2006) into the text of the paper, the author regrets having failed to include their full citation within the Reference Section of my above paper which is: Sinninghe-Damste, J. S. & Schouton, S. (2006). Biological markers for anoxia in the photic zone of the water column. In, Volkman, J. K. (ed.), Marine Organic Matter: Biomarkers, Isotopes and DNA, (pp. 127 – 163). The Handbook of Environmental Chemistry, vol. 2N. Springer: Berlin and Heidelberg. https://doi.org/10.1007/698_2_005 The author also needs to paraphrase a statement made in the last three lines of the 2nd paragraph on page 40 where it reads as: “Thus, we may conclude here that paleo-upfreezing of any conodont-element(s) originally buried in the pre-lithified, light-colored shale occurred in order to account for their presence in black shale”. Instead, in lieu of that statement, it should read as “At this point in time of the study, we may tentatively conclude here while completely concluding later in the study, that conodont-elements originally existing in the underlying, pre-lithified, light-colored shale, had to paleo-upfreeze vertically upward into pre-lithified, black shale sediment in order to account for their presence in lithified black shale”.

Erratum to “A Perspective on Stratigraphic, Vertically-Upward “Displacements or Dislocations” of Conodont-Elements: An Example From the Upper Devonian, Pre-Lithified, Black Shales of the Chattanooga Shale Formation In Tennessee, USA” ...

Even though the author already incorporated the citation of Sinninghe-Damste & Schouten (2006) into the text of the paper, the author regrets having failed to include their full citation within the Reference Section of my above paper which is: Sinninghe-Damste, J. S. & Schouton, S. (2006). Biological markers for anoxia in the photic zone of the water column. In, Volkman, J. K. (ed.), Marine Organic Matter: Biomarkers, Isotopes and DNA, (pp. 127 – 163). The Handbook of Environmental Chemistry, vol. 2N. Springer: Berlin and Heidelberg. https://doi.org/10.1007/698_2_005 The author also needs to paraphrase a statement made in the last three lines of the 2nd paragraph on page 40 where it reads as: “Thus, we may conclude here that paleo-upfreezing of any conodont-element(s) originally buried in the pre-lithified, light-colored shale occurred in order to account for their presence in black shale”. Instead, in lieu of that statement, it should read as “At this point in time of the study, we may tentatively conclude here while completely concluding later in the study, that conodont-elements originally existing in the underlying, pre-lithified, light-colored shale, had to paleo-upfreeze vertically upward into pre-lithified, black shale sediment in order to account for their presence in lithified black shale”.

A Perspective on Stratigraphic, Vertically-Upward “Displacements or Dislocations” of Conodont-Elements: An Example From the Upper Devonian, Pre-Lithified, Black Shales of the Chattanooga Shale Formation In Tennessee, USA

Stratigraphic “displacements or dislocations” are coarse clasts and / or objects (such as unaltered remains or conodont-elements) slowly mobilizing or migrating vertically upward through a fine-grained matrix by a cryogenetic process known as “upfreezing” due to freezing temperatures. The process was originally established by periglaciologists and cold-climate geomorphologists who applied it only to unconsolidated, sedimentary deposits. In this study, the process is applied to the marine, pre-lithified, black shales of the Upper Devonian, Chattanooga Shale Formation, specifically in Tennessee, USA. The importance of this recognition is to alert paleontologists and stratigraphers about the strong possibility of inaccurate age-determinations made concerning coarse objects such as a conodont-element (denticles) (but not fossilized molds) because of their fossilized presence in age-determined, stratigraphic, rock levels when the apatite-composed denticles may have instead been initially deposited at a lower stratigraphic level during pre-lithification of the fine-grained, host-rock (shale) before the paleo-upfreezing process mobilized the denticles upwards. Many lines of evidences are given in this study towards apparent, predominant, freezing temperatures in the pre-existing, Chattanooga Sea of the Appalachian Basin, including particular, supposed, bioturbated, pre-lithified, organic black shale that is reinterpreted here as cryoturbated, pre-lithified, organic, black shale.