Date of Award

8-1-2014

Degree Name

Doctor of Philosophy

Department

Environmental Resources & Policy

First Advisor

Rimmer, Susan

Abstract

Igneous intrusion can change the geochemical and petrographic properties of sedimentary organic matter (such as coals and organic-rich clays or shales) including vitrinite reflectance, maceral petrographic composition, mineralogy, stable isotope composition, trace element composition, and bulk geochemistry. Igneous intrusions into coals and organic-rich rocks may have contributed to global warming in the geologic past by causing the release of greenhouse gases. Evidence for the release of large amounts of thermogenic CH4 from the organics would include significant;13Corg enrichment in the residual organic matter. However, 13Corg of thermally altered organic matter in coals and shales adjacent to intrusions often show negative shifts and, in some cases, ambiguous or positive trends. Previous studies have evaluated 13Corg of bulk samples rather than that of individual components, or macerals. As different macerals have different isotopic compositions, maceral-specific trends may be masked by variations in maceral composition of the whole-coal samples. It is important to explain the evolution of different geochemical and petrographic signatures in coals, coals macerals, and organic-rich sedimentary rocks close to an intrusion. This study evaluates the following three hypotheses: (1) thermally altered coals show different geochemical trends compared with coals that have undergone normal burial maturation; (2) if a large-scale release of 13C-depleted thermogenic CH4 resulted from intrusion of the coal, then it should have produced 13C-enriched coal and vitrinite macerals (the most abundant components of the coal) adjacent to the intrusion due to the release of light gases; and (3) 13Corg gets heavier with the increase in heat alteration approaching an intrusion due to the release of isotopically light gases. The current study reports petrographic, bulk geochemical (proximate, and ultimate), 13Corg data (whole-coal/shale samples and vitrinite macerals separated via density-gradient centrifugation, (DGC)), density data (vitrinite macerals), and Rock-Eval pyrolysis data for occurrences of thermally altered Springfield (No. 5) Coal (Pennsylvanian), Danville (No. 7) Coal (Pennsylvanian), and an organic-rich shale in the southern part of the Illinois Basin. Petrographic analysis shows an increase in vitrinite reflectance (Rm) from background levels of 0.55% up to ~4.80% in the Springfield (No. 5) Coal, 0.66% to 4.40% in the Danville (No. 7) Coal, and 0.71% to 4.78% for organic-rich shale; a loss of liptinite macerals, formation of isotropic coke and, at the intrusion contact, even development of fine-grained mosaic anisotropic coke texture. Volatile matter (VM) content decreases and fixed carbon (FC) content, ash, and mineral matter increase approaching the coal/intrusion contact. Carbon increases whereas nitrogen, hydrogen, and oxygen decrease approaching the intrusions. The presence of carbonate minerals (confirmed by X-ray diffraction and petrographic analysis) has a significant impact on proximate and ultimate data. However, even after removal of carbonates, trends for VM vs. vitrinite reflectance, %C vs. Rm, and H vs. C do not follow typical trends associated with normal burial coalification. Approaching the contacts, free oil content (S1), remaining hydrocarbon potential (S2), carbon dioxide from pyrolysis of the organic matter (S3), and hydrogen (HI) and oxygen (OI) indices decrease whereas thermal maturity (Tmax, ⁰C) increases. In addition, HI vs. VM, S2 vs. Rm, and Tmax vs. Rm diverge from pathways seen in previous studies. Trends in most of the Rock-Eval parameters in the organic-rich shale studied here are less clear due to the degree of variation in organic matter content, but a clear increase in thermal maturity (Tmax, C) is seen. There are no significant changes in 13Corg in the whole-coal samples (WCM) of the Springfield (No. 5) Coal (-25.28 / to -24.88 /), Danville (No. 7) whole coals (-25.37 / to -24.76 /), and in the DGC-separated vitrinites (-25.33 / to -24.96 /) of the Springfield (No. 5) Coal approaching the intrusion. However, the organic-rich shale transect shows a 1.31 / positive shift in 13C (from -25.06 / to -23.87 /) approaching the intrusion. DGC-separated vitrinite densities range from 1.268 g/mL in the unaltered coal to 1.523 g/mL at the coal/intrusion contact. For the vitrinite concentrates, density shows a clear correlation with Rm, %Cdaf, Hdaf, H/C, TOC, and 13Corg. These geochemical data suggest that these coals may have followed a different maturation track because of the geologically rapid heating associated with the intrusive event. It is also suggested here that the natural coke textures produced by such rapid geological heating may differ from those observed for metallurgical cokes produced under standard industrial coking conditions. Typically, in an industrial coke oven, a coal of this initial rank (Ro = ~ 0.6%) would produce an isotropic coke, rather than the fine-grained circular anisotropic coke seen here. The development of this texture may reflect differences due to heating rates or, alternatively, may indicate "pre-heating" of the coal during the intrusion event. Changes in the isotopic signatures are not of a magnitude that would be expected if significant thermogenic CH4 had been generated by the intrusive event. Moreover, there is no petrographic evidence for condensed or immobilized thermal products due to rapid pyrolysis (12C-rich pyrolytic carbon) close to the intrusion. These geochemical and petrographic data suggest there was only minimal CH4 generation associated with the rapid heating of the coals and organic-rich sedimentary rocks by the intrusion. In addition, there is no evidence for 13C-depleted condensed gas or pyrolytic carbon at the intrusion contact that could have moderated the isotopic signature. These data agree with previously reported data from this laboratory (Rahman et al., 2014, in review) and others (Gröcke et al., 2009; Yoksoulian, 2010) that indicate no clear evidence for large-scale CH4 generation due to the rapid heating or igneous intrusion in coals or sedimentary rocks.

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