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C.C. Walters

Publications and source records attributed to C.C. Walters.

3 recordsLinked to original sources

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (<3.4 sulfurs per 100 carbons) due to offsetting preservation and H2S elimination reactions. In contrast, TSR solid bitumens are sulfur rich and nitrogen poor solids. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (>3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Organic Geochemistry

Evaluation of kinetic uncertainty in numerical models of petroleum generation

Oil-prone marine petroleum source rocks contain type I or type II kerogen having Rock-Eval pyrolysis hydrogen indices greater than 600 or 300-600 mg hydrocarbon/g total organic carbon (HI, mg HC/g TOC), respectively. Samples from 29 marine source rocks worldwide that contain mainly type II kerogen (HI = 230-786 mg HC/g TOC) were subjected to open-system programmed pyrolysis to determine the activation energy distributions for petroleum generation. Assuming a burial heating rate of 1??C/m.y. for each measured activation energy distribution, the calculated average temperature for 50% fractional conversion of the kerogen in the samples to petroleum is approximately 136 ?? 7??C, but the range spans about 30??C (???121-151??C). Fifty-two outcrop samples of thermally immature Jurassic Oxford Clay Formation were collected from five locations in the United Kingdom to determine the variations of kinetic response for one source rock unit. The samples contain mainly type I or type II kerogens (HI = 230-774 mg HC/g TOC). At a heating rate of 1??C/m.y., the calculated temperatures for 50% fractional conversion of the Oxford Clay kerogens to petroleum differ by as much as 23??C (127-150??C). The data indicate that kerogen type, as defined by hydrogen index, is not systematically linked to kinetic response, and that default kinetics for the thermal decomposition of type I or type II kerogen can introduce unacceptable errors into numerical simulations. Furthermore, custom kinetics based on one or a few samples may be inadequate to account for variations in organofacies within a source rock. We propose three methods to evaluate the uncertainty contributed by kerogen kinetics to numerical simulations: (1) use the average kinetic distribution for multiple samples of source rock and the standard deviation for each activation energy in that distribution; (2) use source rock kinetics determined at several locations to describe different parts of the study area; and (3) use a weighted-average method that combines kinetics for samples from different locations in the source rock unit by giving the activation energy distribution for each sample a weight proportional to its Rock-Eval pyrolysis S2 yield (hydrocarbons generated by pyrolytic degradation of organic matter). Copyright ?? 2006. The American Association of Petroleum Geologists. All rights reserved.

American Association of Petroleum Geologists Bulle

Thermal maturity of Jurassic shales from the Newark Basin, U.S.A.: Influence of hydrothermal fluids and implications to basin modeling

Organic geochemical investigations were conducted on a series of cores that systematically sampled the uppermost Jurassic strata from the northern Newark Basin. Each sedimentary unit consists of fluvial red sandstones and siltstones with cyclic deposits of interbedded black lacustrine shales and gray deltaic siltstones. In a suite of organic-rich shales from the Boonton, Towaco and Feltville Formations, organic maturation parameters were used to determine aspects of the thermal history of the Newark Basin. Comparisons of model calculations and measured maturities support 39 Ar/ 40 Ar-geochronometer studies that indicate a hydrothermal event occurred ∼175 Ma ago. An increase in the regional geothermal gradient to ∼7.5°C/100 m for ∼5 Ma best conforms to the organic geochemical observations. Biomarker compounds in Boonton and Towaco strata should have been relatively unaltered by this regional event, but anomalous molecular distributions in the organic-rich rocks may have resulted from localized heating by hydrothermal fluids. The effects of this interaction would be very subtle and may be indistinguishable from variations caused by differences in organic facies. Within this uncertainty, sterane and hopane isomerization and steroid aromatization reactions advanced in the Boonton and Towaco Formation strata primarily because of burial and normal geothermal heating that followed the hydrothermal event. Biomarker kinetic models indicate that ∼2400 m of Boonton and post-Boonton strata were eroded after basinal uplift commenced ∼50 Ma ago.

Applied Geochemistry