Clifford C. Walters

The second edition of The Biomarker Guide is a fully updated and expanded version of this essential reference. Now in two volumes, it provides a comprehensive account of the role that biomarker technology plays both in petroleum exploration and in understanding Earth history and processes. Biomarkers and Isotopes in the Environment and Human History details the origins of biomarkers and introduces basic chemical principles relevant to their study. It discusses analytical techniques, and applications of biomarkers to environmental and archaeological problems. The Biomarker Guide is an invaluable resource for geologists, petroleum geochemists, biogeochemists, environmental scientists and archaeologists.

A combination of solid-state 13C NMR, X-ray photoelectron spectroscopy (XPS) and sulfur X-ray absorption near edge structure (S-XANES) techniques are used to characterize organic oxygen, nitrogen, and sulfur species and carbon chemical/structural features in kerogens. The kerogens studied represent a wide range of organic matter types and maturities. A van Krevelen plot based on elemental H/C data and XPS derived O/C data shows the well established pattern for type I, type II, and type III kerogens. The anticipated relationship between the Rock−Eval hydrogen index and H/C is independent of organic matter type. Carbon structural and lattice parameters are derived from solid-state 13C NMR analysis. As expected, the amount of aromatic carbon, measured by both 13C NMR and XPS, increases with decreasing H/C. The correlation between aromatic carbon and Rock−Eval Tmax, an indicator of maturity, is linear for types II and IIIC kerogens, but each organic matter type follows a different relationship. The average aliphatic carbon chain length (Cn‘) decreases with an increasing amount of aromatic carbon in a similar manner across all organic matter types. The fraction of aromatic carbons with attachments (FAA) decreases, while the average number of aromatic carbons per cluster (C) increases with an increasing amount of aromatic carbon. FAA values range from 0.2 to 0.4, and C values range from 12 to 20 indicating that kerogens possess on average 2- to 5-ring aromatic carbon units that are highly substituted. There is basic agreement between XPS and 13C NMR results for the amount and speciation of organic oxygen. XPS results show that the amount of carbon oxygen single bonded species increases and carbonyl−carboxyl species decrease with an increasing amount of aromatic carbon. Patterns for the relative abundances of nitrogen and sulfur species exist regardless of the large differences in the total amount of organic nitrogen and sulfur seen in the kerogens. XPS and S-XANES results indicate that the relative level of aromatic sulfur increases with an increasing amount of aromatic carbon for all kerogens. XPS show that the majority of nitrogen exists as pyrrolic forms in comparable relative abundances in all kerogens studied. The direct characterization results using X-ray and NMR methods for nitrogen, sulfur, oxygen, and carbon chemical structures provide a basis for developing both specific and general average chemical structural models for different organic matter type kerogens.

The second edition of The Biomarker Guide is a fully updated and expanded version of this essential reference. Now in two volumes, it provides a comprehensive account of the role that biomarker technology plays both in petroleum exploration and in understanding Earth history and processes. Biomarkers and Isotopes in Petroleum Exploration and Earth History itemizes parameters used to genetically correlate petroleum and interpret thermal maturity and extent of biodegradation. It documents most known petroleum systems by geologic age throughout Earth history. The Biomarker Guide is an invaluable resource for geologists, petroleum geochemists, biogeochemists, and environmental scientists

The pore size distribution and architecture in gas shales were studied using a combination of small-angle neutron scattering (SANS), mercury injection capillary pressure (MICP), and helium ion microscopy (HIM). SANS analysis shows that the pore size population is not a power-law distribution across many length scales, typical of sedimentary rocks, but contains an anomalous population of pores on-the-order ∼2 nm, housed primarily in the organic matter. A model is presented showing how a “foamy porosity” with such a characteristic size is a direct result of diagenetic evolution of kerogen. Cross-linking of the kerogen combined with phase separation of gas/oil, leads to arrested coarsening with a length scale set by the cross-length density. These pore populations determined by the scattering model are directly supported by HIM images. Pore connectivity determined through pore-size-to-pore-throat analysis, suggests that interpore connections are also distinct from typical sedimentary rocks. The pore/throat ratio, unlike the simple ratios predicted from sphere packing and found for clastic rocks, is nearly constant over all pore sizes. Kerogen diagenesis is a recognized source of excess internal pressure. When this pressure causes failure of the material surrounding the kerogen to create escape pathways for the phase-separated fluid, it is likely that escape pathways will connect intergranular porosity via microfractures, producing the relatively narrow aperture size distribution.