Hydrous pyrolysis (HP) experimentation is a laboratory method used to thermally mature organic-rich sedimentary rocks. It simulates petroleum generation in the closest available analogue to that of a natural system. Artificial maturation of sedimentary organic matter (SOM) to petroleum allows for the examination of its molecular chemistry to address the issue of anomalous reflection measurement and further decipher the petroleum generation process. Investigation of these topics is broadly applicable to the assessment of undiscovered oil and gas resources process and to improving the understanding of the geologic history in petroleum systems and basin analysis worldwide.
Objectives:
The compositional diversity and complexity of SOM prevents the use of one simple kinetic and mechanical model of its conversion to petroleum. Predictive models of petroleum generation therefore rely on evidence from individual case studies to use as an analogue to document the compositional and physical evolution of different SOM types during thermal maturation. Because a variety of factors influence SOM conversion to petroleum, models using case study analogue data may not fully capture the processes involved in petroleum generation. For example, the organic maceral vitrinite undergoes an increase in reflectance of incident light with increasing thermal maturity. In some cases, however, vitrinite reflectance is suppressed relative to expected values. These suppressed values cause difficulties determining the burial history of source rocks and the subsequent timing and extent of petroleum generation.
One objective of this research is to determine the maturation kinetics, as expressed through organic reflectance, of SOM through HP experimentation. The results from this research may be used to reduce uncertainties in burial history modeling and petroleum resource assessments. Another objective is to characterize the in situ physical and chemical transformation of SOM to petroleum under different conditions (such as time or temperature) and in different environments (such as hydrous, anhydrous, or brine) using spectroscopy techniques. The goal of this effort is to improve understanding of the effects that the starting materials and microenvironment have on the chemical parameters of petroleum generation.
Listed below are other science projects or tasks associated with this project.
Petrographic Thermal Indices Research
Vitrinite Reflectance Service
Thermal Indices Innovation
Standardization of Petrographic Thermal Indices
Listed below are data products associated with this project.
Textural occurrence and organic porosity of solid bitumen in shales
TOC, Reflectance and Raman Data from Eocene Green River Mahogany Zone
Solid bitumen and vitrinite reflectance suppression explored using hydrous pyrolysis of artificial source rock (2021)
Reflectance, Raman band separation and Mean multivariant curve resolution (MCR) in organic matter in Boquillas Shale
Petroleum geology data from hydrous and anhydrous pyrolysis residues for coals and shales from the Cambrian through the Miocene (ver. 2.0, January 2023)
Listed below are publications associated with this project.
Reply to Comment by M.D. Lewan
Relating systematic compositional variability to the textural occurrence of solid bitumen in shales
Maturation study of vitrinite in carbonaceous shales and coals: Insights from hydrous pyrolysis
Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy
Molecular mechanisms of solid bitumen and vitrinite reflectance suppression explored using hydrous pyrolysis of artificial source rock
Hydrous pyrolysis of New Albany Shale: A study examining maturation changes and porosity development
Compositional evolution of organic matter in Boquillas Shale across a thermal gradient at the single particle level
Relating Tmax and hydrogen index to vitrinite and solid bitumen reflectance in hydrous pyrolysis residues: Comparisons to natural thermal indices
An integrated geochemical, spectroscopic, and petrographic approach to examining the producibility of hydrocarbons from liquids-rich unconventional formations
Experimental study on the impact of thermal maturity on shale microstructures using hydrous pyrolysis
Application of Raman spectroscopy as thermal maturity probe in shale petroleum systems: Insights from natural and artificial maturation series
Suppression of vitrinite reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial source rock
- Overview
Hydrous pyrolysis (HP) experimentation is a laboratory method used to thermally mature organic-rich sedimentary rocks. It simulates petroleum generation in the closest available analogue to that of a natural system. Artificial maturation of sedimentary organic matter (SOM) to petroleum allows for the examination of its molecular chemistry to address the issue of anomalous reflection measurement and further decipher the petroleum generation process. Investigation of these topics is broadly applicable to the assessment of undiscovered oil and gas resources process and to improving the understanding of the geologic history in petroleum systems and basin analysis worldwide.
Objectives:
The compositional diversity and complexity of SOM prevents the use of one simple kinetic and mechanical model of its conversion to petroleum. Predictive models of petroleum generation therefore rely on evidence from individual case studies to use as an analogue to document the compositional and physical evolution of different SOM types during thermal maturation. Because a variety of factors influence SOM conversion to petroleum, models using case study analogue data may not fully capture the processes involved in petroleum generation. For example, the organic maceral vitrinite undergoes an increase in reflectance of incident light with increasing thermal maturity. In some cases, however, vitrinite reflectance is suppressed relative to expected values. These suppressed values cause difficulties determining the burial history of source rocks and the subsequent timing and extent of petroleum generation.
One objective of this research is to determine the maturation kinetics, as expressed through organic reflectance, of SOM through HP experimentation. The results from this research may be used to reduce uncertainties in burial history modeling and petroleum resource assessments. Another objective is to characterize the in situ physical and chemical transformation of SOM to petroleum under different conditions (such as time or temperature) and in different environments (such as hydrous, anhydrous, or brine) using spectroscopy techniques. The goal of this effort is to improve understanding of the effects that the starting materials and microenvironment have on the chemical parameters of petroleum generation.
- Science
Listed below are other science projects or tasks associated with this project.
Petrographic Thermal Indices Research
A petrographic thermal index is typically an organic matter indicator in sedimentary rocks that allows for estimations of burial temperature. Petrographic thermal indices include the commonly used proxy vitrinite reflectance as well as other approaches such as solid bitumen reflectance, fluorescence, micro-Raman, and micro-Fourier transform infrared (FTIR) spectroscopies. Measurements from these...Vitrinite Reflectance Service
Vitrinite is a maceral group that is derived from the remains of woody material from vascular plants and is composed of the thermally evolved products of lignin and cellulose. A maceral group is a set of organic matter types with similar properties and appearance. Vitrinite reflectance measures the percentage of incident light that is reflected from the surface of vitrinite as calibrated to a...Thermal Indices Innovation
Thermal indices innovation focuses on the utilization of correlative microscopy and spectroscopy techniques for innovative approaches to advance the understanding of thermal indices development. These techniques include correlative light and electron microscopy (CLEM), confocal laser scanning microscopy (CLSM), and atomic force microscopy and infrared microscopy (AFM-IR), among others. Use of...Standardization of Petrographic Thermal Indices
Advent of the shale revolution since about 2005 caused increased demand for reliable petrographic measurements of thermal maturity in shale via vitrinite reflectance, which has long been considered the gold standard approach. The first standardized methodology for vitrinite reflectance measurement in shale became available in 2011. Subsequent interlaboratory studies demonstrated that significant... - Data
Listed below are data products associated with this project.
Textural occurrence and organic porosity of solid bitumen in shales
This study presents Raman spectroscopic data paired with scanning electron microscopy (SEM) to assess solid bitumen composition and porosity development as a function of solid bitumen texture and association with minerals. A series of hydrous pyrolysis experiments (1-103 days, 300-370°C) using a low maturity (0.25% solid bitumen reflectance, BRo), high total organic carbon [(TOC), 14.0 wt. %] NewTOC, Reflectance and Raman Data from Eocene Green River Mahogany Zone
Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of exchangeable hydrogen from water, organic-rich (22 wt. percent total organic carbon, TOC) mudrock sampleSolid bitumen and vitrinite reflectance suppression explored using hydrous pyrolysis of artificial source rock (2021)
The most commonly used parameter for thermal maturity calibration in basin modelling is mean random vitrinite reflectance (Ro). However, Ro suppression, or lower than expected Ro, has been noted in samples containing a high proportion of liptinite macerals. This has been empirically demonstrated using hydrous pyrolysis experiments of artificial source rock containing various proportions of thermalReflectance, Raman band separation and Mean multivariant curve resolution (MCR) in organic matter in Boquillas Shale
The molecular composition of petroliferous organic matter and its composition evolution throughout thermal advance are key to understanding and insight into petroleum generation. This information is critical for comprehending hydrocarbon resources in unconventional reservoirs, as source rock organic matter is highly dispersed, in contact with the surrounding mineral matrix, and may be present as mPetroleum geology data from hydrous and anhydrous pyrolysis residues for coals and shales from the Cambrian through the Miocene (ver. 2.0, January 2023)
This data release contains programmed pyrolysis, organic petrographic (reflectance), and semiquantitative X-ray diffraction mineralogy data for subsurface coal and shale samples from around the world. Samples were subjected to hydrous or anhydrous pyrolysis experiments at varying temperatures and the resulting residues were analyzed via programmed pyrolysis and reflectance to document changes in t - Publications
Listed below are publications associated with this project.
Filter Total Items: 17Reply to Comment by M.D. Lewan
No abstract available.AuthorsK.E. Peters, Paul C. Hackley, A.E. PomerantzRelating systematic compositional variability to the textural occurrence of solid bitumen in shales
This study presents Raman spectroscopic data paired with scanning electron microscopy (SEM) images to assess solid bitumen composition as a function of solid bitumen texture and association with minerals. A series of hydrous pyrolysis experiments (1–103 days, 300–370 °C) using a low maturity (0.25% solid bitumen reflectance, BRo), high total organic carbon [(TOC), 14.0 wt%] New Albany Shale sampleAuthorsMartha (Rebecca) Stokes, Brett J. Valentine, Aaron M. Jubb, Paul C. HackleyMaturation study of vitrinite in carbonaceous shales and coals: Insights from hydrous pyrolysis
The presence of vitrinite in sedimentary rocks of post-Silurian age allows its reflectance to be used to estimate the thermal maturation of organic matter in petroleum systems. Increasing reflectance of vitrinite, which is primarily driven by aromaticity, depends primarily on the time and temperature attributes of its evolutionary pathway. This study evaluated carbonaceous shales proximal to coalAuthorsDivya K. Mishra, Paul C. Hackley, Aaron M. Jubb, Margaret M. Sanders, Shailesh Agrawal, Atul K. VarmaEvaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy
Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon, TOC) mudrock samples from the Eocene lacAuthorsPaul C. Hackley, Aaron M. Jubb, Patrick L. Smith, Ryan J. McAleer, Brett J. Valentine, Javin J. Hatcherian, Palma J. Botterell, Justin E. BirdwellMolecular mechanisms of solid bitumen and vitrinite reflectance suppression explored using hydrous pyrolysis of artificial source rock
The most commonly used parameter for thermal maturity calibration in basin modelling is mean random vitrinite reflectance (Ro). However, Ro suppression has been noted in samples containing a high proportion of liptinite macerals. This phenomenon has been demonstrated empirically using hydrous pyrolysis of artificial source rock containing various proportions of thermally immature Wyodak-Anderson cAuthorsMargaret M. Sanders, Aaron M. Jubb, Paul C. Hackley, Kenneth E. PetersHydrous pyrolysis of New Albany Shale: A study examining maturation changes and porosity development
The characterization of nanoscale organic structures has improved our understanding of porosity development within source-rock reservoirs, but research linking organic porosity evolution to thermal maturity has generated conflicting results. To better understand this connection, an immature (0.25% solid bitumen reflectance; BRo) sample of the New Albany Shale was used in four isothermal hydrous pyAuthorsBrett J. Valentine, Paul C. Hackley, Javin J. HatcherianCompositional evolution of organic matter in Boquillas Shale across a thermal gradient at the single particle level
The molecular composition of petroliferous organic matter and its compositional evolution throughout thermal maturation provides insight for understanding petroleum generation. This information is critical for understanding hydrocarbon resources in unconventional reservoirs, as source rock organic matter is highly dispersed, in contact with the surrounding mineral matrix, and may occur as multipleAuthorsJustin E. Birdwell, Aaron M. Jubb, Paul C. Hackley, Javin J. HatcherianRelating Tmax and hydrogen index to vitrinite and solid bitumen reflectance in hydrous pyrolysis residues: Comparisons to natural thermal indices
Vitrinite reflectance (VRo; %) generally is considered the most reliable technique to determine the thermal maturity of sedimentary rocks. However, it is a time-consuming process to collect reflectance (Ro; %) measurements and is subjective to the interpretation of each trained technician, who must be able to discern between vitrinite and solid bitumen and other organic matter types. Inadvertent mAuthorsCeleste D. Lohr, Paul C. HackleyAn integrated geochemical, spectroscopic, and petrographic approach to examining the producibility of hydrocarbons from liquids-rich unconventional formations
The geochemical and petrophysical complexity of source-rock reservoirs in liquids-rich unconventional (LRU) plays necessitates the implementation of a more expansive analytical protocol for initial play assessment. In this study, original samples from selected source-rock reservoirs in the USA and the UK were analyzed by 22 MHz nuclear magnetic resonance (HF-NMR) T1-T2 mapping, followed by hydrousAuthorsThomas Gentzis, Humberto Carvajal-Ortiz, Z. Harry Xie, Paul C. Hackley, Hallie FowlerExperimental study on the impact of thermal maturity on shale microstructures using hydrous pyrolysis
Hydrous pyrolysis was applied to four low-maturity aliquots from the Utica, Excello, Monterey, and Niobrara Shale Formations in North America to create artificial maturation sequences, which could be used to study the impact of maturation on geochemical and microstructural properties. Modified Rock-Eval pyrolysis, reflectance, organic petrology, and Fourier transform infrared spectroscopy (FTIR) wAuthorsKouqi Liu, M. Ostadhassan, Paul C. Hackley, T. Gentzis, J. Zou, Y. Yuan, H. Carvajal-Ortiz, R. Rezaee, B. BubachApplication of Raman spectroscopy as thermal maturity probe in shale petroleum systems: Insights from natural and artificial maturation series
Raman spectroscopy was studied as a thermal maturity probe in a series of Upper Devonian Ohio Shale samples from the Appalachian Basin spanning from immature to dry gas conditions. Raman spectroscopy also was applied to samples spanning a similar thermal range created from 72-h hydrous pyrolysis (HP) experiments of the Ohio Shale at temperatures from 300 to 360 °C and isothermal HP experiments lasAuthorsPaul C. Hackley, N. Keno LunsdorfSuppression of vitrinite reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial source rock
Mean random vitrinite reflectance (Ro) is the most widely accepted method to determine thermal maturity of coal and other sedimentary rocks. However, oil-immersion Ro of polished rock or kerogen samples is commonly lower than Ro values measured in samples from adjacent vitrinite-rich coals that have undergone the same level of thermal stress. So-called suppressed Ro values have also been observedAuthorsKenneth E. Peters, Paul C. Hackley, J. J. Thomas, A. E. Pomerantz