Xiaowei Zheng Hamed Sanei Fujie Jiang Qingyong Luo Ye Wang Jennifer L. Nedzweckas Brett J. Valentine M. Rebecca Stokes Liu Cao Paul C. Hackley 20250205 tabular digital data Reston, Virginia U.S. Geological Survey https://doi.org/10.5066/P1FOPMCI Xiaowei Zheng Hamed Sanei Fujie Jiang Qingyong Luo Ye Wang Jennifer L. Nedzweckas Brett J. Valentine M. Rebecca Stokes Liu Cao Paul C. Hackley 202506 publication International Journal of Coal Geology vol. 306 n/a Elsevier BV ppg. 104793 https://doi.org/10.1016/j.coal.2025.104793 A series of gold tube pyrolysis experiments (72 hrs, 300–600 °C) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm, namely granular, non-granular, and nodular graptolite. Raman spectroscopy in combination with organic petrology and field emission scanning electron microscopy (FE-SEM) was used to evaluate the thermal evolution process. The three types of graptolite periderm were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Raman spectroscopy, a non-destructive and rapid microstructural analysis technique, has recently emerged as a powerful tool for assessing the thermal maturity of source rocks (Ferralis et al., 2016; Kelemen and Fang, 2001). Applicability of these Raman thermal proxies has been extended to various OM types by correlating the Raman spectral parameters with traditional thermal maturity proxies, such as reflectance and pyrolysis Tmax (Liu et al., 2013; Wilkins et al., 2014; Morga and Pawlyta, 2018), and has thus proven to be useful in determining thermal maturity. This data release makes publicly available the Raman spectroscopy parameters included in the study described in the larger work, Relating systematic molecular and textural properties of graptolite pyrolyzed via gold tube experiments: implications for thermal proxies in lower Paleozoic marine shales. The purpose of this data is to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore the limitations of using specific thermal maturity parameters. The commonly used Raman spectroscopy parameters D1, G-FWHM, and ratios like D1 FWHM/G FWHM and D1/G amplitude (AD1/AG) from this work are compared with previously published data to discuss their utility in evaluating the aromaticity of graptolites and the associated alteration of organic molecular structure during gold tube pyrolysis. Improvement of understanding of these thermal maturity proxies will have significant geological importance for accurate determination of thermal maturity and basin modelling in pre-Devonian sedimentary basins. The file contains data available in comma separated value (.csv) file format. The user must have software capable of opening and viewing a .csv file. 2025 ground condition Complete None planned 22.5000 27.5000 59.5000 57.5000 ISO 19115 Topic Category geoscientificInformation None - Free Keywords Raman spectroscopy graptolite thermal evolution marine shale pyrolysis USGS Thesaurus thermal maturation Paleozoic Devonian sedimentary USGS Metadata Identifier USGS:6793e20ad34e72688d6b71e1 Common geographic areas Estonia None. Please see 'Distribution Info' for details. None. Users are advised to read the dataset's metadata thoroughly to understand appropriate use and data limitations. Paul C. Hackley U.S. Geological Survey, Northeast Region Research Geologist mailing and physical

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Reston VA 20192 USA 703-648-6458 phackley@usgs.gov National Key Laboratory of Petroleum Resources and Engineering, China University of Petroleum, Beijing 102249, China College of Geosciences, China University of Petroleum, Beijing 102249, China Lithospheric Organic Carbon (LOC) Group, Department of Geoscience, Aarhus University, 8000, Denmark School of Earth Science and Resources, Key Laboratory of Western Mineral Resources and Geological Engineering of Ministry of Education, Chang’an University, Xi’an, 710054, China Nicola Ferralis Emily D. Matys Andrew H. Knoll Christian Hallmann Roger E. Summons 20161101 Volume 108, Pages 440-449 publication online Elsevier Carbon https://doi.org/10.1016/j.carbon.2016.07.039 Simon R. Kelemen H. L. Fang 20010328 Volume 15, Issue 3, Pages 653-658 publication online ACS Publications Energy Fuels http://dx.doi.org/10.1021/ef0002039 DeHan Liu XianMing Xiao Hui Tian YuShun Min Qin Zhou PengCheng JiaGui Shen 20121212 Volume 58, Pages 1285-1298 publication online Signature Nature Link Chinese Science Bulletin http://dx.doi.org/10.1007/s11434-012-5535-y Ronald W.T. Wilkins Roger Boudou Neil Sherwood Xianming Xiao 20140801 Volumes 128-129, Pages 143-152 publication Online Elsevier International Journal of Coal Geology https://doi.org/10.1016/j.coal.2014.03.006 Rafat Morga Microstawa Pawlyta 20180315 Volume 189, Pages 1-7 publication online Elsevier International Journal of Coal Geology https://doi.org/10.1016/j.coal.2018.02.012 No formal attribute accuracy tests were conducted. No formal logical accuracy tests were conducted. Data set is considered complete for the information presented, as described in the abstract and process steps. Users are advised to read the rest of the metadata record carefully for additional details. No formal positional accuracy tests were conducted. No formal positional accuracy tests were conducted. Jia Wu Wen Qi Fu-Jie Jiang Qing-Yong Luo Chun-Lin Zhang Huan-Zhen Hu Zi Wang Qi-Sheng Ma Yong-Chun Tang 20211215 Volume 18, Issue 6, Pages 1611-1618 publication online KeAi: Chinese Roots Global Impact Petroleum Science https://doi.org/10.1016/j.petsci.2021.09.029 Digital and/or Hardcopy 20211215 publication date Wu et al., 2021 Gold tube pyrolysis methodology Xiao Jin Jia Wu Renzo C. Silva Haiping Huang Zhihuan Zhang Ningning Zhong Benjamin M. Tutolo Steve Larter 20211015 Volume 302 publication online Elsevier Fuel https://doi.org/10.1016/j.fuel.2021.121050 Digital and/or Hardcopy 20211015 publication date Jin et al., 2021 Gold tube pyrolysis methodology Brett J. Valentine Paul C. Hackley Javin Hatcherian Jing-Jiang Yu 20190102 Volume 201, Pages 86-101 publication online Elsevier International Journal of Coal Geology https://doi.org/10.1016/j.coal.2018.11.004 Digital and/or Hardcopy 20190102 publication date Valentine et al., 2019 Raman spectral parameters and analysis Ting Wu Chunxiang Lu Tongqing Sun Yonghong Li 20220813 Volume 57, Pages 15385-15412 publication online Springer Nature Link Journal of Materials Science http://dx.doi.org/10.1007/s10853-022-07589-8 Digital and/or Hardcopy 20220813 publication date Wu et al., 2022 Raman spectra fitting Gold Tube Pyrolysis A lower Ordovician Tremadocian graptolite-rich Alum Shale core sample collected from Estonia was artificially matured by gold tube pyrolysis to generate a series of pyrolyzed residue samples with different maturity levels. The gold tube pyrolysis experiments were conducted in the State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum-Beijing. The original immature core sample (crushed and sieved to the size range of 1.5–2.5 mm) was loaded into gold tubes (length 40 mm and inner diameter 5.5 mm and 0.25 mm in thickness), together with isovolumetric deionized water, and sealed under an argon atmosphere. The isothermal pyrolysis temperatures were from 300 to 550℃ for 72 h under a hydrostatic pressure of 50 MPa (Jin et al., 2021; Wu et al., 2021). The same samples were observed with white light, grayscale, and blue light fluorescence, and maps of the sample surfaces were created to aid navigation among different fragments of graptolite (i.e., granular, non-granular, nodular), and to guide subsequent Raman analysis (e.g., Valentine et al., 2019). Raman spectral parameters from the three types of graptolite periderm (non-granular, granular, nodular) are presented in this data release. Jin et al., 2021 Wu et al., 2021 Valentine et al., 2019 2024 Raman microscopy Spectra were collected on a Horiba Xplora Plus Raman microscope system at the U.S. Geological Survey (USGS) Raman Spectroscopy Lab in Reston, VA. The setting of experimental parameters included a 532 nm laser with perpendicular polarization, 1200 groove/mm spectral grating, 300 μm confocal pinhole diameter, 100 μm spectrometer slit, with ~75 μW laser power delivered at the sample surface through a 100× objective with a numerical aperture of 0.9. Each analysis was collected across a spectral range of 109–2706 cm-1 in three accumulations of 12 to 15 s. Peak positions, intensities, and widths were averaged over the number of measurements, and the mean and standard deviations are presented. The laser spot size was conservatively estimated to be 1 μm in diameter at the sample surface and the measurement locations were checked post-analysis to ensure that no damage occurred from the laser. Spectra were fit across a range of 800–2000 cm-1 using a linear background function and a sum of five Lorentzian peak functions representing the D4, D1, D3, D2 and G peaks (Wu et al., 2022). Wu et al., 2022 2024 Raman spectral parameters of pyrolyzed samples for three types of graptolites.csv Comma Separated Value (CSV) file containing data. Producer Defined Sample ID Sample identifier Producer Defined Sample identifier Graptolite type Classification of the graptolite sample, either granular, nodular or non-granular Producer Defined granular Granular graptolite type Producer defined nodular Nodular graptolite type Producer defined non-granular Non-granular graptolite type Producer defined n Number of measurements for the sample Producer Defined 2 6 count 1 D1-peak position (cm-1) Wavenumber position of the D1 peak in the Raman spectrum Producer Defined 1353 1368 inverse centimeters 1 D1-peak position SD (cm-1) Standard deviation of the D1 peak position Producer Defined 0.38 3.00 inverse centimeters 0.01 G-peak position (cm-1) Wavenumber position of the G peak in the Raman spectrum Producer Defined 1574 1585 inverse centimeters 1 G-peak position SD (cm-1) Standard deviation of the G peak position Producer Defined 0.16 5.46 inverse centimeters 0.01 G-FWHM (cm-1) Full width at half maximum of the G peak Producer Defined 52.83 87.49 inverse centimeters 0.01 G-FWHM SD (cm-1) Standard deviation of the G-FWHM measurements Producer Defined 0.27 5.83 inverse centimeters 0.01 D1FWHM/GFWHM Ratio of the full width at half maximum of the D1 peak to the G-FWHM Producer Defined 1.25 2.50 ratio 0.01 AD1/AG Ratio of the D1 and G peak intensities Producer Defined 0.58 1.36 ratio 0.01 U.S. Geological Survey - ScienceBase mailing address

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Denver CO 80225 United States 1-888-275-8747 sciencebase@usgs.gov Unless otherwise stated, all data, metadata and related materials are considered to satisfy the quality standards relative to the purpose for which the data were collected. Although these data and associated metadata have been reviewed for accuracy and completeness and approved for release by the U.S. Geological Survey (USGS), no warranty expressed or implied is made regarding the display or utility of the data for other purposes, nor on all computer systems, nor shall the act of distribution constitute any such warranty. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. Digital Data https://doi.org/10.5066/P1FOPMCI None 20251204 Jeremy K Ray U.S. Geological Survey - Northeast Region Data Scientist mailing and physical

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Reston VA 20192 United States 703-648-6415 jray@usgs.gov FGDC Content Standard for Digital Geospatial Metadata FGDC-STD-001-1998