Utah State University DigitalCommons@USU Reports Utah Water Research Laboratory January 1983 Polycyclic Aromatic Hydrocarbons: Are They a Problem in Processed Oil Shales? David L. Maase V. Dean Adams Follow this and additional works at: https://digitalcommons.usu.edu/water_rep Part of the Civil and Environmental Engineering Commons, and the Water Resource Management Commons Recommended Citation Maase, David L. and Adams, V. Dean, "Polycyclic Aromatic Hydrocarbons: Are They a Problem in Processed Oil Shales?" (1983). Reports. Paper 232. https://digitalcommons.usu.edu/water_rep/232 This Report is brought to you for free and open access by the Utah Water Research Laboratory at DigitalCommons@USU. It has been accepted for inclusion in Reports by an authorized administrator of DigitalCommons@USU. For more information, please contact [email protected]. POLYCYCLIC AROMATIC HYDROCARBONS-- ARE THEY A PROBLEM IN PROCESSED OIL SHALES? David L. Maase V. Dean Adams The research on which this report is based was financed in part by the U.S. Department of the Interior, as authorized by the Water Research and Development Act of 1978 (P.L. 95-467). Project No. B-154-UTAH, Contract No. 14-34-0001-8123 WATER QUALITY SERIES UWRL/Q-83/07 Utah Water Research Laboratory Utah State University Logan, Utah 84322 May 1983 Contents of this publication.do not necessarily reflect the views and policies of the U. S. Department of the Interior nor does mention of trade names or commercial products constitute their endorsement or recommendation for use by the U.S. Government. it ABSTRACT Organic residues from processed oil shales were character­ ized with specific attention to polycyclic aromatic hydrocarbons (PAR). Oil shale development in the White River Basin (Utah and Colorado) was projected i1and hydrological and geological param­ eters pertinent to estimations of polycyclic aromatichydrocar­ bons (PAR) flux,were focused. Oil shale samples from the Union B, Paraho, and Tosco II processes were extracted by using organic solvents in a soxhlet apparatus and by mixing shale samples with water (characterization of in situ shales, as mined shales and alluvial samples are also included). Literature reported organic chemistry isolation and identification regimes (applicable to gas, liquid and solid samples) were summarized in a tabular format ('V 50 examples). Selected 3 through 6 ring aromatic hydrocarbons were also characterized in a tabular format ('V 100 examples). More than 100 organic compounds from processed oil shales were identified by gas chromatography coupled with mass spectrometry (GC/MS). Four and 5 ring PAR, i.e., fluor­ anthrene, pyrene, triphenylene, benz(a)anthracene, chrysene, benzo(e)pyrene, perylene, and benzo(a)pyrene, respectively were found to be benzene extractable from processed shales in concen­ trations ranging from <1 to >50 ppb (weight of each PAR/weight shale). These PAR were detected in water extracts at levels below their respective solubilities. Preliminary aqueous chlori­ nation studies using selected 3 to 5 ring PAR resulted in re­ ductions of more than 90 percent for anthracene and pyrene after 1 hour of mixing with >10 mg/l free available chlorine at a pR of 8.0 to 8.5. Reductions of phenanthrene, triphenylene, and benz(a)anthracene were only about 15 to 25 percent after 15 hours of mixing. As a best estimate, fluoranthrene and the study 5 ring PAR concentrations were only reduced by about 50 percent in 15 hours. iii ACKNOWLEDGMENTS We would like to acknowledge the Office of Water Research and Technology (Project No. B-154-UTAH, Contract No. 14-34-0001- 8123), United States Department of the Interior, Washington, D.C., which provided funds for this research (WG 215), as author­ ized by the Water Research and Development Act of 1978, and the State of Utah (WR 215) for providing matching funds. The authors express their appreciation to the Utah Water Research Laboratory, L. Douglas James, Director, for providing the laboratory equipment and facilities necessary to complete this study and to the editorial and secretarial staff for their assistance in preparation and publication of this report. iv TABLE OF CONTENTS Page INTRODUCTION 1 Objectives 2 Hydrology and Geology of Oil Shale Areas 2 In-place Oil Shale Characteristics 9 Industrial Development 15 Water and Land Requirements 22 Shale Waste Characterization 24 Retort oils characterization 25 Retorted shale characterization 33 MATERIALS AND METHODS 49 Extraction of Organics 50 Isolation Approaches 52 Water Extractions 53 GC/MS and GC Identification 54 RESULTS AND DISCUSSION 59 GC/MS of Organic Soxhlet Extracts 59 GC/MS of TLC Fractions 59 GC/MS of Water Extracts. 66 Quantification of Identified PAR in Spent Shale Samples 68 Chlorination Study Results 68 Laboratory Limits to Aqueous Investigation of 5 Ring PAR . 73 CONCLUSIONS AND RECOMMENDATIONS 77 REFERENCES 81 APPENDICES 99 Appendix A: Supporting Data 99 Appendix B: Summary of Organic Chemistry Extraction and Identification Regimes Reported in . the Literature 131 Appendix C: Characterization of Selected Polycyclic Aromatic Hydrocarbons 142 v LIST OF FIGURES Figure Page 1. Oil shale lands--Green River Formation 3 2. Geologic (Uinta and Piceance Basins) and hydrologic (White River Basin, Utah and Colorado) location map of the oil shale regions 5 3. Isoerodent map, R contours, for White River Basin. 8 4. General scheme of oil shale components (adopted from Yen 1975), schematic section of oil shale (Yen 1977), and chemical analysis of a Green River oil shale (Yen and Chilingarian 1976) 11 5. Atomic ratio diagram for selected kerogens and coal macerals as related to other organic materials • 12 6. Components and bridges of a Green River oil shale kerogen (Yen 1976), and kerogen structure of Green River oil shale (Young and Yen 1977) 13 7. Flow diagram for the Tosco II process. 17 8. Flow diagram of the Paraho process 19 9. Moisture content as a function of percent saturation and dry density for Tosco II processed shale 38 10. Typical gas-liquid chromatogram of oil shale polynuclear aromatic fraction 40 11. Example of a gas chromatogram of a pentane soxhlet extraction of processed shale 56 12. GC/MS ion chromatograph of benzene soxhlet leachates. 60 13. Gas chromatogram comparisons of a standard PAR mixture and a 0.6 to 0.8 Rf TLC fraction 64 14. Summary of organic extraction 65 15. GC trace of benzene extracted processed shale before and after water leaching • 67 16. Gas chromatogram comparison of an XAD-2 developed processed shale compared to known PAR .standard • 69 vii LIST OF TABLES Table Page 1. Known available estimates of organic fuel resources 1 2. Estimate of Green River oil shale resources. 2 3. Results of federal oil shale lease offerings 4 4. Summary of Utah and Colorado oil shale area hydrology. 7 5. Summary of geologic units and their water bearing characteristics; a portion of a USGS atlas key . 10 6. Composition of bitumens in Green River oil shale 14 7. Derived relationships relating shale components to the Modified Fisher Assay . 15 8. Comparison of organic carbon and the Modified Fisher Assay of specific Green River Mahogany zone shales to reported world values 15 9. Current oil shale development projects 18 10. Associated operation material balances of planned oil shale developments 20 11. Summary of water needs for oil shale development 22 12. One estimate of needs and summary of water avail­ ability for oil shale ~evelopment in Colorado, Utah, and Wyoming 23 13. Waste characterization of oil shale industry related waters 26 14. Characterization of shale industry related oils 30 15. Physical properties of retorted shale 34 16. Macro elemental characterization of retorted shales 35 17. Permeabilities found in various shale disposal areas. 37 18. Organic carbon content and other disposal character- istics of processed shales 38 ix LIST OF TABLES (CONTINUED) Table Page 19. Polycyclic aromatic hydrocarbons detected 39 20. Particulate polycyclic organic matter (paM) compounds identified in benzene extract of carbonaceous shale coke from Green River oil shale 41 21. Polycondensed aromatic hydrocarbons identified in benzene extracts of carbonaceous spent shale from the Tasca process • 42 22. Evaluation of benzo(a)pyrene (BaP) content in samples of benzene extracts from various spent shale, soils, plants, and leached salt samples 43 23. Evaluation of benzo(a)pyrene (BaP) content in samples of benzene extracts from direct mode retorted shales. 44 24. Benzene and water extractables of retorted shale, and raw shale particulates • 45 25. Summary of electrolytic treatment of retort water. 46 26. Summary of sample characteristics 51 27. Summary of GC/MS study standards 55 28. Identified benzene leachables 61 29. Summary of PARs identified in TLC 0.6 to 0.8 Rf fraction 65 30. Summary of derived indicator relationships (TOC, EC, VS, TDS) of various oil shale leachates and White River water 67 31. Summary of quantification of organic and water de- veloped shale samples 70 32. Summary of standard PAR L/L extraction efficiency and removal chlorination 71 33. Summary of selected PAR concentration in selected waters 75 34. Comparison of human exposure to 3 to 5 ring PAR from other sources with concentrations estimated in drinking water downstream from oil shale areas 79 x INTRODUCTION It is expected that the amount of Recent es t imates of the abundance energy needed in the United States of 0 il shale reserves In the Green will continue to increase In the River Basin of Colorado, Wyoming, and foreseeable future and that the relative Utah, validate the USGS 1915 report. ability of crude oil and gas to meet The Green River oil shales contain a the s e need s wi 11 dec 1 in e • Th us, major percentage of the world's organic alternative sources of fuel must be fuel resources, as shown in Table 1 explored, including synthetic fuel (Hendrickson 1975; Slawson 1979; Slawson produced from marls tone deposits (oil and Yen" 1979) • shale).