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Reports Utah Water Research Laboratory
January 1983
Polycyclic Aromatic Hydrocarbons: Are They a Problem in Processed Oil Shales?
David L. Maase
V. Dean Adams
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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
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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). In the table, designations as "known" quantities imply a more strin The concept of producing oil from gent statistical approximation than do shale is not new. Known to the Indians designations as "estimated." "High as "the rock that burns," 0 i 1 shale grade" deposits imply that exractable was actually used as an energy source oil is about 25 gallons of oil per before Columbus set sail for the New ton 004 liters/metric ton; .Q,/MT) of World. By the early 1900s, oil shale shale (within the range of 15 to 30 industries had been established in gal/ton; 63 to 125 .Q,/MT). "Accessible Australia, Brazil, Canada, France, and rich shale" is considered to be ayail Scot land. A United States Geological able through a combination of room and Survey (USGS) report in 1915 indicated pillar mining and in situ develop the richest source of oil shale in this ment; while being "recoverable (present country was found in the Green River technology)" assumes surface retorting. Basin of the Rocky Mountains. By the The "selected tracts" refer to reserves early 1920s, potential oil shale de in areas with present industrial activ velopers had formed nearly 200 corpora ity. tions and filed more than 30,000 mining claims on federal lands in the Rocky Hendrickson (1975) estimates that Mountain area (Dassler 1976). the Green River formations contain the
Table 1. Known available estimates of organic fuel resources.
Od (billions of bbl (109 m3» World petroleum crude (ultimate resources) 2,000 (31S) World oil shale (known) 3,000 (4S0) U.S. oil shale (knqwn) 2,000 (3lS) Green River Formation (estimated) 4,000 (636) High grade (known) 600 (95) Accessible rich shale 130 (21) Recoverable (present technology) SO (13) Selected tracts 54 (S.6)
1 oil con ten t summa r i zed in Tab 1 e 2 • and land requirements; 2) documentat ion Hendricks and Ward (1976) estimate that of estimated PAH content of oil shale only 1800 x 109 bbl (286 x 109 m3) are process wastes requiring surface dis recoverable. Characterization of the position (processed shale and incor Green River oil shale resource is porated wastewater) and an inventory of included on Figure 1. The results of other process wastes; 3) analysis of federal oil shale lease offerings are White River hydrological and geological presented in Table 3. As a specific data pertinent to estimations of PAH example, the oil shale sequence (45 to flux via surface runoff, sediment 50 feet; 14-15 m) at the combined U-a transport, and alluvial drainage; and 4) and U-b sites reportedly averages 30 an expansion of literature-available gallons of oil per ton of shale (gall characterizations of extractable organic ton) 025 t/MT). About 500 x 106 bbl res idue in processed oil shales, with (80 x 106 m3 ) of oil could be developed specific attention to PAH. The selected at these sites by underground room and PAH (anthracene, phenanthrene, fluor pillar mining at depths ranging from 90 anthene, pyrene, triphenylene, benz(a) to 400 m below the land surface (Slawson anthracene, chrysene, benzo(e)pyrene, and Yen 1979). perylene and benzo(a)pyrene) were subjected to aqueous chlorination Objectives to investigate their destruction poten tial during this water treatment disin The primary purpose of this report fection process. is to provide information which can be used in evaluation of the long term risks to human health associated with Hydrology and Geology of Oil chlorine disinfection of drinking water Shale Areas supplies containing organics from oil shale development. Polycyc lic The majority of the commercial oil aromatic hydrocarbons (PAH) were chosen shale development in Utah and Colorado as an indicator of aquatic organic is located in the southeastern quadrant concentration increases. Field informa of the Uintah geological basin, and tion was obtained to estimate their flux within the Piceance geological basin from processed oil shale surface coincident with a hydrological basin of disposal sites in the White River Basin the same name (Figure 2). These inter (Utah and Colorado). Data develop mountain geological basins are within ment objectives included: 1) summariza the Green River drainage basin. Histor tion of predictions of White River oil ical developments of Piceance shale shale developments and concomitant water reserves were centered within basins
Table 2. Estimate of Green River oil shale resources (in billions of barrels (109 cubic meters».
Extractable od Utah Colorado Wyoming Total gallton (R./MT) Uintah Basin Piceance Creek Green River 109 109 109 109 109 109 109 109 bbl m3 bbl m3 bbl m3 bbl m3
25-65 004-270) 90 04.4) 500 (80.0) 30 (4.8) 620 (99.2) 10-25 (41.7-104) 230 (36.8) 800 (128.0) 400 (64.0) 1430 (228.8) 5-10 (20.9-41. 7) 1500 (240.0) 200 (32.0) 300 (48.0) 2000 (320.0) Total 1820 (291.2) 1500 (240.0) 730 016.8) 4050 (648.0)
2 COLORADO .. ~'-'+--- ~ Non-federal land
• •. • Federal land with unpatented oil shale ~• • placer claims UTAH Federal land with recent unpatented D metalliferous mining claims Federal land for which existence of possible encumbrances has not been ascertained
WYOMING
TOTAL
o 1000 2~ 3~ 4000 5000 6000 7000 8000 9000 (404.7) ( 809 • 4) ( 1214. 1 ) ( 1618 • 8) (2023.S) (2428.2) (2832.9) (3237.6) (3642.3) ACRES, thousand (HECTARES, thousand)
Figure 1. Oil shale lands--Green River Formation (National Petroleum Council 1972) (from Slawson and Yen 1979), I,
Table 3. Results of federal oil shale lease offerings (Slawson 1979).
Recoverable Resource Estimate High Bonus Area Bid (104 m2) (106 bbl) (106 m3) ($ million) Original Lessee
Colorado
C-a 2,060 1,300 200 210 Rio Blanco Oil Shale Project (Standard of Indiana, Gulf Oil Corp.) C-b 2,062 723 116 118 Atlantic Richfield, Ashland Oil, Shell Oil, The Oil Shale Corp. (TOSCO)a
Utah
U-a 2,073 331 53 76 Sun Oil Co. and Phillips Petroleum Co.b U-b 2,073 271 43 45 Sohiob
Wyoming
W-a 2,070 359 57 None W-b 2,070 359 57 None
apresent lease partners are Ashland Oil and Occidental.
bWhite River Shale Project will jointly develop Tracts U-a and U-b. I I WYOMING I 110 0 109 0 108 0 ---'T l------l------1----UTAH COLORADO , . , ,.------...... ----.- verna.-...... ' I //' / . I \ UINTA " \ BASIN 0 40 -) ( '- ..... \ ' ...... -- " '\ BASIN Junction t miles scale 1.1,000, 000 Figure 2. Geologic (Uinta and Piceance Basins) and hydrologic (White River Basin, Utah and Colorado) location map of the oil shale regions. (See Appendix A, Tables A-22 and A-23 for specific oil shale development areas.) draining to the Colorado River above (1.5 m) deep. As the flows move down Grand Valley. stream, water quality degrades in all watersheds. Waters passing through the The White River is characteristic alluvial soils (often > 30 m deep) of the Upper Colorado Basin in regard to dissolve weathering products, and mountainous, high runoff producing additional loadings enter from waters headwaters. Headwater area soils and diSCharging into the stream from con outcrops contribute very little loading solidated aquifers. of total dissolved solids (TDS) and suspended solids (8S). Upland soils are The upland climate of the oil shale rocky, shallow (ranging from 2 to 10 area is typical of a continental high inches; 5-25 em) and very sandy. desert (5,000 to 9,000 feet 0500-2700 Alluvial valley soils are classified as m) elevation) with summer daytime loams and are generally about 5 feet temperatures averaging BO°F (27°C) and 5 winter daytime temperatures of about Federal leases U-a and U-b (Figure 32°F (O°C). It has been estimated that 2) are near the confluence of Evacuation approximately 39 inches (99 em) of Creek with the White River. Seventy-one potential evaporation occurs between May cfs (2 m3 /sec) on the average are and September in the Piceance Basin. contributed to the White River from Potential evaporation in the Utah Evacuation Creek (282 mi2 (73 x 107 development areas is a~out 48 inches m2 ) drainage area). Little published (120 em). Annual precipitation amounts information is available to allow to approximately 10 inches (25 em) in characterization of watersheds of the the Uintah Basin. Precipitation in White River shale development areas the higher Piceance Basin is about 17 further downstream (see Figure 2). inches (43 em) per year, In both the Piceance and Uintah shale industry Alluvial sediments of the Piceance areas, snow amounts to 60 percent of the Creek Basin average about 1.0 ppm precipitation average, contributing (ranging from 0.025 to 2.5) organic snowmelt to the streamflow between March matter (Ringrose 1977). Surface weather and June. Streamflow during the ing of Piceance Creek has been estimated rest of the year originates in ground at 3 tons/ac-yr (6.7 metric tons/ha water drainage and occasional thunder yr). Eros ivi ty isopleths are shown on storms. Figure 3. Soil permeability is up to 3 inches per hour (2 x 10-3 em/sec; Most of oil shale development is ranging from 0.2 to 3 cm/hr) (Slawson anticipated to occur in the White River 1979), Basin. The largest Green River trib utary, the White River, drains the The Uintah Basin is morphologically Piceance Basin and flows through the similar to the Piceance geological northeastern Uintah Basin, where it basin, both being composed of Eocene collects runoff from additional oil fluvial and lacustrine deposits (Green shale areas. Flows at selected points River Formation) overlain by Quaternary are summarized in Table 4. The total alluvium. The geometric character of White River drainage is about 5120 mi 2 these basins was sculptured by the 03,260 km 2) , (USGS hydrology station Laramide Orogeny. Outcrops of the at mouth near Ouray) with a total members coincident with oil shale population of 5600 0970 census). The deposits are shown in Figure 2. headwaters of the White River originate on a 12,000-foot (3650 m) plateau Snowmelt recharges the consoli of the same name. Runoff from the White dated formation aquifers at higher River Plateau, less than 20 percent elevations via direct percolation and at of the total drainage area (762 mi2 upland alluvium intersections with total; 1970 km2), contributes 90 per aquifer outcrops. Above 6500 feet (2000 cent of the White River discharge to m), alluvial drainage could be classi the Green River. In contrast, less than fied as potab Ie waters. The alluvium one-fourth of the basin salt load is intersecting aquifer outcrops at contained in this good quality plateau lower elevations contain water of high drainage (TDS about 240 mg/U. Irri TDS concentrations (Cashion 1967). gated areas of about 10,000 acres (4050 x 104 m2) contribute less than 2 per The geological units in the oil cent of the salt load. Abandoned oil shale area and their waterbearing test holes, which now discharge saline characteristics are summarized in Table water, reportedly contribute some 15.4 4. The Garden Gulch member of the Green percent of the total White River TDS River Formation is described as fine load (EPA 1971). Average TDS concentra grained magnesium marls tone of low shale tions in the water available for oil con~ent. The Parachute member contains shale development are about 400 mg/l most of the oil shale in the Green (FEA 1974). River Formation in its Mahogany zone 6 " Table 4. Summary of Utah and Colorado oil shale area hydrology. Drainage Flow cfs (m3/sec) Total Dissolved Solids Area Ave. Range mg!l ton/day mi2 (107 m2) (MT/day) Upper Colorado (Lees Ferry)a 107,900 19,263 499 26,160 (27,950) (545) (23,730) Green River (near G.R., UT)a 40,600 6,292 427 - 473 7,260 00,515) (78) (6,590) White River above mouthb 4,020 702 (8.5 - 28) 426 - 439 905 (1,040) 09.9) (821) upper bas inc 762 638 244 402 (97) 08.1) (365) Piceance Creekd 629 17 (0.03-16) at mouth (63) (0.48) Ye 11 ow Creekd 258 1.37 (0 - 0.3) at mouth (67) (0.039) Evacuation Creeke 282 71 , 3800g (73) (2.01) Roan Creekf 321 40 (0.9 - 0.35) (83) 0.13) Parachute Creekf 200 30.3 (0 - 0.25) (52) (0.858) aUSGS water supply papers 441 and 442; Irons et ala (1964, 1965) bat Watson, USGS, 1923-1976 Cat Meeker, USGS, 1974-1976 dSlawson and Yen (1979) and Slawson (1979) eUSGS 1974-1975 fSlawson and Yen (1979) and Slawson (1979); drain immediately to Colorado River above Grand Junction gNa+' and S04=, dominate constituents WYOMING ,s- ,.- I I ..:..~ ______L2 ~------171622 22 : 20 20 31 " Figure 3. Isoerodent map, R contours, for White River Basin (prepared from state maps as directed by Fletcher (1979), see Appendix A, Figures A-4 and A-5). (named for its color). The Douglas upper aquifer and 20 x 106 ac-ft (2.5 Creek member of the Green River Forma x 1010 m3) in the lower aquifer. Within t ion is composed of interbedded shale, the Uintah Basin development area the me d i um - g r a i ned qua r t z, san d s ton e , upper aquifer is referred to as the siltstone and limestone. Bedding Bird's Nest Aquifer. Both aquifers is continuous, even and uniform. outcrop above U-a and U-b areas and discharge waters into the White River Consolidated aquifers immediately and Evacuation Creek. above and below the oil shale rich Mahogany zone have been identified in As recharge to the lower aquifer in both the Piceance and Uintah Basins. the Uintah and Piceance geological The Mahogany zone appears to impede basins occurs at outcrops at higher flow between the two aquifers over most elevations, static water levels of the of the Piceance geological basin. lower aquifer are greater than those of Estimated water volumes amount to about the upper aquifer. Storage coefficients 25 x 106 ac-ft (3.1 x 1010 m3) in the of the aquifers range from 10-4 to 8 10-5. Transmissibility coefficients (at 30 to 100 atmospheres) indicate: range from 103 to 105 (gallons/day/foot permeability of in situ oil shale to bt (10-4 to 10-2 m3/sec/m». One thousand about 100 darcys(10-1 cm/sec). Thl gpm (6 x 10-2 m3/sed can be developed mineral matter in the raw shale has tht from wells in these Green River Forma typical composition: tion aquifers. Local alluvial aquifers can also supply water at this rate; wt% wt% however, being shallow, they have Dolomite 32 Albite TO a limited storage capacity (Weeks et Calcite 16 Microline 6 a1. 1974). Quartz 15 Pyrite 1 Illite 19 Analcite 1 Lower aquifer waters can contain TDS concentrations ranging from 30,000 to 70,000 mg/l (Draft Environmental Other macrocharacteristics of raw oil Statement 1975). However, more recent shales are summarized in Figure 4. sampling indicates that concentrations of upper and lower aquifer waters As shown in Figure 4, the organic cont iguous to t he Mahogany zone are 0 f matter amounts to about 13.8 percent by better quality (500 and 1500 ppm TDS, weight of the raw oil shales and is respectively). Lower elevation upper and classified as kerogens and bitumens. lower aquifer outcrops discharging to The Green River shales contain 2 to it the White River alluvial drainage percent bitumens and 9 to 12 percent contain TDS concentrations averaging asphaltene/resin (kerogen). 2000 mg/l and 80,000 mg/l, respectively. A few samples of lower aquifer waters Kerogens are high molecular weight contain fluorine concentrations ten organic materials, more or less 1n times raw drinking water supply criteria soluble in common organic solvents (Slawson and Yen 1979). Identified (Schmidt-Co1lerus 1974). Orr (1977) reference. detailing macroconstituents postulates that kerogen is an inter and trace elements of area environmental mediate between humic acids and fossil waters are indicated in the Reference resources. Saxby (976) compares thE section with an (1). ratios of numbers of hydrogen and oxyger atoms to carbon atoms for selected ra" In-place Oil Shale Characteristics shales to those for other organic forms and development lines for coal macerals Raw shale of the Mahogany zone is (Figure 5). repotted to have a bulk density of about 126 pounds per f t 3 (2020 kg /m3 ) and Kerogen is a large complex molecul by weight contains about 1.6 percent belonging to the multipolymer class water or 3.9 gallons of water per ton Its insolubility in organic solvents i (16.3 t/MT; Woodward-Clyde 1976). related to the nonuniform three dimen· Laboratory investigations associated sional gel nature of its giant cross· with this study indicated a slightly link network. The three dimensiona higher bulk specific density of 2140 organic matrix is composed of polycycli kg/m3 (+ 100). Burkwell et a1. (974) "protokerogen" subunits (dominantly 2 t report-that oil shale is a highly 4 rings) or nuclei of tetralin, terpe· consolidated organic-inorganic rock noid, phenanthrenoid, and steroid typ system, with no significant micropore structures. About 5 percent of th s truc t ure, pore volume or int e rna 1 kerogen can be cons idered as polycon· surface. Over 99.9 p~rcent of the densed. These units are imagine inorganic part ic les have equivalent to be int erconnec t ed by long chai spherical diameters of less than 44 Il m; alkanes and isoprenoids. The linkage 75 percent are 2-20 Ilm, and 15 percent can also contain double bonds an are less than 2 Ilm. Prethermal testing heteroatoms. 9 Bit um ens are sma 1 1 e r 0 r g ani c species trapped within the three dimen sional matrix (see Figure 6). Molecu lar weights range from 605 to 749 CSOH60N203.4S0.2 g/mole with estimated molecular formulas (Yen et ale 1977). ranging from Table 5. Summary of geologic units and their water bearing characteristics. Th:1eknesa t System Series Geologie Unit Physical Character water Quality Hydrologic Character fe (m) water Is under artesian pressure Sand I gravel. and clay partly £:111 Near the headwaters of the' _jar where sand and gravel are over _jor valleys as IDIJ.Ch && 140 ft streams. dissolved-solids concen lain by beds of clay. Reported (43 m); sene.rally les4 than half trations range from 2S.0 to ]00 Mg/l. yield!! as much as 1500 gpm (950 x aUle wide. Bed. of clay may Dominant ions in the !Jater are e. 1O-4m3/s). Well yields will de be as thick as 70 ft (21 m) ~ gen generally c:alciUl'Q. magnesiUlQ, and crease with time because valleys Alluvium ()'140 arally thickest near the center bicarbooate. In IIKl"st of the area, are narrow and the valley walls of valleys. Sand and gravel coo disaolved solids range from 700 to (0-43) act 88 relatively impermeable tain str1ngeu of clay near as much as 25,000 mg/l. Above boundaries. Transmissi vi ty ranges mouths of sull tt'1butar1es to 3,000 IDS/l the dominant ions are from 20.000 to150.000gpd/ft (3xlO-3 qjor atreau. sodium and bicarbonate. to 20xlO-3m3/s per Ill). The storage coeffiCient averages 0.20. Intenonguing an.c1 gradational beds Water ranges from 250 to 1,800 mg/l Beds of SandStOne are predominantly of sandstone. siltstone, and marl... d1.9aolved BoUds. Une grained and have low penne .. stone; contains pyroc!sstic rocks abUity. Water moves primarily and a few conglomerate lenses. through fractures. The part of Fot'IIUI aurface rock over 1JIOst of the member higher than valley Evacua tion Creek ()"'l 250 the thina apprec1.ably floors is mostly drained. Re Member (a-1St) ported to yield as much as 100 gpm (60xl0-4m3/s ) where tested in the nOTtbcentral part of the basin. Member has not been thoroughly tested. and larger yields Dlay be possible. Kerog''''''':'o,,, dolomitic _rlstone Water ranges in dissolved-soUds High resistivity zone and !ia.hogany and shale, contains content frOID 250 to about 63,000 tone are relatively imper.neable. PYt'oc.I •• «c beds; fractured mg/l. Below 500 ms/l. calcium. is The leached zone (middle unit) at least 1,800 ft. the dominant cation;: above 500 mg/l, contains water in solution open Abu:ndan t saline tIl1.nerals sodium. is generally dominant. ings and is under sufficient of the basin. 1'1\_ Bicarbonate is generally the artesian pressure to cause flow divided into three dominant anion regardless of concen.. ing wells, Transmissivity ranges 4 Parachute Creek tration~ Fluoride ranges from 0.0 from less than 3000 gpd/ ft (4xlO- 50()'1.800 Member to 54 mg/l. m3/s per m) in the marZins of the (150-550) basin to 20.000 gpd/ft (3xlO-3m3!s per m) in the center of the basin. Est:i:nated vields as much a.s :000 gpm (600xlO-4 m3/s). Toral water in Storage in leached zone 2.5 1I1illion acre ... feet or more. and flaky marlstone and One water analysis indicates dissolved- Relatively impermeable and probably contains some beds of solida eoneentradon of 12,000 mg/ L contains few fracture!L Prevencs 011 and. locally, thin downward movement of v.tter. In Garden Gulch beds of sandstone .. the Parachute and Roan Cree\;s ().900 Member (0-274) drainages~ .springs are found along contact with overlying rocks. Not known to yield water to wells. Sandstone, shale, and 1.11lle8tone; The few analyses available indicate Relatively low permeability and containa oolite8 and ostt'acods. that dissolved-sr>lids content ranges probably little fractured. Maxi Douglas Creek ft'om 3.OGO·to 12,000 mg/I. Dominant Mum yield is unknovn, but Member ions a-re sodium and bicarbonate. or probably less than 50 gpm Ox sodium and chloride. 1O-3m3/s ) • 118ndStOn.y and marlstone The principal ions in the water are Sands tone beds have low perme trtj,thin a short dUtance generally =.3sue:slum and sulfate. ability. A few wells tapping westward into the liouglas The diSsolved-solids content Anvil Points ()'1.B10 Carden Gulch. and luwer ranges from about 1.200 to 1,800 Member ~:::~o(:x~~~m~~:t~ !::~n~:an (0-510) the Creek. '111.8/ 1• issuing from fractures yield Beds sandstone are as much .as 100 gpm (60xlO-4m3/s ) ~ fine grained. lenticular sandstone? Gypsum contributes sulfate co both Reds of clay and shale are rela surface-watel': and ground-water tively impermeable. Beds of Wasatch of conglomerate and )Q()..5,OOO sandstone are poorly permeable. Forroation lim.estone. Seds of clay and shale $uppU.es. (90-1500) are the !!lain constituents of the Not known to yield water to formation. Contains gypsum. wells. (After Coffin at al,? 19H). 10 ,I fes,. 0.86 .... ~~~~AR NoAISI 0 HZO -4.3 .... (Ul..ITE AND CHlORITE) ollole II. Z 6 II'KYRGANIC I1\TRIX ClAy { CARBoNATES (CAlCITE AND OOLctlITE) PvRITE AND OTHER MINERALS quarlz SIOZ 8.6% OIL SHAlE Bnu·\ENs (SOWBLE tN ~) illile ile monl:-:\~~~~~nIe KAI4 Si7 A1020 (OH\t 12.9 .... KERoGENS (INSOLUBLE IN 1::S2) ese (CONTAINING U, FE, V, NI, Mo) OSI COAIZSIZ08 16.4 ..... Miner~6~q.}~ .... Oil Shale delom ile 0 CoM\! 22.2% (C°;S)Z -43.1·1. Co 9.5"1. Mg 5.8% ,0 ------r'o C 5.6°/. Bitumen C 1 Kerogen organil.~.;!ler 1.4 2% 11.1% PORE SPACE ------ Figure 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). Basic nitrogen compounds in oil probably present as ether linkages and shales are mainly quinoline-types and as furans. Sulfur is present in place of tertiary alkylamines (latter about 63 a carbon along linkages and in hetero percent). Weakly basic compounds cyclic aromatics. Most of the sulfur in present include indole-types and kerogen is present as 2,2' dithienyls, 2 secondary alkyl amines. Oxygen is phenylthiophenes, thionapthenes and Waxes ~ 2.0 ~ , .. ats 1 Animals (Average) Alginite .r I ."...... Carbohydrates ~ I Bacteria, Fungi (Cellulose) 1.5 'C .... Protein '-Wood Exinite ..... Plants (Average) f ..... Lignin ; ; HIC Vitrinite 1.0 ..... Humic Acids 0.5 Loss of CO 2 Loss of CH4 a 0.2 0.4 0.6 0.8 1.0 OIC .. Legend A = Coorong sediment E = Sydney Basin bituminous coal B julia Creek oil shale F = Colorado soil shale (USA) C Sydney Basin oil shale G Kohat oil shale (India) D Sydney Basin carbonaceous shale H = ST Hilaire oil shale (France) Figure 5. Atomic ratio diagram for selected kerogens and coal macerals as related to other organic materials (Saxby 1976). 12 COMPONENTS BRIDGES ISOPRENOIDS D S-S DISULFIDE (0 0 -0- ETHER cS 0 E -C-O- ESTER STEROIDS '\ 0 -=, ISOPRENOIDS TERPENQIDS H 0 0 HETEROCYCLIC CAROTENOIDS 0 A CH3-dH-(CH2)15-dH-C~-CH2)7-CH3 ALKADIENE Q" \ ENTRAPPED SPECIES UNBRANCHED ALIPHATIC STRUCTURE ! II!' I BRANCHED ALIPHATIC STRUCTURE ---- POLYMETHYLENE BRIDGES Figure 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 1 thiophenes (Saxby in Yen 1976, and 25 gallons of oil per ton of shale (104 Moussavi 1n Yen and Chilingarian 1976). ~/MT; ranging from < 15 to > 30 gal/ton (63 to 125 £/MT» as determined by the One to ten percent of the organic Modified Fischer Assay. The Fischer matter soluble in pentane is aromatic assay was developed during early oil. About 12.4 percent of the Green coal research in 1920 to provide an River (core 1) oil shale organic matter indicator of extractable organics. The was not soluble in pentane. The pentane assay employs a miniature retort. The "soluble" portions were characterized as standard Fischer assay requires that 100 percent weight as follows (Robinson and grams of < 8 mesh sample be raised to Cook 1973): 932"F (500°C) in 40 minutes, then held at this maximum temperature for 20 n-alkanes 3.7 minutes. Retort gasses are condensed to aromatic oils 2.6 oil. in a cooled receiver. Cooling branched and cyclic alkanes 23.9 conditions are coarsely specified resins 57.4 (Stanfield and Frost 1949, and Hubbard Further characterization of Green River 1965). Heistand (1976) describes the oil shale organics are included in Table standard Fischer assay as a performance 6. test similar in concept to obtaining the octane rating of motor fuels or the Oil shales of the Green River tensile strength of fibers. Many Formation are estimated to contain about authors have demonstrated the variabil- Table 6. Composition of bitumens in Green River oil shale (Yen 1976). Percent Principal Components Classes of Components by Weight n-alkanes 3.4 - 3.9 C13-C35 with C17 and C29 as maxima Odd-to-even predominance at 3:1 or 4:1 Branched and cyclic 23.6 - 30.3 Chain isoprenoids (farnesane, pristane. and alkanes phytane) C27. C28, C29 stearanes C30 and C31 pentacyclic triterpanes C40 carotanes Aromatic oil 2.7 - 3.3 Alkyl benzenes Alkyl tetralins Mixed aromatic and naphthenic compounds Resins 54.4 - 57.4 M.W. tV 625 Indanones Tetralones, acetylindanes Hydroxypyrrole, diketopyrrole Asphaltenes (including 9.0 - 12.5 M. W. tV 1,320 fatty acids) Porphyrins Cl0-C34 fatty acids (n, iso, anti-iso) C2rC29 sterols 14 ity of the assay results in regards to The first successes were found in laboratory techniques (present and retort ing surface mined shal es, and changing in time), sample texture, these techniques have progressed to retort construction, and receiver the pilot plant operation stage. In the cooling conditions. However, the 1920s Union Oil began land and water Fischer assay is largely accepted acquisition in Parachute Creek. In the as the standard analytical procedure early 1950s they experimented with a 2 for the oil shale industry. tons/day (1.8 nT/day) retort process. Pilot scale work reached 50 tons/day (45 Allred (1976) has derived relation MT/day) and a demonstration plant (350 ships for using the Modified Fischer tons/day; 320 MT/day design) was able to Assay (MFA) to estimate other shale retort 1000 tons/day (900 MT/day) during components in any consistent units as operat ion (Cozzart et al., personal shown in Table 7. Specific data for communication. 1978). shales in the Mahogany zone are compared wi th world values in Table 8 (Slawson Two other principal processes, and Yen 1979). called Paraho and Tosco II, began deve lopment in the 1950s. The Tosco II Industrial Development process was studied during 1955-1956, with a pilot plant handling 24 tons/day Experimentat ion with both surface (22 MT/day). Initial investigations for mining and in situ development of the Paraho process, 1951 through 1955, Green River 0 ales is underway. resulted in an operation handling 150 Table 7. Derived relationships relating shale components to the Modified Fisher Assay. Total organic (carbon) = 1.644 x MFA (Stanfield and Frost 1949) Organic residue = 0.361 x MFA Gas + Water + Losses 0.282 x MFA Water (from pyrolysis) = 0.077 x MFA Note: MFA is the volume of oil per weight of shale as estimated by the modified Fisher Assay. Gallons per ton or other consistent units may be used. Table 8. Comparison of organic carbon and the Modified Fisher Assay of specific Green River Mahogany zone shales to reported world values. Organic Carbon MFA (wt%) gallons/ton (~/MT) Piceance Creek, Colorado 12.4 28.0 (17) Soldier Summit 1925 Study-Utah 13.5 17.0 (70.8) World, Maximum 54.0 13.9 (57.9) World, average 31.0 Typical 14.0 25.0 (104) 15 tons/day (135 MT/day), rising to 300 As to other comparisons among the tons/day (270 MT/day) during 1964-1966. three principal surface retorting Paraho semi-works demonstrations between processes, Tosco II technology requires 1964-1972 were able to process 100 tons a raw shal e feed size of 1 ess than of oil shale/day (90 MT/day) (Slawson one-half inch (< 1.3 cm) and uses a and Yen 1979). Recently, 100,000 bbl preretort rotary grinder and heat (16,000 m3) of oil were produced by exchanger with ceramic balls. The Union the Paraho semi-works retort during 56 B oil process utilizes an upflow rock days of operat ion (Cozzart et al., pump which requires greater than one personal communication, 1978). eighth inch () 3.2 mm) and less than 3 in « 7.6 cm)' feed size. The Paraho The shale industry proposes to gas combust ion process al so uses a advance production to a commercial level vertical kiln and requires greater than via a modular stage. Modular develop one-fourth inch () 6.4 mm) and less than ment is cons idered to be a wise way to 4 in « 10.2 cm) down flow feed. A develop new technology in order to flow diagram of a commercial scale optimize water needs and production Paraho process is included in Figure 8. e ffic iencies. The proposed Paraho In all three cases, both indirect and modular unit design could produce direct retort heating modes are being between 100-300 bbl/day (17 to 32 investigated. Retort temperatures m3 /day) of oil (Cotter et al. 1978). are about 1000°F (540°C) (ranging from A 10,000 ton/day (9070 MT/day) modular 800 to l200°F; 425 to 650°C). Sources demonstration is proposed by Union oil containing further descriptions of (Slawson and Yen 1979). To provide a processes are indicated in the Refer comparison, at 25 gal/ton (104 2/MT) ences as (p). this module could produce about 6000 bbl/day (950 m3/day). A flow diagram Occidental and Geokinetics plan to of a modular Tosco II unit producing use modified in situ processes. Occi 15,000 bbl/day (2400 m3/day) is in dental plans to mine 20 percent of the cluded as Figure 7. Commercial projects ore prior to in situ retorting. The presently planned range from 300,000 to area needed f07 surface disposal would 500,000 bbl/day (total; 48,000 to 79,500 range from 40-60 acres (16 to 24 x m3 /day). Total production of 1.0 x 104 m3) per year for shale containing 106 to 2.0 x 106 bbl/day (1.6 x 105 to 15 gallons of oil per ton (63 2/MT) to 3.2 x 105 m3 ) has been predicted. A 20-30 acres (8 to 12 x 104 m3 ) per list of current oil shale development year at 25 gallons per ton (104 21MT). projects is outlined in Table 9. These estimates are associated with surface retorting producing 50,000 bbl/day (8000 m3 /day). Superior Oil Most of the modular units being plans to develop by-products of nacolite considered are smaller than one might and dawsonite, and thus will be able to expect from the size of the resource and return processed shale to the under expected markets. Among the reasons ground mine. Lurgi-Rurgas have designed cited for the caut ious approach to a fluidized bed surface retorting commercial developments are uncer process (Slawson and Yen 1979). tainties regarding both production costs and product prices, the lack of a Outputs of 50,000 to 100,000 definite energy policy, questions about bbl/day (8 to 16 x 103 m3 /day) at a the ability to meet ambient air quality single site constitute commercial scale standards, and the threat of environ development. The material balances mental li tigat ion (S lawson and Yen associated with planned developments are 1979). In situ research may also make summarized in Table 10. These data surface retorting obsolete prematurely. reflect the combination of Paraho and 16 I" , H S/C0 30 TmPD ...... GAS TREATING 2 2 SULFUR (33 TPD) -.,. BALL HEATER "'" RECOVERY ... WARM BALL PLANT FUEL PLANT SULFUR -.. .. ~ 0.4 MSCM/D HOT (14 MSCF/D) BALL ~~ GAS " 2,400 M3/D (15,000 BPD) .. TO UPGRADING 16,326 TmPD TOSCO II CRUDE SHALE OIL .. (18 000 TPD) ...... RETORTING 220,944 LPD CRUSHED FINE SHALE UNIT (58,374 GPO) ... TO WASTE WATER TREATING RETORT WATER .. WARM BALL PROCESSED TO" BALL HEATER SHALE ., 929 LPM PROCESSED 14,726 TmPD (246 GPM) .... 06.236 TPD) --.... -.. SHALE r TO DISPOSAL AAW WATER DISPOSAL SPENT SHALE Figure 7. Flow diagram for the Tosco II process (Slawson 1979). .. Table 9. Current oil shale development projects (Slawson 1979). Syncrude Capacity Estimated Project or Location Sponsor Technique bbl/day Cost ($ million) Federal Tract C-b Occidental Petroleum and Modified in situ retorting 57,000 442 (Colorado) Ashland Oil (no surface retorting) (9,060) Colony Development Atlantic Richfield and Room-and-pillar mining; 47,000 1,132 (Colorado) The Oil Shale Corp. TOSCO II retorting (heated (7,470) ceramic spheres) a Federal Tract C-a Gulf Oil and Standard Modified in situ retorting 1.500 93 (Colorado) Oil (Indiana) (with surface retorting) (240) b Mul timineral Superior Oil Room-and-pillar mining; 13,300 300 :;; (Colorado) circular-grate retorting; (2.115) recovery of soda and alumina Sand Wash (Utah) The Oil Shale Corp. Combination in situ and 75,000) 1,000 surface retorting (11,925) c Parachute Creek Union Oil of California Room-and-pillar mining; 7,,800 123 (Colorado) direct heated rock pump (I,240) retorting White River Shale Sun Oil, Phillips Petro Room-and-pillar mining and 100,000 1,61Od Project (Utah) leum, and Standard Oil surface retorting (Paraho (15,900) [Federal Tracts (Ohio) and TOSCO II) U-a and U-b] a For 5-year development program with intermittent production in demonstration units; projected com- mercial capacity is 76,000 bbl/day (12,100 m3/day). b For the first module of stated capacity. d Much smaller demonstration unit would be part of $246-million development program proposed as joint ven cFor prototype module. ture with ERDA. 61.2 MSCMjD 31.5 MSCMjD (2,151 MSCF/D) GAS (1,122 MSCF/D)... RECYCLE GAS TREATING PRODUCT GAS ... 18.7 MSCM/D ..... (646 MSCF/D) U ... AIR ... GAS 3 ~, 13,600 M/D 144,152 TmPD 122,502 TmPD PARAlIO (85,000 BPD) ... SECONDARY CRUDE SHALE OIL ... TO UPGRADING (158 .856 TPD) ... CRUSHING (135,605 TPD) .... RETORTING ..... II'" ... UNIT 1,264,639 LPD -0 MINED RAW CRUSHED RAW SHALE SHALE (334J1~8 GPD) .... TO WASTE WATER ~ RETORT WATER TREATING PLANT 21,649 TmPD 87,368 TmPD .... (23,868 TPD) (107,355 TPD) ..... FINE SHALE PROCESSED SHALE 6,758 LPM PROCESSED 107,109 TmPD SHALE (1 785 GPM) .. (118,091 TPD). TO DISPOSAL DISPOSAL RAW WATER P' SPENT SHALE Figure 8. Flow diagram of the Paraho process (Slawson 1979). , I I .. I, Table 10. Associated operation material balances of planned oil shale developments. Area Models Tosco II Tosco & Paraho Tosco & Paraho Sand Wash Ua & b Phase IV Phase II, Ca Oil/time 50,000 bbl/day 50,000 bbl/day 16,000 m3/day 8,930 m3/day (8,000 m3/day) (8.000 m3/day) Water/time 34 m3/min 108.000 MT/day Shale mined/time 26.9-29.9 ton/day 55,000 MT/day (24.4 - 27.1 MT/day) Gal. oil/ton shale 30 30 [26.45]a [19.75] (125 Q,/MT) (125 Q,/MT) 000 Q,/MT) (84.2 UMT) Water/oil {3.06] Processed shale/time 72,000 ton/day 48,300 MT/day 117,400 MT/day 107,700 MT/day (65,300 MT/day) Other wastes/time S=2,400 MT/day S=150 MT/day S = 153 MT/day Fines=I,264 NH3=374 MT/day NH3= 210 MT/ day Coke = 727 Coke = 425 MT/day Disposal depth 250 ft (76 m) Bulk density 1004f/ft3 71-75 :ffIft3 85 4f/ft3 (1600 kg/m3 ) (1400-1200 kg/m3) (1360 kg/m3) Volume/time 10,860 ac-ft/yr 0.168-0.196,0.126- 117,500 MT/ day (0.13 x 108 m3/yr) 0.146 x 108 m3/yr (wet) Area/time 43.4 ac/yr 2.210-6,650 ac 2,300 ac 3.720 ac (I.8 x 105 (8.9 x 106 - 27 x 106 m2) (9.3 x 106 m2 ) (15 x 106 m2) m2/yr) lie ffected" 30 20-30 yrs 20-30 yrs yrs. Comments 200 ac (8 x 105 85-95% vol. re 14% water 15,200 m3/day sur face mining m2)/3 yrs, 30 covery, In situ 4-5% Carbona upgraded oil Phase 1<1/10(11) ac 0.2 x 105 775 ac with 60% ceous matter room and pillar "Mesa 84 11 dis m2/yr with 60% returned to mine Phase II=1/2(IV) posal area returned to mine Phase I<1/20(IV) Re ferences Prein et a1. Conkle et ale Slawson & Slawson & Slawson & 1973 1974 Yen. 1979 Yen, 1979 Yen, 1979 a{] indicates values estimated from other reported data. Table 10. Continued. Tosco & Paraho Union Dissertation Model Phase III Cb full scale Oil/time 50,000 bbl/day 50,000 bbl/day 5 x 106 bbl/day (8,000 m3/day) (8,000 m3/day) (8 x 105 m3/day) Water/time 12.3 m3 /min Shale mined/time 60,000 MT/day Gal. oil/ton shale [31.761 25 15 30 (132.5 Q,/MT) (104 2/MT) (63 2/MT) (125 2/MT) Water/oil [3.791 Processed shale/time 60,000 MT/day 15.5 x 106 8.4 x 106 ton/day 14 x 106 1 x 106 tons/stream "total wastes" (13 x 106 MT/ (6 x 106 MT/ year (7.6 x 106 MT/day) day) day) (14.1xl06 MT/ stream year) Other wastes/time S = 175 MT/day NH3 = 136 MT/day Coke = 727 MT/day N ...... Disposal depth 200 ft 200 ft 500 ft (61 m) (61 m) 052 m) Bulk density 904f/ ft3 85 4f/ ft3 60 4f/ ft3 100 4f/ft3 0400 kg/m3 ) 0360 kg/m3) (960 kg/m3) 0600 kg/m3 ) Volume/time Area/time 900 ac 323 mi 2 764 mi 2 91.6 mi2 (4 x 106 m2) (8.4 x 108 m2) (2 x 109 m2 ) (2.4 x 108 20 yrs 25 yrs 25 yrs m2) 25 yrs Comments Room & pillar 20% water module = 6% full scale Re ferences Slawson & Slawson, Yen, 1979 1979 a[l indicates values estimated from other reported data. Tosco II processing technology proposed of water and land area. In fact, the by the shale industry and an expectation availability of water may limit the rate that about 25 gallons of oil. are ex of production. Slawson and Yen (979) pected from processing a ton of shale estimate that a 2.4 x 106 bbl/day (I 00 Q/MT). (0.38 x 106 m3 ) oil shale industry could be supported with competition Water and Land Requirements among western water users assuming a ratio of water need to oil produced of The development of oil shale approximately 3.7 (Table ll). White et resources can require large amounts al. (1977) report that cooling water Table 11. Summary of water needs for oil shale development. oil Production Water needs Water to oila References 103 bbl/day 103 ac-ft/yr Volume ratio (I03 m3/day) (107 m3/yr) 47 0.5) 9.05 (1.0_ 4.1 USDI, 1973 50 (8) (underground 8.74 (l.l) 3.7 DES, 1971 mining) 100 (16) (surface 16.75 (2.1) 3.56 DES, 1971 mining) 400 (64) 64.95 (8.0) 3.45 DES, 1971 1000 (160) 155 (19~1) 3.29 DES, 1971 50 (8) (in situ) 4.5 (0.5) 1.9 DES, 1971 100 (16) (C-b) 18 (2.2) 3.83 USDI-BR, 1974 100 (16) (U-a & U-b) 18 (2.2) 3.83 USDI-BR, 1974 300 (48) (C-a) 57 (7.0) 4.04 USDI-BR, 1974 1000 (160) 159 (19.6) 3.38 FEA, 1974 50 (8) 6.7 - 10.6 (0.8 - 1.3) 3.7 Conkle et aI., 1974 50 (8) (in situ) 3.0 - 5.7 (0.4 - 0.7) 1.85 Conkle et --- aI., 1974 2000 (320) (max) 320 09.5) 3.4 Slawson, 1979 aAverage water to oil ratio (excluding of in situ needs) is 3.66 + 0.27. 22 amounts to only 20 percent of the water to the FEA projections would largely budget. In contrast, in coal to oil have to come by purchasing supplies from conversion, cooling water needs range irrigated agricul ture. Th is woul d from 50-90 percent of the water budget. require moving the water from present Sc hmid t-Co llerus (1974) pos tul ates farming areas to the oil shale sites, that water needs for a 50,000 bbl/ day The most cost effective way to do so may (8000 m3 /day) oil shale development be through development of new reservoirs would amount to 20 x 103 ac-ft/year close to the oil shale areas. (2.5 x 107 m3/yr). Of the process water, 45 percent would be used to FEA (974) states that "ultimately moisturize the processed shale; 30 regional development must be supported percent for mining, crushing and retort almost entirely by surface water," In ing; and 25 percent for hyd rotreat ing localized instances, suffic ient ground (Schmidt-Collerus 1974). Additional water would be made available by mine water may be needed to supplement dewatering. Initially, the mine de disposal area snowmelt in providing watering associated with Piceance Basin the leaching required for revegeta ope rat ions could provide produc tion tion. Total shale development water needs. However, it should also be noted needs (including needs to supply induced that aquifer dewatering would reduce development in nearby communities) Piceance, and thus White River, dis reported in the literature are compared charges (Weeks 1974). Development of a in Table 11. Assuming that a total of local and regional water supply reser 8.25 x 106 ac-ft/year (1.02 x 1010 voir in the White River Basin is the m3/yr) of water is available for upper most economical approach to provide basin uses, the needs and uses estimated needed water (USBR 1974). by FEA are compared in Table 12. As to land needed for disposal The water currently available for areas, given oil extractability and use in oil shale development according disposal depth, the disposal area Table 12. One estimate of needs and summary of water availability for oil shale development in Colorado, Utah, and Wyoming (FEA 1974). 80,000 bbl/day 100,000 bbl/day Water Needs 02,700 m3 /day) (16,000 m3 /day) 103 ac-ft/yr (106 m3/yr) underground surface mining mining In situ Shale industry water requirements 6.1 - 9.6 12.1 - 18.4 2.2 - 7.3 (7.5 - 11.8) 04.9 - 22.7) (2.7 - 9.0) Associated urban 0.8 - 1.0 1.2 - 1.7 0.78- 0.93 0.0 - 1.2) (1.5 - 2.1) 0.0 - 1.1) Total 6.9 - 10.6 13.3 - 20.1 5.0 (Ave) (8.5 - 13.1) 06.4 - 24.8) (6.2) Water Availability 103 ac-ft/yr (106 m3/yr) Colorado Utah Wyoming Total Not identified -64 (-79) 116 (43) 33 (41) 85 (05) Total Conceivable use for Oil Shale 90 (11) 128 (158) 223 (-287) 451 (556) 23 --! compaction density is the major variable 106 m2 calculated from data in Craw dictating needs. Tests on field plots ford et al. 1977 and Slawson and Yen consisting of mixed volumes of Tosco and 1979), for a total of 1.6 x 109 yd3 Paraho retorted shales have indicated (1.22 x 109 m3 ). A total planned waste that in-place compaction densities of area of 2300 acres (9.3 x 106 m2) for 101 Ibs/ft3 (1.62 g/cm3 ) can be at 950 x 106 yd3 (725 x 106 m3) at a maxi tained. However, in certain situations mum depth of about 500 feet (150 m) in it may only be possible to achieve a Southum Canyon is planned for U-a and specific density of 55 Ibs/ft3 (881 U-b operations. Compaction moisture kg/m3 ), and 85 1bs/ ft3 (1362 kg/m3 ) content would be about 15 (+5) percent was chosen for purposes of estimating with an expected permeability of 1 to 2 disposal area needs. inches per hour (1 + 0.3 x 10-3 em/sec) (Slawson 1979). -Further data for USDI (1973) estimated surface estimating disposal requirements are disposal area requirements of about 800 included in Table 10. acres (3.2 x 106 m2 ) in 20 years for a 47,000 bbl/day (7.5 x 103 m3 /day) Shale Waste Characterization operation. Hughes et al. (975) estimated 4.75 ac/l06 bbl (12.1 m2 / All operation wastes would be m2/102 m3 ) of oil produced for shale included with shale disposal volumes, containing 30 gallons/ton (125 ~ /MT). particularly process wastewater streams, According to DES (1975), for 30 years and perhaps lower aquifer mine water. operation at 100,000 bbl/day (16,000 Processed shale requiring disposition m3/day), surface disposal needs would would amount to about 97 percent of the amount to 5000 to 6300 acres (20 x 106 raw shale feed by weight. During m2 to 25.5 x 106 m2) and the disposal processing, polycondensed aromatic of wastes from underground mining could hydrocarbons (PAR) are distributed among require about 2000 acres (8 x 106 m2). shale retort water and spent shale as For a 106 bbl/day (1.6 x 107 m3 /day) the oil soluble, water soluble, and industry and assuming a mix of ml.nl.ng insoluble high molecular weight frac methods, the total could reach 22,500 tion. Other important wastes, amounting acres (9.11 x 107 m2). to about 3 percent by weight of the total waste volumes, include process Union Oil's proposed operations at water wastes, air quality control 9,000 bbl/day (1430 m3 /day) would wastes, catalysts and coke/NR3, etc. require 320 acres (I.3 x 106 m2 ) at The coke/NH3 etc. volumes are small, 800 feet (240 m) depth for a tot al relatively, and can also be exploited as volume of 57 x 106 yd 3 (4.36 x 106 by-products. An estimate (Hughes et al. m3 ) in 20 years (assuming 100 Ibs/ft3 1975) of 236,000 Ibs/hr (107,000 kg/ (1600 kg/m3 » and 20 percent water hour) of uncontrolled air emission (Cozzart et al.; personal communicat ion, particulates associated with 100,000 1978). For the Colony development bbl/day (16,000 m3 ) oil produced per operation 400 x 106 tons (360 x 106 day Tosco II operation suggests the MT; 12 percent water) would fill Davis volume of air quality control wastes Gulch (with surface leaching and re requiring disposition. vegetation at a compacted density of 85 to 95 Ibs/ft3 (1362 to 1522 kg/m3». As a specific example, retort About 1200 acres (4.8 x 106 m2 ) sur water, a major water waste stream, face area needs are estimated for 20 contains a complex array of organic and year operations for a disposal depth of inorganic compounds and would ultimately 200 ft (61 m). At 120,000 tons/day be used to cool and moisturize processed (109,000 MT/ day; Phase II) C-a opera shale to optimize compaction. Init ial tions 1184 Mesa" surface area disposal retort water is reported to be 10 needs would amount to 3720 acres (15 x percent crude oil. After oi I removal, 24 retort water can contain 25 percent from 0.05 to 14 percent with most organic carbon by weight of TDS con oils ranging from 0.1 to 3 percent. stituents (Slawson 1979). Retort water Most of this sulfur is in organic constituents are generally less than combination in aliphatic and aromatic 0.45 \.1m in size (Analysis and Quality compounds. The aromat ic rings present Assurance Symposium 1979). Total are dominantly five-membered rings such organic carbon (TOC) concentrat ions of as thiophene. These rings are also found retort water range up to 10,000 mg/l in combination with six-membered carbon (Leenheer 1979, and Analysis and rings in polycyclic aromatics (Orr Quality Assurance Symposium 1979). Both 1976). Examples include benzothiophenes phenols and furans have been identified and napthiophenes. These compounds may in retort waters. Ident ified phenols be extractable in acidic fractions inc lude orth-, meta-, and para-cresols (Fruchter et al. 1977). Other examples and p-ethylphenol. Concentrations of are included in Appendix A as Figure these species generally range from 10 to A-I • Mo s t 0 f the 0 r g ani c suI fur is 40 mg/l each. Piceryl chloride has also found in the high boiling fraction and been identified (Slawson 1979). Retort more polar subfractions (i.e., as water organics also include acidic, phaltene and resi~s). Associated molecu basic and neutral refractory organics. lar weights average 802 g/mole and range Polar nitrogen compounds identified in from 738 to 1019 g/mole (Orr 1977). retort water include maleimides, quinolines, succinimides, and alkyl The nitrogen content of coal and pyrolines. shale derived oils ranges from 1.0 to 2.0 percent while an average crude Biological treatment of retort petroleum content is about 0.05 to 0.1 waters may not achieve 65 percent percent (Ho et ale 1979). Crude shal e reduction in COD and TOC. Ninety oil contains on the order of two percent of the organics and other retort times the nitrogen content of high water constituents (at pH of about 8.5) nitrogen content crude oils (Slawson can be electrolyt ically separated to a 1979). The nitrogen compounds that have II cathodic solution" (Slawson 1979), been identified 1n shale oils include suggesting the predominance of nega pyridines, indoles, acridines, amides, t ive ly charged species in retort water pyrrols, quinolines, carbazoles, and constituents. nitri1es. These compounds can be present as oxygenated and/or alkylated The waste contents of retort water, species (Poulson 1975; Fruchter et process water and other oil shale a1. 1977). Nitrogen compounds seem industry related waste waters are separable to neutral and/or basic characterized in Table 13. As shown, fractions. Other examples are presented the wastewaters are comparable with oil in Appendix A, Table A-I. refining industry streams. Two to 3 ring nonheteroatomic examples of PAH concentrations in coal and polycyclic aromatic hydrocarbons (PAH) shale oils are two to three times (and have been identified at concentrations sometimes 10 to 100 times) higher than of 0.1 to 1.0 ppm in shale and coal those found in crudes. Tars and high conversion waters (see Table A-IS). boiling oil products from coal can consist of 40 percent by weight PAR. In Retort oils characterization comparison with those found in crudes. the PAR present in shale oil are gen Oil from oil shale processing is erally more alkylated. Reteroatomic similar to oil developed from lignites, and hydroaromatic constituents are also coals, and other kinds of materials more dominant. PAR content of shale cont'aining kerogens and bitumens (Table extracts and the distribution of paraf 14). Sulfur content by weight ranges fins in retort water are lIidentical" to 25 Table 13. Waste characterization of oil shale industry related waters (ppm except as indicated). Water tort Water TOC 10,000-29,000 9.16% 0.42% 4.04% 5870 3400 34-38 TIC Baslc Organks COO 100-2,000 I) ,000-20,000 24,000a 17,000' 1000-20,000 Total solid residue 1.68% 1.05% 2.01% 30,600 18,100 TIlS 17,400 251-762 2000-3000 BOil 50-500 5,000-12,000 6,000a 4,000. 100-14,000 NH4-N Amines 0& G 50-1000 5,000' l,oooa 6-230 tv C1\ CN-/chelator Phenols 0-210 Neutral 01 Ls Benzene leach abIes 0.45% 0.05% 0.24% Organic acids Nitrogen 4,000-12,000 19.48% 1.88% 22 .98% TKN 4590 Oxygen Sulfur Hydrogen Comments 8000 .,1 oil1 Di reet Mode Retort water t ['estment Sung et Sung et Sung et Sung et day) flow-4.1 m31 Paraha GCR (Values in % of TOS residue) al. t 1977 a1.. 1977 ai., 1971 aLI min., Slawson Organic acids Slawson, 1979 1977 and Yen. 1979 Prime con- st ituent Slawson & Yen 1979 aSingle va lue reported. Table 13. Continued. In situ Simu- Paraho Direct Paraho I nd i r- Pond Leach ate Omega Condensate Condensate U./Ub lated Mode ect Node In situ Paraho Oi reet Paraho Ind i reet Phase III TOC 3,182 29,200 9,800 1003+ 192 29,200 9,800-36,900 TC 0.72-1.79 TlC 3340+390 9,800 1,600 Bas it: Organics COD 20,000 19,400 17,100 8100+5700 19,400 17,100 50-1500 Total so lid residue 1,219-11,900 EC 25,000 22,000 429 TDS 2,454-24,018 14,210 BOD 5,500 12,000 4,850 12,000 4,800 NH4-N 4,790 14,600 16,800 Ami nes 1-82 a & G 1-100 580· 502 50-100 tv CN- /chelator -.J Phenols 169 46 42 60+30 42 46 50-150 Neutral oi Is Benzene leachab les Organic acids Nit ragen o-N 1,510 o-N 17,340 0.0-0.79% o-N 148-630 Oxygen SuLf ur lIydrogen Comments LERC 10 ton Slawson, 1979 Slawson, 1979 Only dripping Organi cs Cotter et al .• Cot t er et aI., Sour water Slawson, 1979 Woodward- po lar & 1978 1978 stripper Clyde, 1976 carboxyl i c bot toms I Q= acids, 17.7 m3/min + Standard Slawson and deviation Yen, 1979 Farrier et al. I 1979 I , I J I, Table 13. Continued. TOC 14,200-21,000 TIC Basic Organics COD 24,600-21,000 Total so lid res idue 196 (excluding organics) TOS 15,000-2,000 7,253-2,225 1,980-15,300 BOD 9,000-10,800 NH4-N 4,000-1,700 989- 420 Nil) 15 NH3 1,740-4,025 NH3 30 Aml Res 410 602-1,600 410 1,900 0& C 3,000-2,000 880- 506 N 00 CN-/cheiator 5(1.81) Phenols 315(98) 390- 115 124- 44 315 115- 390 315 60 Neutral olls 960(295) 960 1,950-2,840 960 Ben~ene leachables Organic acids 1,330(409) 1,330 515-6,480 1330 1,000 Nitrogen Oxygen Sut fur (sulfide) 768-1,230 Hydrogen Comments surface (j kg/hr) 8000 Slawson. 1979 Tosco II, 4 days pro- used to re lnrt f m3 oil/day Slawson , duction USDI) moisture Sung et Slawsun and 1979 1973 spent shale, al. l Yen, 1979 amoni a & pri 1977 mary .Hipped treated Slawson. 1979 I, , Table 13. Continued. TOC 3,182-19,000 2,830-10,660 I-51 2-38 45.3% 50.3% 63.8% TIC 8asic Orga.nics 7-10%~ NEtS, quinollnes, pridines. maleioides, £uccinimides, thio phenes. sultides COD 12,500&20,000 12,544-14,064 Total solid residue TOS 61-113 251-162 250&5,500 NIl3 4,790 NH3 10,690 Antines 0& G etC/chelator Phenols 2.2-169 31 Neutral oi Is 3~5% subs t i cued benzense &: n alkanes Benzene Leachables Organic acids 10-15% Acidic carboxylic CI-C24J phenols Nitrogen D-N 1510 D-N 654 Oxygen 5.41% 1.68% 6.18% SuI fur 12.95% 0.19% 0.04% Hydrogen 6.28% 9.11% 8.96% Comments 10 gal/ton (2-5) Treatment 10 ton in situ Values presented as % of TDS ave. study Jackson et a1 .• Jackson et al ~ J Jackson et al., res idue, Larami e 10 toll 5 imu- Slawson, 1979 Slawson, 1979 1975 1915 1915 lated 1 Wen and Yen~ 1978 ,I ..I Table 14. Characterization of shale industry related oils ( percent by weight except as indicated). Tosco II Dlrect Mode Unlon B Occldental Petroleum Coal Tosco II crude shale oil Paraho Oil oil in-situ oil crude SyncTude crude shale oil Carbon % 85.1 84.90 84.8 84.86 86.4 82.5 84.68 Ash 0.66 0.005 Sped fic gravi ty 0.927 0.9383 0.812 0.904 (g/cc) API gravity 21.2 19.3 22.7 22.5 15-44 Fischer Assay 24.2 15.25 % recovered 100 91.0 Pour Pt ·C 27 85 F ( 30) 21 OF 95 F ( 35) w 0 Oil 96.0 26 Resin 2.8 48 Asphaltene 1.0 IS Carbene/Carboid 0.2 11 Ni trogen 1.9 2.19 1. 74 1.50 1.14 0.8 1.82 Oxygen 0.8 1.4 0.90 1.13 0.16 7.2 Sulfur 0.9 0.61 0.81 0.71 0.1 0.3 0.83 Hydrogen 11.6 11.5 11.61 11.8 11. 7 9.0 II. 27 References Slawson and Slawson SI awson and Slawson and Slawson Slawson Slawson, Yen 1979 1979 Yen 1979 Yen 1979 1979 1979 1979 Table 14. Continued. Crude Gas Union Tosco In s itu Petroleum Tosco III shale oil Sync rude combustion shale oil shale oil shale oil crude shale oil Carbon % Ash Specific gravity (glee) API gravity 280 46.2 19.1 20.7 28.0 36.2 15-44 22 Fischer Assay % recovered Pour Pt ·C 24 10 28 32 23 -13 w...... Oil Resin Asphaltene Carbene/Carboid Ni trogen 1. 7a 0.035a 2.18 2.01 1. 70 1.14 0.01-0.65 1.9 Oxygen Sulfer 0.8a 0.005a 0.74 0.77 0.80 0.79 0.04-4.1 0.9 Hydrogen References Conkle et a1. Conkle et al. Conkle et Conkle et Conkle et Conkle et Slawson Slawson, 1974 1974 at. 1974 a1. 1974 al. 1974 at. 1974 1979 1979 tempertures. I , I J j I !! Table 14. Continued. LERC in situ Paraho Kerogen x & Benzene extract Organic x & (S) of Fl.scher Assay shale oil shale oil (reported S)b of direct mode matter in shale "oil sIt of TOSCO retorted oil raw shale (n=15 to 19) Carbon % 80.5 (0.4) 81.41 80.5 80.1 (7.15) 85.23 Ash Specific gravity 0.930 (g/ce) APt gravity 28 19.3 20.7 Fischer Assay 26.7 % recovered 100 Pour Pt ·C 23.8 w tv Oil Resin Asphaltene Carbene/Carboid Nitrogen 1.4 2.19 2.39 (0.1) 2.05 2.4 2.54 (0.98) 1.80 Oxygen 5.75 (0.49) 2.22 5.8 3.03 0.23) Sui fur 0.7 0.61 1.04 (0.08) 7.79 1.0 1.26 (1.3) 0.98 Hydrogen 10.3 (0.08) 10.7 10.3 9.53 (2.72) 11.38 References Slawson Slawson Schmidt- Cotter et ai. Cotter et Wen and Yen Slawson 1979 1979 Collerus, 1978 ai. 1978 1978 and Yen 1974 1979 bx , mean; S, standard deviation, O. constituents of shale oil (Guerin 1977). oxides, and the organic content ap "Synthoil" (from a coal) contains ten proaches zero (Schmidt-Col.1erus 1974). times the PAR content of "shale oilll and IIprudhoe crude." Shale oil is dis Processed shale could be described tinctive due to its concentration of as silty gravel or sandy loam (McKell highly methylated aromatics, five or six 1978). Reported physical properties of sites being .common (Jones etal. 1977). retorted shales are presented in Table Comparisons of PAR content of various 15. Coarse waste shales (USBM) have crude and synthetic oils are presented a permeability of about 0.5 darcy while in Appendix A, Table A-2. PAR content that for the finer Tosco shales is about of petroleum products is summarized in 0.05 darcy (Ks '" 8.0 and 0.8 gal/day Table A-22. ft2, or 5 and 0.5 x 10-3 cm/sec, re spectively). The shale residue would In hydrogenated coal oils, the be 10.7 to 11.8 pH with 6000 to 20,000 dominant carcinogenic potency resides in ppm soluble salts (Slawson 1979). the higher boiling fractions. Potency Further data for retorted shale char increases with increasing boiling point acterization 1.S summarized in Table distillation fractions above 260°C (TRW 16. 1976). The permeabilities of the retorted Shale oil contains normal and shales found in various disposal areas branched alkanes and alkenes. Cyc 10- are summarized in Table 17. The bottom hexane with and without alkyl side portion of Table 17 indicates how much chains are present. A comparison of permeability is reduced by compactive C11 to C36 n-a1kane concentrations effort. Permeability of Paraho process in shale oil, petroleum crude, and an e d s hal eat a com pac t ion 0 f 1 2 , 375 oil produced from coal is presented in ft-1bs/ft3 (5.9 x 105 Pa) is 1.4 ft/yr Appendix A, Table A-I. (0.4 m/yr). Associated bulk density and optimum water content would be 92.5 The relative distribution of PAR Ibs/ft 3 (1482 kg/m3 ) and 22 percent me thy 1 isomers 1.n shale 0 il , s yn t hoi 1 respectively (Slawson 1979). The (synthetic oil) and Prudhoe Bay crude moisture content decreases with density oil is compared in Table A-3. As a as shown for Tosco in Figure 9. further comparison, a quantitative analysis of samples collected at coal For estimation purposes, the conversion plants is presened in Appen organic residue in processed oil shales dix A Tables A-4 and A-5. was assumed to range from 3 to 5 percent assuming 86-95 percent volume efficient Retorted shale characterization extraction (Conkle et al. 1974). The total carbon content of shales ranging During retorting the oil shale from 17.8 to 51.8 gallons of oil per ton kerogen undergoes thermal decomposition (74.2 to 216 ~/MT) averages 8.16 percent to oil, gas, and insoluble coke. At by weight. Inorganic carbon averages retorting temperatures (900-l000°F; 480 4.41 percent. and organic carbon aver - 540°C) little decomposition of the ages 5.41 percent (Slawson 1979). carbonates occurs, and reported residual Reported organic carbon content and organic carbon content of the spent other disposal characteristics of shale ranges from 2 to 5 percent. processed shales are summarized 1.n Even at 1200°F (650°C), 2 to 3 percent Table 18 (Slawson and Yen 1979). organic carbon content should be ex pected. At l800°F (980°C) (not present Like the developed oils, the ly a commercial operation possibility) processed shale carbonaceous organic carbonates are calcified and fused to matter contains polycondensed organ1.C 33 I · .. 1 J Table 15. Physical properties of retorted shale '(Ward et a1. 1971 t Woodward-Clyde 1976, Guerin 1977). Retorting Method Property Gas Comb us t ion Union Toseo II Geometric mean size t in 0.081 Not Reported 0.003 (em) (0.205) (0.007) 2 Permeability, in 5. 36xl0-~0 Not Reported 3.88xlO-11 (enh (3.46xl0- ) (2.5xlO-1O ) 3 Bulk densi ty t Ib/ft 89.90 112.37 81.16 (gl ee) (1.44 ) (1.80) (1. 30) Solid density, Ib/ft3 153.58 169.19 155.45 (glee) (2.46) (2.71) (2.49) Maximum size t in 1.50 Not Reported 0.19 VJ (em) (3.81) (0.476) .j::- Minimum size, in 0.0003 Not Reported 0.0003 (em) (0.00077) (0.00077) J I, " Table 16. Macro elemental characterization of retorted shales (percent by weight). CarDon Inorganic Organic Total Nitrogen Sulfur Other Mined Shale 14.7 0.39 (Ward et al., 1971) BOM retorted 8.2 0.28 (Ward et al., 1971) Tosco retorted 10.2 0.38 (Ward et al., 1971) USBM retorted 3.25-4.3 2.69-4.96 0.22 (Woodward-Clyde, 1976) Paraho retorted 4.15& 1. 84 2.18&4.95 (Woodward-Clyde, 1976) w V1 Mined shale 4.84 11.4 0.22 H2O 1.9 (Woodward-Clyde. 1976) Ash 67.8 Direct mode retorted 2.15 0.8 0.13 0.08 S04 Ash 92.88 (Cotter et al., 1978) 0.74 8x Mined particulates 4.67 9.58 0.43 0.01 804 Ash 70.91 (Cotter et al., 1978) 0.04 Sx In situ retorted 2.4 & 2.6 0.21&0.l2 0.55&0.61 H 0.235 (Wen and Yen. 1978) Mined shale 16.53 0.46 0.75 H 2.15 (Slawson. 1979) I ! , I J I, Table 16. Continued. Carbon Inorganic Organic Total Nitrogen Sulfur Other Tosco II retorted 4.94 0.28 0.62 H 0.27 (Slawson, 1979) Mined shale 12.4&13.5 0.39&0.41 0.28&0.63 Ash 65.7&66.1 (Slawson, 1979) MFA 17 & 28 World shales-mean (standard 30.8 0.51 1.08 Ash 54.7 deviation) (Slawson, 1979) MFA 56.8 I J II " Table 17. "Permeabilities found in various shale disposal areas. Permeahil1ty References USBM retorted 3.46 x 10-9 cm2 Ward et al., 1971 Tosco II retorted 2.5 x 10-10 cm2 Ward et a1., 1971 Paraho leach studies Kn = 10-3-10-6 em/sec Ward et al. , 1971 Review 10-9-10-10 cm2 Conkel et aI, 1974 In situ retort tests Field infiltration Kn = 4.24 x 10-6 em/sec Holtz, 1976 (pond studies) 2 x 10-3 em/sec Holtz, 1976 Uncompacted 1000-3000 ft/yr (305-915 m/yr) Holtz, 1976 Compacted @ 100 Ibs/ft3 (1600 kg/m3) 1.0 ft/yr (0.3 m/yr) Holtz, 1976 Surface percolation 1 - 2 in/hr (2.5-5.0 cm/hr) Slawson, 1979 Paraho (WRSP, 1976a): Permeability ft/yr (m/yd Compactive effort psi (105 Pa) ft-lb/ft3 (105 pascal, Pa) SO (3.4) 100 (6.9) 200 03.8) Low 6200 (3.0) 15.5* (4.7) 5.5 0.7) 1.7 (0.5) Moderate 12,375 (5.9) 7.0 (2.1) 1.4 (0.4) 0.8 (0.2) High 56,250 (26.5) 1.1 (0.3) 0.6 (0.2) 0.08 (0.02) (*maximum permeability values seen 10 to 30 + ft/yr (3 to 9 m/yr» matter (POM) or polynuclear aromatic A-9 to A-II), aquatic organisms and food hydrocarbons including heterocyclic (Appendix A, Table A-12) and waste species such as azaarenes (Schmidt waters/river waters (Appendix A, Tables Collerus 1974), thiophenes, and furans. A-13 to A-15) are also provided. Examples of polycyclic aromatics PAH through 5 rings (and perhaps coro detected in processed shales are shown nene, 7 rings) have been detected in the in Tables 19 to 21 and Figure 10. To Paraho and Tosco II processed shales provide a comparison, selected estimated (see Tables 19 to 21 and Figure 10). As PAR concentrations of soils and sedi yet, the quantification of identified ments (Appendix A, Tables A-6 to A-8) , PAH species has not advanced to a state air emissions and ambient air particu of,comparability with reported environ late concentrations (Appendix A, Tables mental PAH concentrations. A major constraint to quantification of PAR in processed oil shales is that develop ment of standard methods for working with complex shale matrices is in early IOO'T""'------__,---r--..,--¥----r development stages (Slawson and Yen 90 1979; Slawson 1979; and Analysis and Quality Assurance Symposium 1979). SO c: .270 Three to four-cyclic PAH from ~60 processed oil shales have been identi fied by thin layer chromatography (TLC) , ~50 ultraviolet spectroscopy (UV), high c40cu pressure liquid chromatography (HPLC), (.J 4i 30 gas chromatography (GC), mass spectro a. metry (MS) , and gas chromatography/mass 20 spectrometry (GC/MS) (Tables 19 to 21 (0 and Figure 10). An initial benzene o ~-~-~--_r-~----~--~-~-~ soxhlet extract ion has most often been 70 SO 90 100 110 (20 130 140 used to develop processed shale organic (IJ 21) (1282) (442) li602) (lT62) (1923) (2083) (2243) samples. The weight of dry concentrated benzene leachables per amount of sample extracted can be used as an indicator (assuming a standard assay). Soils, Figure 9. Moisture content as a func alluvium, plants, raw crushing particu tion of percent saturation lates, and associated operat ion waters and dry density for Tosco II have also been evaluated using benzene processed shale. leaching (Tables 22 to 25). Water Table 18. Organic carbon content and other disposal characteristics of processed shales. D~rect Mode Paraho 2-3% organic carbon Tosco II about 4.5-5% organic matter 14% H20 60% < 200 mesh 35% < 325 mesh Union B 4.3% organic carbon 16% H20 uncompacted 61 lbs/ft3 (980 kg/m3 ) compacted 90 lbs/ft3 (1442 kg/m3 ) 38 I, , Table 19. Polycyclic aromatic hydrocarbons detected (Coomes 1976). Raw Tosco II Processed Shale Laboratory Compound DRI Eppley TaSCa Compound DRI Eppley TaSCa Battelle Benzo(a)pyrene (BaP) x x x Benzo(a)pyrene (BaP) x x x x Alkyl.l (BaP) x Alkyl I (BaP) x x Benzo(ghi)fluoranthene x Alkyl II (BaP) x x Benzo(e)pyrene x Benzo( gh:U fluoranthene x x Perylene x x x Benzo(e)pyrene x x x Benzo(ghi)perylene x x Perylene x x x w Anthanthrene x x x Benzo(ghi)perylene x '" Pyrene x x Anthanthrene x x x x Fluoranthene x x Pyrene x x x Benz (a) anthracene x x Fluoranthene x x x Triphenylene x Benz (a) anthracene x x x Phenanthrene x Triphenylene x 7. 12-Dimethylbenz(a) anthracene x Phenanthrene x x 3-Methylcholanthrene x 7. 12-Dimethylbenz(a)anthracene x Coronene x 3-Methylcholanthrene x Chrysene x Coronene x Chrysene x x J I. 5 15 TIME SPEeT 50 100 150 200 250 300 350 400 450 500 550 2 t. C3·8ENZENE 2. INDENE s<'3% .SP2100 20H2.120-250oI6 3. METHVLINDENE 4. NAPHTHALENE 5. DIMETHVLlNDENE STARTING MASS 50 &. METHVLNAPHTHALENE 4 7. METHVLNAPHTHALENE 8. Cl·ANISOLE 9. IIIPHENVL OR ACENAPHTHVLENE II 19 to. DIMETHVLNAPHTHAlENE 18 tt. DIMETHVLNAPHTHALENE 17 t2. IIIPHENVLENE ... 13• DIMETHVLlNDOLE i5 14. DIMETHVLINDOLE AND 0:: DIMETHVLNAPHTHALENES a:: 16. ACENAPHTHENE a 6 16. DIMETHVLINDOLE .po z 11. TRIMETHVLlNDOLE 0 Q 12 lB. TRIMETHVLNAPHTHALENE 19. flUORINE ..J 12 7 20 .. TRIMETHVLlNDOLE ~ 10 2t. TETRAMETHVLlNDOLE ~ 22. TETRAMETHVLINDOLE 23. METHVLFLUORINE AND PENTAMETHVLlNDOLE 3 24. PENTAMETHVLlNDOLE 25. PHENANTHRENE AND ANTHRAceNE 26. Ct;·INDOLE 21. METHVLPHENANTHRENES 28. METHVLPHENANTHRENES 29. Ct6H16 3D. DIMETHVLPHENANTHRENE 3t. TRIMETHVLPHENANTHRENE SPECT 500 550 600 Figure 10. Typical gas-liquid chromatogram of oil shale polynuclear aromatic fraction (Schmidt-Collerus et a1. 1976). Table 20. Particulate polycyclic organic matter (POM) compounds identified in ben zene extract of carbonaceous shale coke from Green River oil shale (from Schmidt-Collerus 1976). Name of Compound Potential Carcinogenicitya Phenanthrene Fluoranthene Pyrene Anthanthrene (dibenzo(c,d,j,k)pyrene) Benz(a)anthracene (1,2-benzanthracene) + Benzo(a)pyrene +t-+ 7, 12-Dimethylbenz(a)anthracene ++++ Perylene Acridine Dibenz(a,j)acridine (1,2,7,B-dibenzacridine) ++ Phenanthridine ? Carbazole 3-Methylcholanthrene ++++ aNumer of + symbols indicates increasing potential as carcinogen. samples are first evaporated prior to al. 1978). Slawson (1979) reported 0.45 soxh1et leaching of the resulting percent benzene leachables for 16,600 residue to determine the benzene 1each ppm TD S ret 0 r twa t e r ( Tab 1 e 25). abIes and contained constituents. In another report process water of 15,000 to 20,000 mg/l TDS yielded Processed shales generally contain 0.737 percent benzene leachables. On between 0.02 and 0.2 percent (2000 ppm) this basis, the benzene leachables in benzene leachables. USBM shales were processed shales range from one to two 0.2560 percent; Tosco shales ranged from orders of magnitude higher than back 0.007 to 0.26 percent (lower value from ground soils, and those in processed a sample sealed in drum for 7 years). shale leachate waters were estimated to Pristine soils ranged from 0.0075 to range three to four orders of magnitude 0.0593 percent. One 7-year-old shale higher than in groundwater. Further, sample yielded only 0.0005 percent assuming 41 I , I J I, , Table 21. Polycondensed aromatic hydrocarbons identified in benzene extracts of carbonaceous spent shale from the Tosco process. a Fluorescence Compound TLC. Color Retention Spectrum Remarks Time phenanthcene x benz (a) anthracene x x x dibenz(a,h)anthracene x x 7, 12-dimethylbenz(a)anthracene x x Fluorescence spectrum indicates a possible mixture with another compound; separation of these by HPLC in progress fluoranthene x x 3-methylcholanthrene x x Further confirmation by HPLC in progress ..,.. pyrene x N benzo(a)pyrene x x x dibenz(c,d,j,k)pyrene x x x Separated by HPLC from BaP perylene x x x benzo(g,h,i)perylene x Fluorometric identifi cation in progress bThin-layera chromatography, TLC High pressure liquid chron~tography. HPLC I'I " Table 22. Evaluation of benzo(a)pyrene (BaP) content in samples of benzene extracts from various spent shale, soils. plants. and leached salt samples (Schmidt-Collerus 1974). Sample Size of Weight of Weight of BaP in Size Benzene-soluble PAH in BSF, BaP in BSF. Sample (g) Fraction, BSF, g g g (ppm) Spent shale (6 4000 9.24 3.06 (33.11)a 0.000074 (0.0008) 0.019 months old) 4000 9.24 3.06 (33.U) 0.000185 (0.002) 0.046 Spent shale (6 2000 4.66 1. 37 (29.31) 0.000093 (0.002) 0.046 months old, water 2000 4.66 1.73 (29.31) 0.000233 (0.005) 0.U6 leached) Spent shale (6 2000 5.12 1. 29 (25.15) 0.000031 (0.0006) 0.015 .!'- months old, weathered) VJ Water soluble salts 50 0.09 0.000001 (O.OOU) 0.0002 from spent shale Soil for Middle Fork, 1097 0.32 0.05 (16.70) 0.000001 (0.0002) 0.0000337 Parachute Colorado 200 10.20 0.000010 (0.0001) 0.00059 aNumbers in parentheses and percent of total benzene-soluble fraction. BSF. , I J il " Table 23. Evaluation of benzo(a)pyrene (BaP) content in samples of benzene extracts from direct mode retorted shales (Cotter et aI. 1978). Benzene BaP BaP in BaP in BaP in BaP/TLC BaP in Extract % Benzene Shale Benzene Sample Designation Spot Sample Quantity Benzene Extract Sample Extract ( lJg) ppm Analyzed (mg) Extract (lJg/kg) (llg/kg) ppm Pilot Plant 8.7 0.050 0.000 4.7 x 1 2.0 4.7 0.2 x 10-2 (Direct Mode) 3 2 8.7 0.038 0.000 3.6 x 10 1.5 3.6 0.2 x 10- ~ Retorted Shale ~ 0/12/76, 1000 hrs) Ave. 0.044 0.001 4.2 x 1 1.8 4.2 0.2 x Retorted Shale 3 2 Ave. 0.189 0.001 14 x 10 1.50 0.2 x 10- (Direct Mode) 14 Semi-Works (3/7 5) Table 24. Benzene and water extractables of retorted shale, and raw shale particulates (Cotter et al. 1978). Benzene Solubles Benzene Solubles Total Benzene Water Solubles Sulfur Removed of Water Solubles Solubles Wt % Wt % Wt % Wt % Pilot Plant (Direct Mode) Retorted Shale (3/12/76, 1000 hrs) 0.03 0.03 3.39 0.00 Raw Shale Collected as Air Particulate in the Crushing Area (3/15/76 to 3/17/76) 2.05 ND ND ND ND = Not determined. Comparison of PAH to polar compounds in solid samples. Sample Designation Wt. % PAH Wt % Polar Compounds Pilot Plant Retorted Shale, Direct Mode (3/12/76, 1000 hrs) 43 57 Raw Shale Air Particulate (3/15/76 to 3/17/76) 16 84 j Ii 1I a Table 2S. Summary of electrolytic treatment of retort water (Slawson and Yen 1979). Total Benzene- Organic b Nitrogen Solid COD Soluble Carbonb c Color d Portion (% wt) Residue (mg/l) Material Intensity (% wt) (% wt) (% wt) Original retort water 9.16 19.48 1.68 16,600 0.4S 3441 Processed solutions Anodic solution 0.42 1.88 LOS 6,283 O.OS 255 Cathodic solution 4.04 22.98 2.01 9,991 0.24 1214 .f:"- a- 2 aTreatment in U-type membrane cell at current density of 20 mamp/cm , cell voltage of 15 volts, and 10-hour treatment time. b Elemental analyses of the lyophilizing solids (ELEK Microanalytical Lab., Torrance, California) . cValues for wa ters subject to lyophil iza tion. 7S0 nm dColor intensity = f A dl, where A is adsorbance and l is the wavelength. 2S0 nrn Based on similar initial assumptions, It must be emphasized that reported operation of a 100,000 bbl/day (16,000 estimates of the BaP content of benzene m3 /day) surface retort plant would leachables of shale related wastes may yield 1.8 x 106 tons/year (1.6 x not be an adequate representation of 106 MT/yr) of processed shale requiring complex shale related matrices. In disposition. Associated with these relation to other materials, coal tar wastes are 100,000 tons/year (90 x 103 and petroleum pitch contain about 107 MT/yr) benzene leachables. If process times as much BaP as does processed water is used to moisten processed . shale benzene leachables. Oils and shale, a four-fold increase of benzene petroleum products contain BaP concen solubles, to about 400,000 tons/year trations of 10 to greater than 103 (360,000 MT/yr) should be expected ppb. In review the BaP content of (Schmidt-Collerus 1974, 1976; Slawson benzene leachables from processed shales 1979). has been estimated to range from about 1 to more than 102 ppb. Further, 103 Benzo(a)pyrene (BaP) is often ppb BaP is most characteristic of shale used as a single indicator of PAR and coal derived oils. As a specific content of samples. The content of BaP reference, BaP of shale oil has recently in benzene leachables from processed been estimated as 1800 - 4250 ppb shales reported in the literature ranges (acridine = less than 20 - 34 ppb from 2 to 115 ppb (Guerin 1977; Cotter (Analysis and Quality Assurance Symposi et al. 1978; Analysis and Quality um 1979». Background water BaP concen Assurance Symposium 1979). From an trat ions are generally less than 10-2 evaporated shale water leachate, 0.2 ppb ppb. However, the average BaP content BaP were estimated by developed benzene of soils and sediments as well as of leachables, using two-dimensional TLC many foods, range from 10-1 through 10 and UV (Schmidt-Co llerus 1974; and ppb. Further. city air particulates Cotter et al. 1978). Shale and coal average about 10 ~g/g BaP and thus range proces~ waters contain from 1 to 103 from 10-2 to 1 ng/m3 (see Appendix ppb BaP (Guerin 1977). A, Tables A-6 to A-19). 47 MATERIALS AND METHODS Western shale organic content gime s, and water regimes. The samples estimates have been reported by U.S. investigated include three processed Geological Survey and Bureau of Land oil shale samples from t he Union B Management since the turn of the cen operations, two Paraho operation sam tury. More recently, because of in pIes, and one Tosco II operat ion sam creasing attention to this fossil fuel pIes. Shales associated with in situ reserve, methods and estimates of oil retorting (one simulated geokinetics extractability and characterizations of processed sample), two mined samples, organic constituents have been re and collected alluvial samples (from ported. In the past decade, many Sand and Cottonwood Wash tributaries of investigations of oil shale kerogens and the White River in Utah) were also bitumens have focused on macroconstitu studied. ent determinations. Others report One large Paraho processed shale development of laboratory regimes sample originally used to investigate designed to isolate and identify the me thods to opt imi ze res t ora t ion of organic residue from processed oil surface shale disposal areas (Malek, shale. More intensive investigations of personal communications 1979)~ was the organic matrix of produc ts and composed of material from recent demon wastes derived from shales, tar-sand, stration operations at the USBM site, coal, and high boiling crude oil dis where 100,000 bbls (~16,000 m3 ) of tillates are also reported. Isolation synthetic oil was produced to investi methods have included 1 iquid/ 1 iquid gate refinerability. Left exposed to (L/L) extractions, thin layer chromato winter weathering this shale sample graphy (TLC), and liquid column chroma cleaved along sedimentary planes to fine tography (LC). Extraction and elution particles. Up to palm-sized, slate solvents employed have ranged from shaped hard particles were inc luded in low polarity solvents (i.e., benzene, t his b 1 ac k pro c e sse d s hal e sam pIe. cyclohexane, hexane(s), pentane) through polar solvents (i.e., acetone, ethanol, A second Paraho sample was used to methanol, CH2C12, CHC13). Basic, investigate indirect heating mode neutral, and acidic isolation conditions operations and in shale/plant growth and TLC/LC media have been used. studies. This sample was a < 1/4 inch Reported identification methods employed sieve fraction of the initial processed include nuclear magnetic resonance shale (Richardson 1979). Only a moder (NMR) , mass spectrometry (MS), infrared ate amount of this sample was available (IR), high pressure liquid chromato (abou t 50 kg). graphy (HPLC), gas chromatography (GC), and gas chromatography/mass spectrometry Three Union B shale samples were (GC/HS). A selection of these investi received from Union Oil in 1977. One gations is summarized in Appendix B (including associated references). sample was a blond colored, raw shale, with a maximum size of less than 1/4 inch « 0.64 em) hard particles. The Laboratory investigations conducted other sample was black, and easily as part of this study explored sample crushed to fine particles. These two characteristics, organic solvent re- samples were less than 5 gallon volumes 49 (IV 19 Q,). A third Union B shale sample of ing classical organic chemistry pro about 50 pounds (23 kg) is believed to cedures, were used to extract and be reflective of incomplete retorting. concentrate the organic materials This material was also black, and in the shale samples. Second, water was crushed with ease. The bulk of this used for ext ract ion. The water ex material was used in revegetation tracted organics were either sorbed by a studies (Richardson, personal communi- resin in a packed column and eluted with cation 1979). polar solvents or partitioned to organic solvents by liquid/liquid extraction in Only about 25 pounds (11 kg) of a separatory funnel prior to concentra Tosco II processed shale was available. tion and GC/MS identification of con The sample obtained was the most homo stituents. geneous of all the shales, and consisted of dark black fine particles. The Tosco A low level of light was maintained II shale was produced at the Parachute during laboratory procedures to limit Creek Colony site, but was obtained at photolysis. All laboratory equipment the Colony site in Utah. This shale utilized was made of glass, metal, or was used in reclamation studies at the teflon. Reusable glassware was washed Utah Sand Wash project (Cozzart et al., in three organic solvents of increasing personal communication 1978). polarity (benzene, methanol, and ace tone), acid/base washed, distilled water The findings of the anaiyses for rinsed and oven dried. Extraction and total organic carbon (TOC), volatile concentration glassware was heated for·l solids, and benzene leachables are hour at 550°C prior to washing. presented in Table 26. TOC was deter mined by employing methods for sediments A soxhlet extraction method was as presented by Oceanographic Inter employed to develop extracts for GC national Corporation (College Station, GC/MS investigations. As cited in the Texas). Evaluation of TOC data sug literature, soxhlet extractions have gested that this indicator of processed included the use of redistilled (in shale organics is interfered with by the glass) pentane, cyclohexane, benzene, high bicarbonate character of the and benzene:methanol mixtures. However, samples. Farrier et al. (1979) also the bulk of the soxhlet extraction noted these interferences while investi work was conducted with benzene. gating "Omega-911 in situ retort water. Volatile solids-;e-;;-determined by After initial investigation with drying the samples at 103°C to determine soxhlet operation conditions, samples dry weight and then heating the samples were extracted for 3 days in benzene, for 12 hours at 550°C. Benzene leach followed by 3 days in methanol. Four abIes were determined gravimetrically by hundred gram samples (as mined or we ighing dried residue .obtained from a processed shales, or alluvium) were benzene soxhlet extraction. The results placed in each soxhlet and 1.2 Q, of are in harmony with values reported in leaching solvent was used. Soxh let the literature. However, the reported operation cycles were maintained at 5 characterization values represent the min/eye Ie. The more polar concen products of pilot plant retorting and trated methanol extracts were used should not be considered as necessarily in the Ames test for mutagenicity reflective of commercial scale processed testing (Dickson et al. 1979). shales. Extraction of Organics Each soxhlet extraction sample was divided in half. One part was then Two approaches for extracting concentrated by flash evaporation organics from spent shal es . we re em (Buchler Instruments) and the other part ployed. First organic solvents, follow- concentrated by Kuderna-Danish heat 50 ! J I, Table 26. Summary of sample characteristics (percent by weights). Proximate & Ultimate Analysis (ASTM)b Benzene Fixed Volatiles Leachable TOCd Carbon Carbon Nitrogen Sulfur Volatiles BTU/lb (l05 J/kg) Parahoa 14 4.96 2.66 8.38 0.39 0.52 0.56 23.6 543 (12.6) Paraho 7 0.0155 2.0 6.8 0.2 0.28 0.75 20.7 38 ( 0.9) Tosco 9 0.188 2.44 9.82 0.05 0.35 0.60 26.7 470 (10.9) Uniona 15 7. 73 2.39 Union processed 13.8 1.17 10.53 0.02 0.52 0.56 27.2 631 (14.7) Union as mined 27.0 1. 74 Geokinetics 17 .8 0.863 as mined Geokinetics 5.51 0.0039c processed In situ as mined 17.4 Insitu processed 15.0 0.0255 U1..... Sand wash 2.59 0.0031 aluvium Cot tonwood 2.51 0.0075 aluvium :Believed to be examples of incomplete processing. American Society of Testing of Materials; performed by Commercial Testing and Engineering Co., Denver, Colorado. cBased on benzene leachables from 400 g samples; other benzene leachables presented based on 1. 6 kg. dOceanographic International Corporation method (P.O. Box 2980, College Station, Texas). Note: The shale samples are identified by process source but are judged representative only of early shale development investigations and should not be considered reflective of commercial scale processed shales. evaporation (500 ml Kontes with a 10 ml gel, fractions were sonicated (Bronwill/ concentration tube and macro Snyder VWR Scientific) to homogenize the condenser). A solvent removal rate of methanol silica gel mixtures. The less than 10 ml/min was maintained silica gel was removed from these wi th both Kuderna-Danish and flash emulsions by filtration at '\J 0.5 atmo evaporation concentration methods. The spheres (5 x 104 Pa) (GFC filters). concentrated solutions ('\J 10 ml) were The filtered sample fractions were then further concentrated to 5 ml at concentrated in a nitrogen atmosphere. room temperature using a gentle stream The separated TLC silica gel showed no of nitrogen. The concentrates were fluorescence under the UV hand lamp. stored in the dark at 4G C in 5 ml glass bottles with teflon-coated caps. Activated carbon as well as acti vated alumina LC was reported to yield Concentra~ion attempts often poor performance when at tempt ing to resulted in the formation of a tarry isolate fractions from tar (Natusch and matrix. Several hundred milliliters of Tomkins 1978). Cited work with carbon the tarry soxhlet concentrates were air black. coal tar and pitch had indicated dried on a large watch glass (teflon that 35 percent extraction losses can be lined 55 gallon drum lid). Dried expected when using alumina LC columns. residue was chipped, weighed, and Comparatively, 6 percent separation stored dry when appropriate, or washed efficiency losses during TLC have been quantitatively and combined in an reported (Schmidt-Collerus 1974). asphaltene/resin like tar in preweighed Comparison of gas chromatography (GC) glass jars and stored. Characterization integration areas of TLC and LC (A1 203 of these samples is presented in Table and silica gel) developed samples 26. support the above observations. Isolation Approaches Experiments with LC, TLC, known PAH and constituents of soxhlet developed Thin layer chromatography (TLC) was concentrates indicated that the more utilized to fractionate some of the polar solvents could play important concentrated soxhlet extracts. Concen roles in the separation and identifica trated extracts equivalent to a combined t ion of PAHs. It mus t be not ed, how soxhlet charge of 1.0 kg were applied to ever, the solubility of PAH is limited silica gel plates (EM Laboratories Inc., in methanol concentrates. In addi 20 cm x 20 cm x 2 mm, PLC 60F-254 tion when compared with less polar Plates); and developed in benzene:cyclo solvents, GC column performance was hexane (3:2). Separated compounds were reduced. Thus many samples developed in visualized by means of an ultraviolet more polar solvents were taken to near hand lamp. As observed in ul traviolet dryness and redissolved in benzene prior light ('\J 254 nm), the ten compounds to GC/MS. included in a standard PAH mixture ( S u pe 1 co, Inc • ) res 0 1v e din t 0 f i v e Gel distribution column chromato fractions. Based' on the TLC resolution graphy, LH-20, has also been used in of the PAH standard mixture, the re hopes of concentrating PAH while ex solved sample TLC plates were fraction c luding alkanes and large "polymers. II ated by Rf value as < 0.1, 0.1-0.25, The LH-20 gel was swelled overnight in 0.25-0.6, 0.6-0.8 and> 0.8 of the 85 percent methanol (15 percent water) developed solvent front. The silica gel eq uil ibrated wi th n-hexane. Tarry as fractionated was scraped from the TLC soxhlet concentrates (low polar solvent plates and the associated resolved soxhlet extractions from 0.2 to 1.0 kg sample components were extracted with of processed shale samples) were passed methanol. To ensure a maximum recovery through a column (20 cm x 1 cm) of the of the sample components from the silica LH-20 gel. As passage was slow. pres- 52 sure (N2) was applied to maintain flow ini tia 1 inves t igations. Losses of at > I ml/min. The gel was washed with residue during lyophilization was noted. n-hexane and then removed from the Lyophilization of water samples was column and mixed with about 500 ml followed by benzene soxhlet extractions isopropanol. The mixture was filtered of the resulting gray/white crystalLine and concentrated by roto evaporation and residue. The concentrated benzene stored as described previously. samples showed no quantifiable peaks during GC screening. However, Cotter et Water Extractions al. (1978) have used lyophilization to concentrate retort water residue prior Shale samples were subjected to to benzene soxhlet extraction. Organic soxhlet water extraction (previously concentrations in retort water are described), column leaching, and direct believed at least 103 times the con mixing. Combined use of soxhlet centration of processed shale aqueous and XAD sorpt ion was also explored. leachates. An upflow column was designed and As required for soxhlet and shale successfully operated for the purpose of mixing developed samples, water samples flow through generation of processed were filtered (Buchner funnel; Whatman shale leachates. Dry weight column #2 filter) and analyzed for solids, TOC, capacity was about 2.5 .kg. The water pH, and EC and sensory observations were throughput rate was controllable to recorded. Filtered precipitated salts allow replication of expected spent associated with soxhlet developed shale disposal site geohydrological samples showed little fluorescence characteristics (i.e., Darcy k less than response to UV light (254 nm) but were 10-4 em/sec). Dry bulk densities of stored with filters and subsequently studied column packs ranged from extracted. Samples developed using the 72.5 to 88.7 Ibs/ft3 (1161 kg/m3 to upflow column did not require filt ra 1420 kg/m3 ). tion. As another approach, a 55 gallon Water samples were either passed teflon-lined drum was used as a mixing through a non-ionic sorpt ion resin or chamber for the water extractions. L/L extraction was used to develop GC/MS Mixing run compositions varied from 5 to samples. Often water samples subjected SO kg dry spent shale « 1 mID sieve) and to resin adsorption were subsequently from 10 to 100 liters of water. After L/L extracted to allow comparisons of mixing (from 2 to 12 hours) and investi differential resin efficiency. gation of post mixing physical settling characterist ics (about 90 minutes), 20 For preparation of the XAD-2 resin, liters of near surface water were drawn three soxhlet extractions of 8 hours off and filtered through Whatman Quali each were required. The XAD-2 resin was tative #2 filters. placed in a soxhlet and extracted first wi th acetonitrile, then ether, and Freeze rotation and lyophilization finally with methanol. The resin was (freeze drying) were explored as methods stored under methanol. A detailed for concentrating water samples. description of XAD preparation and Considering the inability of separating column operations is presented in Junk the high TDS concentrations to a single et ale (1974). Others (Yamasaki and solutio.n during freeze rotation (Baker Ames 1977; Stepan and Smith 1977; 1968), it was concluded that this method Chriswell et al. 1977) report other was inappropriate for quantitative preparation techniques •. concentration of proce.ssed shale/water deve loped organics. The freeze-drying A glass chromatography column (20 x approach was also discontinued after 1 em id) with a 20, 4 or 1 liter de- 53 livery tank was used for the XAD-2 concentration tube and macro Snyder resin. The length of XAD-2 resin packs condenser). As with organic concen were maintained at 10 cm. Silanized trates, final drying was done with a glass wool plugs were used on each gen tl e stream 0 f ni trogen (in this side of the XAD-2 column resin pack. case to < 1 ml). Samples were stored in After activation of the resin with 40 ml the dark at approximately 4°C in labeled deionized water (Milli Q System, Milli 5 ml bottles with teflon-coated tops pore Filter Corp.) Bedford, Mass.), prior to GC/MS characterization. water samples were passed through the column at 10 to 30 ml/min. Stepan and Using a simplified L/L extraction Smith (1977) report that best PAH technique (pH between 7 and 9 only) sorption efficiencies are associated samples resulting from chlorination of a with column flow rates less than 20 known PAH mixture were also developed. ml/min (study minimum). After sample The standard PAH solution used contained passage and washing the res in with 10 species (3 to 5 rings; 178 to 252 mw) deionized water (twice with 25 ml each indicated with asterisks in Table 27. time) 2 x 25 mt) an ether e lutant was Between 1 and 10 llg of each of the PAH taken (3 x 10 ml with a 10 minute species was subjected to chlorination equilibrium wait). The ether elutant was in a series of tests. Contact times then dried with anhydrous MgS04 .and ranged from less than one hour to more concentrated to 1 ml in a gentle stream than two days. Chlorine concentrations of nitrogen. ranged from 0 to 1000 mg/l. Free available chlorine was determined by The sorption resin in the chroma using a Hach kit (Model CN66). The tography column was eluted with methanol accuracy of the kit results was con (3 x 10 ml) and reused for water soxhlet firmed using both amperometric titra extracts developed from identical tion and the standard iodometric tech samples. Finally, the methanol regen nique (Standard Methods, APHA, 1975). eration elutants were combined with the The developed samples were extracted resin in a soxhlet extraction (500 with CH2C12. Concentrates for GC/MS ml methanol for 3 days). The methanol investigations were developed as pre soxhlet extract was concentrated by the viously described. Kuderna-Danish technique as previously described. GC/MS and GC Identification Water samples were L/L extracted Organics in the concentrated using a method recommended by the EPA extraction samples were identified with (1977). The pH was first raised to > 11 a Hewlett-Packard gas chromatography with 6N NaOH and serially extracted with mass spectrometer (HP 5985 GC/MS Sys CHZC12 (Z liter water batches, CH2C12 tem). A 10 meter glass capillary column serial extractions = 125 ml x 50 ml x 50 coated with SPZIOO was temperature ml). The pH was then changed to < 2 and programmed from 90 to 250°C at 5°/min to again serially extracted with CH2C12 resolve sample components. The mass (this time 2 liter water batches, spectrometer ionization voltage was CH2C12 100 ml x 50 ml x 50 ml). Ex maintained at 70 ev. Injection port and tractions were continued until CH2C12 transfer line temperatures were Z50° and solvent recovery was greater than 85 275°C, respectively. percent. "Emulsion plugs" which de veloped at the CHzCIz/water interface, An HP-5750 gas chromatograph were also combined with respective equipped with a 180 cm x 0.3 cm stain CHZCIZ extractions, and all were dried less steel column packed with 10 percent with anhydrous Na2S04. Dried extracts SP2100 on 801100 mesh Supelcoport was were concentrated with a Kuderna-Danish used for sample screening work. This evaporator (SOO ml Kontes with a IS ml column performed adequately (Figure 11) 54 , I J Table 27. Summary of GC/MS study standards. Standard Species Molecular GC Retent10n UnH MS Detector ResEonse Weight Time (min) Iu/nga (Iu/ng r2 n)b Carbazole 167.21 12. 10. 4-Azafluorene 167.21 7.8 11.4 Acridine 179.22 10.9 9.5 2-Aminofluorene 181.24 15. 0.5 Dibenzothiophene 184.26 9.8 9.53d Anthracene* 178.24 10.4 9.55 0.997 8 Phenanthrene* 178.24 10.2 10.3 0.992 7 Fluoranthene* 202.26 15.5 19.5d 20.1 0.997 5 Pyrene* 202.26 16.4 20.2 0.989 6 Thianthrene 216.32 13.5 7.5 Aminopyrene 217.27 24. 1.4 Triphenylene* 228.30 22. Benz(a)anthracene* 228.30 22. 13.7 33 0.998 5 Chrysene* 228.30 22. Benzo(e)pyrene** 252.32 27.3 U1 Perylene** 27.5 d 34 U1 252.32 l1.85 0.834 4 Benzo(a)pyrene** 252.32 27.7 4.5 13H dibenzo(a,i)carbazole 267.33 33. 1.14 7,12 dimethylbenzo(a)anthracene 256.32 26.5 0.77 Benzo(g,h,i)Ferylene 276.34 32. 9.31 Dibenzanthracene 278.36 32. 6.7 Dibenz(a,c)anthracene 278.36 (c) Picene 278.36 (c) Pentacene 278.36 (c) Coronene 300.36 (c) 1,2,4,5 Dibenzopyrene 302.36 (c) 3,4,8,9 Dibenzopyrene 302.36 (c) 3,4,9,10 Dibenzopyrene 302.36 (c) Sulfur 13.5 Hexachlorobenzene 9.1 *&**PAH Standard Solut10n, Supelco Inc., Bellefonte, PA. aRelative single ion integration units (Iu) per ng injected, single values using ~0.5 pg/ul injection; except d. bRelative single ion integration units (Iu) per ng injected, average values from a serial dilution study (> 500 to < 5 ng/Wl injection (r2, coefficient of determination and n, number of samples). CPAH not determined at injection concentrations < 10 ng/pl on SP2100 capillary column. dThree or greater determinations using 0.1 to 10 ug/ul injections. yet at higher operating temperatures (> even of the larger molecular weight 250°) column bleed was excessive. isomers. GC/MS 1 ibrary ident ifica tions were possible with injections equivalent to less than 1 ng/~1 for the A liquid crystal packed column was 3 and 4 ring PAR indicated in Table 27 also used to resolve a standard PAR with a single asterisk (*). About 5 ng/ mixture for comparison with the above ].11 GC/MS injection concentrations were study columns. The liquid crystal necessary for MS identifications of the column yielded excellent resolution, 5 ring PAR indicated in Table 27 (**). HP-5750 gas chromatograph 180 x 0.3 em stainless stell column 10% SP2l00 on 80/100 mesh Supelcoport Carrier gas He at ~25 ml/min. FID detector; sensitivity 10/32 Injection temp. 190; Detector temp. 230 Column programming 100-300 at 6°C/min. Retention time Figure 11. Example of a gas chromatogram of a pentane soxhlet extraction of processed shale. 56 However, according to the literature are listed in Table 27. These and other review, liquid crystal columns have not examples of PAH considered in this study been used to resolve complex environ are included in Appendix C. The focus mental samples (see Appendix B). of Appendix C selection was 3 to greater than 6 ring aromatic hydrocarbons PAH standards used to develop GC (molecular weights of < 200 to > 300). retention times and mass spectrums (MS) Examples of both nitrogen and sulfur for comparison with resolved sample PAH heterocyclic species are included. 57 RESULTS AND DISCUSSION Shale samples with higher organic GC trace was obtained from an injection content produced a tarry matrix during volume equivalent to the benzene extractions with benzene, cyclohexane. leachables from about 50 mg of a Tosco pentane or with benzene :methanol mix shale sample. Alkanes from Cll to tures. Under these conditions, the C30 were identified by interpretation cellulose soxhlet thimbles can have of mass spectra data (Table 28). The "tar" plugging problems, with resulting following aromatics were identified: washover of solids. Concentrations of peaks 1, 2, 3 as alkyl substituted these tarry extracts often led to the benzenes and peaks 22 to 27 and 38, 39, development of an asphaltic-like and 42 and 53 have been identified as tar complex. Similar tar extraction and alkyl substituted naphthalenes. Alkyl concentration problems have been re substituted phenanthrenes (peaks 73, 74) ported by researchers working with oil and pyrenes (peaks 85, 86) were identi shales, tar sands, and other bitumens fied. A methyl substituted dibenzo and kerogens. Various laboratory thiophene was also identified (peak 63). methods have been devised to investigate Peak 67 was identified as elemental tar matrices (see Appendix B tables). sulfur. However, as it is believed that these high carbonaceous tar producing content GC/MS of TLC Fractions samples are not representative of potential commercially developed pro A c h r om a tog rap h i c t r ace 0 f a cessed shales, the study investigations standard PAH mixture and an example of a focused on extraction samples which 0.6 to 0.8 Rf. TLC fraction concentrate could be concentrated to less than 5 mI. GC/MS injection are compared in Figure These concentratable samples are thus 13. This injection is equivalent to the reflective of lower organic content benzene leachables from about 2.5 grams processed shales, such as those shown in of shale developed as described 1n Table 26. Figure 14. Single ion mass spectrum reconstructions indicate the pres Kuderna-Danish heat evaporation and ence of 3, 4, and 5 ring aromatic vacuum evaporation allow quantifiable hydrocarbons. From mass spectrum organic separations. Comparison of GC information the ring compounds are traces of split extracts concentrated by further identified as shown in Table 29. these methods show slight differences in The 4 ring 228 mw PAH, benz(a)anthra relative peak responses. Further, Junk cene, chrysene and triphenylene, et al. (1974) have noted differential could not be individually identified by concentration efficiencies of low the GC/MS computer library since these molecular weight PAH when comparing PAH were not resolved by the SP2100 differing Kuderna-Danish designs. glass capillary column used. The mass spectrum of benzo(c)phenanthrene was ident ified. Five ring aromatics (benz GC/MS of Organic Soxhlet Extracts (a) and (e) py·renes and perylene) were indicated by GC retention time compar1- A sample of a benzene soxhlet son with gas chromatography of the extract has been resolved into more than standard PAH mixture. However, insuffi 120 peaks, as shown in Figure 12. The cient concentrations of the 5 ring 59 , I J I .. Hewlett-Packard gas chromatography-mass spectrometer (HP 5985 GC/MS system) 10 meter glass capillary column coated with SP2100 Temperature programmed from 90° to 250° centigrade at SO/min. 66 4 58 41 29 11 28 52 71 67 77 84 89 94 97 181 184 186 118 128 (min. ) i. Figure 12. GC/MS ion chromatograph of benzene soxhlet leachates (assigned peak numbers correspond with those pres~~~~~ ~~ ~~~~~ 28). Table 28. Identified benzene leachables (peaks as identified in Figure 12). Peak Molecular Formula Compound Number Weight 1 C H l34 Benzene, di~ or tri-alkyl substituted 10 14 2 C H l34 Benzene, di- or tri-alkyl substituted 10 14 3 Cll H22 154 1-undecene and C H 134 Benzene, di- or tri-alkyl substituted 10 14 4 Cll H24 156 Undecane 5 C H 132 Benzene, di-alkyl-alkenyl-substituted 10 12 148 Benzene, alkyl substituted 7 Cll H16 8 C H 128 Naphthalene or azulene 10 8 C H 146 ? 9 11 14 10 C H 168 1-dodecene 12 24 11 C H 170 Dodecane 12 26 12 C H 184 Undecane, dimethyl l3 28 16 C H 142 Naphthalene, methyl ll 10 17 142 Naphthalene, methyl Cll H10 18 C H 182 1-tridecene 13 26 20 C H 184 Tridecane l3 28 22 C H 174 Naphthalene, 1,2,3,4-tetra hydro l3 18 tri-alkyl substituted 23 154 1,1'B:phenyl or acenaphthycene, 1,2-dihydro 25 156 Naphthalene, mono- or di-alkyl substituted 26 156 Naphthalene, mono- or di-alkyl substituted 27 156 Naphthalene, mono- or di-alkyl substituted 28 C H 196 l-tetradecene 14 28 29 C H 198 Tetradecane 14 30 30 C H 156 Naphthalene, mono- or di-alkyl substituted 12 12 36 ? ? Alkane, substituted 37 ? ? Alkane, substituted 38 170 Naphthalene, trim~thy1 substituted 61 Table 28. Continued. Peak Molecular Formula Compound Number Weight 39 C H 170 Naphthalene, trimethyl substituted 13 14 40 C H 210 1-pentadecene 15 30 41 C H 212 Pentadecane 15 32 42 C13H14 170 Naphthalene, trimethyl substituted 43 C H 170 Naphthalene, trimethyl substituted 13 14 44 C13H14 170 Naphthalene, trimethyl substituted 46 C H 184 Naphthalene, alkyl substituted 14 16 47 ? ? Alkane, substituted 48 ? ? Alkane, substituted 49 ? 182 ? 51 C H 224 1-hexadecene 16 32 52 C H 226 Hexadecane 16 34 53 C H 184 Naphthalene, alkyl substituted 14 16 55 ? ? Alkane, substituted 56 ? 196 ? 57 C H 238 I-heptadecene 17 34 58 C H 240 Heptadecane 17 36 59 C H 268 Alkane, substituted 19 40 60 ? ? Alkane, substituted 61 ? ? Alkane, substituted 63 C H S 198 Dibenzothiophene, methyl substituted 13 lO 64 C H 252 l-oc tadecene 18 36 65 C H 254 Octadecane 18 40 66 ? ? Alkane, substituted and 192 Phenanthrene or anthracene, methyl substituted 67 S6 or S8 Sulfur 70 C H 266 I-nonadecene 19 38 71 C H 268 Nonadecane 19 40 73 C H 206 Phenanthrene, dimethyl substituted 16 14 C H 206 Phenanthrene, dimethyl substituted 74 16 14 62 · 83 Table 28. Continued. Peak Molecular Formula Compound Number Weight 76 C H 280 l-eicosene 20 40 77 C H 282 Eicosane 20 42 83 C H 294 1-heneico sene 21 42 C H 296 Heneicosane 84 21 44 C H 216 Pyrene, methyl substituted or 85 17 12 11 H-benzo[a]fluorene 86 C H 216 Pyrene, methyl substituted 17 12 88 C H 308 I-docosene 22 44 89 C H 310 Docosane 22 46 93 C H 322 I-tricosene 23 46 94 C H 324 Tricosane 23 48 96 C H 336 I-tetracosene 24 48 97 H 338 Tetracosane C24 SO 100 H 350 I-pentacosene C2S SO 101 C H 352 Pentacosane 2S S2 103 C H 364 I-hexcosene 26 S2 104 C H 366 Hexcosane 26 S4 105 C H 378 I-heptacosene 27 S4 106 C H 380 Heptacosane 27 S6 107 ? 253 ? 108 ? 217 ? 109 C H 392 l-octacosene 28 S6 110 C H 394 Octacosane 28 S8 112 ? 217 ? 113 C H 408 Nonacosane 29 60 114 ? 217 ? 115 ? 217 ? 117 ? 217 ? 119 H 422 ? C30 62 63 i J I, A. Single ion, 228.1 mw, reconstruction of TLC fraction B. Single ion, 202.1 mw. reconstruction of TLC fraction #' C. Single ion, 178.1 mw, reconstruction of TLC fraction D. GC/MS ion chromatogram of TLC 0.6 - 0.8 Rf fraction (rw 228 PAH Triphenylene Benz(a)anthracene Chrysene E. PAM standard mixture 3 ring PAH (~ 178 mw) 4 ring PAH (~ 202 mw) Phenanthrene Fluoranthene Anthracene Figure 13. Gas chromatogram comparisons of a standard PAR mixture and a 0.6 to 0.8 Rf TLC fraction. ....------, (Rf) Solvent front TLC Plate Desorbed in ~------~ 1.0 methanol concen trated to 0.14 mI. ---:.------0.8 2.1 ~l injected to GC/MS. GC/MS on re xJYtif~~~r~w~~___ 0.6 ~ Figure Resolved PM! x 13. Constituents x 0.25 Solvent Development Benzene:Cyclohexane 0.1 t (3: 2) Known PAR Concentrated Sample mixture ~ ______~ ______~O ~ Benzene extract from 200 g sample concen- TLC of ex.ttracts from 1 kg procejssed shale trated to 4 mI. "II 1. Kuderna Concentration Vacuum ~ ~l to GC/MS. (GC /MS Danish Methods Evaporation Figure 12.) Soxhlet Extractions Solvent and Operation Conditions Described in Methods and Procedures. Figure 14. Summary of organic ex.traction regime. Table 29. Summary of PAHs identified in TLC 0.6 to O.S fraction. Number GC/MS Retention Molecular Aromatic Identified Formula Time Wt. Rings Compound (min) 3 anthracene 178.1 C H 10.2 14 lO 178.1 C H 10.4 3 phenanthrene 14 10 pyrene 202.1 C H 15.6 4 16 10 4 fluoranthene 202.1 C H 16.3 16 10 4 228.1 C H 22.0 benz(a) anthracene 1S 12 chrysene triphenylene benzo(c)phenanthrene 65 aromatics were present above background more than 60 to less than 10 mg/l in 10 to allow identification of mass spectra. days. Quant ification of ident ified PAH is presented later. As expected, TDS correlates with EC for water developed samples (from all GC/MS of Water Extracts water developed samples; column soxhlet and drum mixing). The resulting rela Soxhlet operation with water and a tionship is compared below with one from low organic content Paraho shale re Ward et al. (1971)* reflecting disposal sulted in the development of samples shale leachate concentrations (n is with specific conductivities (EC) of number of samples): 3000 (200-3450) umhos/cm at 25°C. Soxhlet sample amounts ranged from r2 n 138-400 gj operation times ranged from 2 to 7 days; and extract pH ranged TDS=EC(0.9004) - 116; from 9.03 to 9.65. At longer operation for EC>130 0.998 51 times precipitation reactions control *TDS=EC(0.9727) - 48.6 0.926 24 pH. Wh e naIL t he wa t e r de vel 0 p e d Extract concentrates from soxhlet samples are considered collectively, EC water leached samples showed no identi (and thus TDS) correlates poorly with fiable GC peaks. This statement is also TOC as shown below (as would be expected true for combined samples subjected to since a fundamental relationship is not 1) lyophilization prior to benzene obvious). As a comparison, shale 1 e a chi n g , 2 ) c om bin a t ion sox hie t related groundwater TDS:TOC relation and XAD sorpt ion resin approaches, and ship reported in Jackson et al. (1975)* 3) singular post soxhlet XAD and CH2CL2 is also shown. L/L extraction routines. Both XAD-2 and -4 were prepared as previously described r2 n and used to develop water extracts. An XAD-2 resin prepared by the manu Total samples EC:TOC 0.51 24 facturer was also used. GC of combined *Groundwater TDS:TOC 0.60 27 water sample concentrates (Union, Paraho, and Tosco samples combined On an individually grouped basis, good separately) contained alkane peaks and relationships can be obtained as shown perhaps alkylated 1- and 2-ring PAH in Table 30. species. These combined samples were representative of water leached samples Further illustration of the using I to 4 kg of shale samples. leachability of organics from processed shales is seen in Figure IS. The GC Investigated shale leachates from traces reflect benzene 'soxhlet extrants the upflow column procedures (four runs) from processed shales pre- and post have been temporally characterized in water leaching (20 liters of water using regard to pH, specific conductance (EC) the previously described upflow column and total organic carbon (TOC). At procedure). GC column and operating 10-4 cm/sec flow rate, leachate pH conditions are included on the figure. remained above 7.5. Initial EC declined The peak responses after leaching from more than 25,000 lJmhos/ cm (at are seen to be reduced significantly. 2 SOC) t 0 abo u t 6, 000 wm h 0 s / c min Subsequent GC/MS investigations showed 50 hours of operation. After one month the majority of the peaks are alkanes operation (throughput about 30 liters) and alkenes. Pyrene is believed EC concentrations still exceeded 250 included in the peak indicated by the vmhos/cm2 (at 25°). TOC declined from asterisk. 66 Table 30. Summary of derived indicator relationships (TOC, EC, VS, TDS) of var10US oil shale leachates and White River water. Equat10n ---r2 n Paraho (column 3): TOC=EC(9.94 x 10-4 ) - 0.844 0.981 9 Paraho (column 2) oven dry: TOC=EC(2.26 x 10-3) + 10.2 0.934 9 Paraho (column 0: TOC=EC (3.21 x 10-4 ) + 1.2 0.923 4 Paraho (column 1) oven dry: VS=EC (6.08 x 10-2) + 24 0.923 15 White River (USGS): TOC=TDS(1.16 x 10-4 ) - 0.04 0.698 9 HP-5750 gas chromatograph 180 x 0.3 cm stainless steel column 10% SF 2100 on 80/100 mesh Supelcoport Carrier gas He at ~ 25 ml/min. FID detector; sensitivity 10/32 Injection temp. 190; Detector temp. 230 Column programming 100-300 at 6oC/min. *Indicates peak which contains pyrene QJ CIl C as based on GC retention time o Q.. CIl QJ p:: Q H ~ Uo Retention After time Figure 15. GC trace of benzene extracted processed shale before and after water leaching. 67 A portion of a GC trace of an XAD-2 were favored to allow consistent GC area developed processed shale water mix quantifications. (developed in a 55 gallon drum) is compared to the PAH standard in Figure With few exceptions, comparisons of 16. Three ring 178 mw and 4 ring 202 mw mass spectrums of selected 5 ring PAR PAH were indicat.ed by retention time and (B(a)P, B(e)P, and perylene) were not identified by comparison of GC/MS possible from shale/water extraction library mass spectra (in three of samples. A maximum of more than 10 kg six samples). The 5 ring 252 mw benzo of processed shale was involved in (e)pyrene, perylene and benzo(a}pyrene production of these samples. Utilizing seem to be extractable by the shale/ a frame of re ference provided from water mixing technique (one of six working with known PAR concentrations samples). Rowever, the concentration (MS identification limits and GC identi above background of the 4 and 5 ring fication and quantification 1 imits) and aromatics was not high enough to allow considering extraction efficiencies, the comparison of mass spectra. More than lowest organic content processed shale 10 kg of processed shale was used allowed about 0.1 ppb* aqueous extract in generation of these samples contain able 5 ring PAR (weight of extractables/ ing identifiable 200 to 300 molecular weight of shale). Associated aqueous weight PAR. The presence of the 5 ring concentrations of 5 ring PAH ranged 252 mw species was only indicated from a from 0.01 to 0.1 jlg/l. Three to 5 sample developed by mixing> 10 kg shale ring PAR were available at concentra with > 100 liters of water providing a t ions 1 ess than one percent of re study maximum driving force (i.e. spective solubility as summarized in greatest differences between estimated Table 31. shale PAH concentrations and reported solubilities, see Table A-2l). Chlorination Study Results Quantification of Identified PAH Chlorination study and extraction in Spent Shale Samples efficiency (controls) m1x1ng times ranged from less than 1 hour to 3 days. As previously described, most of the 35 Single ion GC/MS areas were used to samples were mixed for 15 hours. Mixing estimate spent shale sample PAH concen time was not determined to be a signifi trations. GC retention times and cant variable in assessing extraction calculated es·timates of GC/MS area units efficiencies. The results of the 15 per ng' of PAH injected have been sum hour mixing studies are summarized in marized in Table 27. During ideal Table 32. Reduction in PAH concentra performance, standard 3 and 4 ring PAH tions associated with the 15 hour (indicated by a single asterisk in mixing/chlorination period represent the table) can be identified at GC/MS well the results obtained for all injection concentrations of 1 ng/jll by mixing/chlorination studies « 1 hour both GC retention time and comparison o'f through > 2 days) for anthracene, mass spectrums. Considering 1) SP 2100 phenanthrene, benz(a)anthracene, column detrioration, 2) GC/MS and chrysene, and triphenylene. As shown operator conditions, 3) high background in Table 32, the reduction in concen associated with polar solvents (column tration of the above 3 and 4 ring PAH bleed), and 4) storage life of PAH standard solutions,S ring PAH could be ident ified routinely at GC/MS injection *"'1 ng/ III (GC/MS SP 2100 injection) concentrations of > 5 ng/ jll. More x (> 1 percent of sample concentrate) x than 10 ng/jll of each PAH (particularly (< 10 percent extraction efficiency for for 4 and 5 ring PAH) GC/MS injections XAD-2) (> 10 kg processed shale). 68 A. Single ion, 252.1 mw, reconstruction of XAD-2 fraction 252.1 mw B. Single ion. 228.1 mw, reconstruction of XAD-2 fraction ~~-~.~-~---~-----..-.-~--~ ..----~-.------~~~---~------~------.~--.------ C. Single ion, 202.1 mw, reconstruction of XAD-2 fraction D. GC/MS ion chromatogram of shale/water mix XAD-2 E. PAH standard mixture 4 ring PAH (~ 228 mw) knowns 5 ring PAR (~ 252 mw) knowns 4 ring PAH (~ 202 mw) knowns Triphenylene Benzo(e)pyrene Fluoranthene Benz (a) anthracene Perylene I Pyrene Chrysene Benzo(a)pyrene (min) Figure 16. Gas chromatogram comparison of an XAD-2 developed processed shale compared to known PAH stan dard. Table 31. Summary of quantification of organic and water developed shalea samples; ppb dry shale except as indicated. Standard Species Organic developedb Water developedc Solubilityd max. mean mIn. max. mean aqueous (J.lg!U concentration (J.lg/l) Carbazole 69 32 0.16 ND ND 4-Aza fluorene 43 15 0.25 ND ND Acridine 50 18 0.22 ND ND 2-Aminofluorene T ND ND ND ND Dibenzothiophene 134 50 ND 20 9.3 10 Anthracene 62 20 ND ND ND 50 Phenanthrene 483 165 9.9 61 50 10 1250 F1uoranthene 85 22 1.1 10 3.5 1.0 250 Pyrene* 97 34 1.6 10 3.4 1.0 150 Thianthrene T ND ND T Aminopyrene T ND ND T -J 0 Triphenylene Benz(a)anthracene 54 10 0.69 1.0 0.5 (0.01 - 1.0) 10 Chrysene 5 Benzo(e)pyrene Perylene 56 1.0 0.13 0.17 0.1 (0.01 - 0.1) Benzo(a)pyrene 13H dibenzo(a.i)carbazole T ND ND 7.12 dimethy1benzo(a)anthracene T ND ND Benzo(g.h.i)pery1ene T ND ND Dibenzanthracene T ND ND aUnion. Tosco and Paraho shales included. bSix samples. CMinimum for all species sought was below detection limit (ND not detectable). dfrom Appendix A. Table A-21. Note: ND is not detectable (i.e. below detection limits); T is trace. was only about 15 to 25 percent, were shown to be mixing time related except for anthracene. Reduction in with values of about 20, 45, and anthracene concentration due to chlori 75 percent for 1 hour, 15 hours, and 2 nation was about 95 percent for all days mixing, respectively. study reaction mixing times and free available chlorine concentrations. Free available chlorine concentra Mixing times of 15 hours and 'greater tion was less sensitive than reaction resulted in about 90 percent reduction (mixing) time. The concentration of in pyrene concentrations while 1 hour free ,available chlorine ranged from zero mixed chlorination resulted in only 35 in the controls (extraction efficiency percent reduction in concentration of studies) to 1000 mg/l; as previously this 4 ring PAH. Reductions in fluor described, most of the samples ranged anthene concentration and the 5 ring PAH from 10 to 100 mg/l. The results are Table 32. Summary of standard PAH L/L extraction efficiency and removal chlorina tion (~ 15 hrs. mixing), PAH Extraction Efficienc! Chlorination Removal Species % cv n % cv n Phenanthrene 72 33 11 13 20 8 Anthracene 50 31 11 95 6 9 Fluoranthene 76 21 12 39 53 9 (73) (7) (6) Pyrene 83 24 10 90 4 8 (84) (5) (6) 228 mwa 89 29 9 28 76 9 (BaA) (88) (0) (5) Benzo(e)pyrene lOOb 74 25 7 Perylene 100b 98 2 7 (69) (3) (5) Benzo(a)pyrene 100b 75 27 7 (0) (0) (5) Total 3 above 100 27 13 SOc 17 10 252 mw PAH a228 mw species (triphenylene, benz(a)anthracene, chrysene). ( ) values from Harrison et al., 1976. cv - coefficient of variation; n - number of samples. bEstimated from total 252 mw PAH data. CBest estimate of 5 ring PAH removal. 71 well-represented by the values presented Based on experimental resul ts and in Table 32 for 15 hour chlorination discussions by Dore et al. (1978), exposure. Aqueous concentrations of Jolley (1975), Deinzer et al. (978), initial PAH species (> 10 to 25 Il g each Brinkman and Reymer (1976), Smith et al. per 2 t) provided an additional measure (977), Roberts and Caserio (1965) and of GC/MS and SP 2100 column limits. Morrison and Boyd (1973), the PAH Utilizing the extraction efficiencies chlorination products were expected to reported in the table, about 1 ng of be 1) CHC13, CHZCIZ. CH3Cl; Z) mono each 3 and 4 ring PAH/Ill GC/MS injection to peri substituted initial PAH species, was required for identification and up and 3) a host of disintegrating PAH with to 10 ng/lll GC/MS injection seems chlorinat ing alkane and alkene side required for consistent quantification chains. Chlorine substituted PAH with (including 5 ring PAH). or without side chains were not obvious in the extracts of chlorinated samples Extraction efficiencies presented (GC/MS), and to date have not been in Table 32 compare well with those observed. reported in a chlorination study (values in parentheses) by Harrison et al. (976) who used 100 to 500 ng of each selected PAH. In the Harrison et al. Chloromethanes, dominantly CHCl3, were identified in reaction waters using (1976) study, reaction volumes of 5 a Teckmar concentrator (model LSC-l) liters were used and the chlorina with 10 cm tenax and 5 cm chromasorb t ion concentrations and reaction times 10Z, followed by GC (HP5750 with elec employed were consistent with conditions tron capture detector) using a 6 foot x in actual water treatment processes. As 1/8 inch stainless column packed with free available chlorine concentrations 0.2 percent carbowax 1500 on 80/100 mesh and/or contact time and/or temperature carbopack C. Analysis procedures increased, so did the reduction in were comparable to those reported in the concentration of PAH (associated rates of reduction were estimated). literature. A "purgeable A" standard Water pH during chlorination was deter solution (from Supelco Inc.) was used to mined to be the major reaction variable confirm the identified halogenated under treatment conditions of 5 minutes methanes. The presence of chlorinated contact time, 2.2 mg/l free chlorine, short chain hydrocarbons was also probable (Peters, personal communi and 20°C. Pyrene and benzo(ghi)perylene cation 1979). Quantification of the show linear reductions from about 70 chlorinated methanes, was not done since percent at pH of 4.5 to 20 percent at a it was determined that comparable pH of 7.5. At neutral water pH, all 4 chlorination of benzene controls re to 6 ring PAH concentrations in the sulted in formation of essentially equal study were reduced by 20 percent. concentrations of identified species. As previous 1y described, the study PAH In contrast to the above results of were dissolved in benzene at 0.5 mg/ml, Harrison et al. (1976), the reduction in and this solution was used as a PAH concentration of PAH due to chlorination source for chlorination studies. l.n the present study (Table 3Z) is associated with a water .temperature of 20°C, pH of 8.5 (characteristic of White and Green Rivers), reaction times of 15 hours, and free available chlorine Hexachlorobenzene was positively concentrations of 10 to 100 mg/l. Even identified (GC and MS, with knowns) in after the harsh chlorination conditions concentrates developed from washing used in this study, PAH reductions were reaction flasks with benzene after not complete (Table 32). CH2CIZ extraction procedures. 72 Laboratory Limits to Aqueous based on study water concentrations ~hat Investigation of 5 Ring PAR are orders of magnitude higher than solubility. Extraction efficiencies of Associated with the chlorination 4, and part icular ly 5, ring PAH de studies and quantitative identification ve loped from water s amp 1e s near as so of PAR in shale/water developed samples, ciated solubility limits is general efficiency of resin sorption and L/L ly absent from the literature. extraction regimes were explored. A recovery efficiency from XAD-2 on the Criswell (1977) using 100 ~g/l order of 1 to 10 percent was observed monocyclic aromatics (e.g., phenols and with the known PAR standard mixture at a benzenes) showed less than 10 percent concentration of 10 to 20 ~g/liter (ea). recovery using activated carbon. A The study PAR were not detected on 1) nonionic sorption resin (XAD-4) has been the analytical regime glassware nor 2) compared with activated carbon treatment were they present in MeOR XAD regenera of chlorinated pesticide waste streams. tion solvents. The known PAR stan A flow rate of 1.0 gpm/ft3 (2 x 10-3 dard aqueous mixture, after passage (m3/s)/m3 ) was used in these sorption through the XAD-2 column was L/L ex studies; total pesticide concentrations tracted with CR2C12 (modified EPA ranged up to 200 mg/l. Isopropanol was 1977 procedure). No PAR were observed shown to be a better regeneration agent by GC/MS analysis of combined concen than methanol (Kennedy 1973; dollar trated extract samples. Drying agents estimates for treatment included). and filters were soxhlet ext racted in Recoveries from XAD-2 resins of less isopropanol and concentrates showed than 40 to 80+ percent for 2 and 3 unquantifiable amounts of known PAR. ring PAR were reported by Junk et al. When avoidab Ie, however, drying agent s (1974) and Criswell (1977). Ten to 100 should not be used. PAR were also not llg/l amounts of PAR were used in these extractable from combined XAD resins studies. Considering the monocyclic using isopropanol or acetone. As aromatic species investigated in another previously reported, CR2C12 L/L batch study, extraction efficiencies using extraction efficiencies for 3 to 5 XAD-2 and XAD-7 resins generally ranged ring PAR were found to be higher, from 25 to 60 percent. Extremely high rang1ng from 50 to 90 percent (see Table study concentrations were used ("v 1 mg 32). per < 1 t). Increasing extraction efficiency at lower column flow rates Concentrations well below 10 ~g/ 1 was demonstrated. The lowest flow used, should be a maximum if solubility in 20 ml/min, was found to be best. Re water is a limit for laboratory investi covery of study compounds was also gations of 5 ring PAR. Assuming 1) greater at a lower pH with the most laboratory extraction efficiencies of 1 complete destructions occurring at the to 10 percent for resins or 25 to 75 study minimum pH used 4.0 (Stepan percent for L/L extractio~s; 2) quanti 1976). fiab Ie minimum concentrate volumes of about 100 wI; 3) GC/MS injection volume Some authors have suggested the of about 100\11, and 4) quantifiable presence of sulfur in water samples GC/MS 5 ring PAR concentrations of more interferes with XAD extraction effi than 10 ng/~l; about 100 liters of ciencies. It is important to maintain reaction water is required to study 5 specific conductance of sample waters 0 ring PAR below water solubility limits. be low 2000 ~mhos/ cm at 25 C (Denver A primary problem is the low recoveries 1979). Urine to which 80 ~g (in 100 ml) of sorbed PAHs from the res ins, or low BaP was added allowed XAD-2 recoveries i/L extraction efficiencies. It should of about 19 percent. Other 3 to 4 ring also be noted that reported recovery/ PAR also had recoveries less than 20 extraction efficiencies are often percent (Yamasaki and Ames 1977). An 73 extraction efficiency study by Webb initial concentrations of 1 mgll were (1975) of XAD resins (2, 4, 7, 8; alone reported. A 50 percent extraction and in combination) demonstrated efficiency was estimated for the that recoveries can be expected to range n-hexane L/L extraction approach used from 20 to 80 percent for monocyclic (Burleson et ale 1979). aromat ics (see Table A-23). Fifty ~/l concentrations were used. A CHC13 L/L Harrison et ale (1976) conducted a extraction used to provide a comparison near solublity 1 imits study of 4 to 6 and recovery efficiencies were consis ring PAH. They utilized PAH at concen tently 80 percent (Webb 1975). trations of 0.1 to 1.0 ~/l. However, 5 liter reaction volumes were required Generally 30 to 80 percent re for quantitative identification using a coveries of pyrene and benzo(ghi)pyrene CH2C12 L/L extraction approach. This were demonstrated using a dichloro compares to the PAH concentrations methane L/L extraction procedure. High ranging from 5 to 25 ]1 gil used in the suspended solids concentration and long chlorination studies reported herein. storage times lowered recoveries of Considering that 3 to 5 ring PAH were studied PAH compounds. Study 5 ring PAH investigated, both studies utilized PAH concentrations ranged from 0.1 to concentrations up to 10 times solubility 1.0 mgll (Acheson et ale 1975). McGinnes limits as summarized in Table 33. It is and Snoeyink (1974) have estimated UV believed that the solubility limits degradation of Ba and BaP "suspended" in affected chlorination results in water at 1.0 mgll concentrations. Ozone the Harrison et al. (1976) study for 6 destruction of BaP, 3-methylcholanthrene ring PAH and also for 5 ring PAH in the and 7,12 dimethylbenz(a)anthracene at study reported herein. 74 Table 33. Summary of selected PAH concentration in selected waters. Range of PAH concentration (ng/l) 2 3 4 5 6 Ring Ring Ring Ring Ring Aqueous 104 < 103 Solubilitya 107 max < 106 max 'V 105 < 104 '[ Rivers Effecteda (All 10 to 102 ng/l possible)b Waste Watersa 105 104 103 102 105 max Shale and Coal (2 to 5 ring 105+ 102) Conversion Watersa Disposal Area (All 7) Erosion and Leachatesa Literature Study 2 and 3 ring 103(c) 102(c) 10 2(c) Concentrations 004 to 106 ) <106 < 106 max This Study Laboratory (3 to 5 ring 123 to 104 max) Concentrations aSupport provided by Appendix A, A-IS - 17 and A-27 exhibits. bUnderlines reflect judgment of the most representive value cHarrison et al., 1976. 75 ...... , CONCLUSIONS AND RECOMMENDATIONS The presence of 5 ring polycyclic affected sediments would also playa aromatic hydrocarbons (PAR) in aqueous role in the movement of PAR from post extracts from processed shale samples development disposal areas. has been indicated by comparison of gas chromatography (GC) retention times. Alluvial drainage would be first to Selected 3 and 4 ring PAR (anthracene, experience the spread of PAH from phenanthrene, fluoranthene, pyrene, affected oil shale areas. Considering triphenylene, benzo(a)anthracene, the groundwater leaching source alone, chrysene) were identified by GC and mass potential outflows from the White River spectrometry (MS). Quantification of Basin of 4 and 5 ring PAH could amount these and other PAH (summarized in Table to about 0.1 kg/yr (or 10-3 ppb at 3l) indicate that 4 and 5 ring PAH were average flow) as an approximation available in filtered water extracts at under the following assumptions: about 1 percent of their respective solubilities. These PAH were also • A maximum development in available in benzene soxhlet leachates which 1 percent of White River from the lowest organic content pro Basin area is used for dis cessed shale investigated at concentra position of processed shales. tions of about 1 ppb (weight of each PAH/weight shale). Considering benzene • Low flow from the White River leachables of shales as an indicator, reflect ive of alluvial drain this value compares with other 1 itera age is about 300 cfs (8.5 ture estimates ranging from 1 to 100 m3/ sec). ppb for BaP alone. However, further work with complex processed shale • Disposal area leachate rates matrices is required to adequately controlled and comparable with doc ume n talI est im ate s 0 f pro c e sse d background of 1 ft/yr(rv shale PAH concentrations. 10-4 cm/sec} (designable control noted). Movement of identified PAH from the waste products of oil shale development • Disposal area generated would be associated with erosion and leachate PAH concentrations groundwater drainage. For large scale would be 0.1 ~g/l for 4 and 5 developments with surface disposition ring PAH. of processed shales along with other wastes, disposal area characteristics Of these four assumptions, the determine the potential PAH degradation greatest uncertainty is associated with of water resources (Table 10). As the the estimates of leachate PAH concentra oil shale is being processed, the PAH tion and other residue characteristics. entering the aquat ic environment would Once these materials enter the water, be dominantly associated with precipita considerably more uncertainty is asso tion of air emissions since no direct ciated with the rates at which they move discharge of waters to the Colorado downstream and the changes in residue system is anticipated. Air transport of characteristics associated with that the PAH in eroding processed shale and movement. The methodologies available 77 from the Ii terature concerning PAR: The above 7 x 10-4 MT/m3-yr White sorption, precipitation, chelation/ River erosion estimate was based on an complexation, solubility, sediment area weighted comparison of the erosiv transport, and biodegradation mechanisms ity index (Figure 3). From this analy require focusing, advancement and sis, estimated average White River application specifically to oil shale Basin fluvial erosion is well repre deve lopment environs. Sorpt ion and sented by its major tributary (the related low solubilities of 4 ring Piceance Basin contributions of 6.7 :x and larger PAR are expected to strongly 10-4 MT/ m3-yr). Further, Malek (1979) control disposal area leachate mobility reports that 5 x 1'0-4 to ZO x 10-4 Mr/ (Karickhoff et a1. 1979). Righ TDS m3-yr is a realistic range reflective concentrations of processed shale of potential shale disposal area erosion leachates may further limit PAR leachate rates. Additional perspectives related concentrations (May 1978). Precipitated specifically to applicable river PAR formats, along with larger particles sedimentation mechanics are found in wi th sorbed PAR, could, however, be Bronson and Owen (I 9 70), Shen (I 973) , mobile as suspensions in processed Vanoni (1975), Jurinak et al. (1977) and shale leachates.' Total leachate or Nezafati (1979). ganics could increase PAR concentra tions. Furthermore, carboxylic hydrogen The amounts of 3 to 5 rings PAR bonding is believed to play an important found in oil shale wastes are compared role in the mobility of both PAR and with amounts found in selected other metals (Weber 1974). Southworth (979) environmental materials in Appendix A, concludes that volatilization would Table A-ZO. A second, very important not play an important role in reducing factor is the degree of human exposure large molecular weight PAR in the to these materials. In order to provide aquatic environment. some perspective as to this situation, maximum exposures caused by oil shale Sediment transport of eroding wastes are compared with exposures in processed oil shale is an equally wa'ter, food, ingested dirt, and air in significant potential source of PAR to Table 34. The most severe exposure, air the aquatic environment. PAR flux from (worst case), is associated with smoking. the White River associated with sediment transport alone could amount to 0.1 The preliminary chlorine disin kg/yr under the following assumptions: fection studies indicate that chlorina tion does not protect well buffered • PAR content of eroding sedi drinking water supplies with a pR of ments would be 1 ppb for 4 8 to 8.5 from potential carcinogenic and 5 ring PAR. hazards caused by PARs. Further, the chlorination of PAR and other • Approximately 1 percent of the organics associated with oil shale 5120 miZ (13,250 km 2) White development will produce of increased River Basin would be affected concentrations of CRZC12, CR3Cl, and (Table 10). other chlorinated organic species in affected drinking water suppl ies. The • Erosion rates would be con reduction in concentration due to trolled and comparable chlorination (more than 10 mg/l free with background (7 x 10-4 ava ilable chlorine and 15 hours mixing MT/m3-yr), (about 1 x 10-4 time) of phenanthrene, benz(a)anthra MT/m3-yr as suspended solids cene, chrysene, and triphenylene (USGS data, 1974 to 1977 at was only about 15 to 25 percent. Mixing mouth». times of 15 hours and greater resulted 78 Table 34. Comparison of human exposure to 3 to 5 ring PAH from other sources with concentrations estimated in drinking water downstream from oil shale areas. Source Estimated Estimated Concentration Exposure From From oil Shale Other Sources Wastes ( IJg/yr) Water 10 ng/l 10 Food 1 (.:!:. 102) ppb 1 100 Dirt injestion <2 kg/yr @ 1 ppb 1 Background al.r <0.01 0.01 Air (worst case) 10 ng/m3 100 ' in about 90 percent reduction in pyrene results with the work reported by others concentrations; while I hour mixed l.n the literature. chlorination resulted in only 35 percent concentration reduction of this 4 ring Perhaps the most important needs PAH. Reductions in fluoranthene for research on the potent ial degrada and the 5 ring PAH concentrations were tion of PAH originating in oil shale shown to be mixing time related with development relate to the biological values of about 20, 45, and 75 percent aquat ic environment. In oxygenated for 1 hour, 15 hours, and 2 days environments, Pseudonomas, Vibrio, mixing, respectively. Sprillum, Bacillus and Flavobacterium are known to degrade PAH (Post, personal Future research should focus on the communication 1979; Rheinheimer 1971). physical, chemical and biological flux PAH degradation is believed to proceed of 3 to 6 ring PAH through water treat via intermediates to smaller PAH with ment processes and the natural environ hydroxy groups and finally to aliphatic ment. Considering the inherently low acids. Soil bacterial PAH degradation water solubilities of these PAH, labora rates have been shown to be high, with tory investigations of transport mechan half-lives less than 8 days for BaP; isms should employ large closed cyc Ie while 80 percent reduction of 2 ring flumes and pressurizable leaching PAH, napthalene, in organic rich river volumes (> 20 atm (20 x 105 Pa». For environments required 3 weeks (Harrison repeatable water based investigations, 1975). processed shale amount s greater than I MT should be used. It will be difficult , Initially, microcosm studies should to obtain such volumes of representative be conducted to explore PAH/microbe processed shales which have a document interactions. The use of a large able history. Methods used to char recirculating flume and lysimeters would acterize shales in this report should be then be 'a logical extension. As large employed to aid coord~nat ion of study land areas become involved in the 79 production of oil from shale, larger concentration of about 50 and 160 ppb, experimental "laboratories" (immediately respect ively. Fluoranthene and pyrene affected environs) will be available. were available at about 20 and 35 ppb. Selected 4 ring PAR, triphenylene and/or Further research quantifying PAR benz(a)anthracene and/or chrysene were photolysis is needed, both to evaluate found to be present at about 10 ppb. degradation potential in the high Five ring benzo(e)pyrene and/or pery altitude, cold desert environment of the lene and/or benzo(a)pyrene were present Wh ite River and in regard to water at a mean concentration of 1 ppb, treatment. Ba and BaP decomposition ranging from 0.1 to 50 ppb. rates ranged from 0.1 to 0.44/day and 0.009 to 0.29/day, respectively, Phenanthrene was found to be water in UV light ranging from 1 to 10 percent extractable at a mean concentration of average sunlight intensity. Turbidity about 50 ppb. Both fluoranthene and was not shown to be a significant pyrene were present in water extracts at variable (McGinnes and Snoeyink 1974). about 5 ppb. The 4 ring PAR, tripheny The use of UV to speed reactions is well lene and/or benz(a)anthracene and/or known by organic chemists. The use of chrysene were found to be present at UV to aid ozonation treatment of arsenal wastes and pesticides has been recently about 0.5 ppb. Five ring benzo(e) pyrene and/or perylene and/or benzo(a) reported by Buhts (1978). pyrene were present at a mean concentra tion less than 0.1 ppb. Concentrated attention to research concerning ozonation of drinking waters with elevated PAR concentrations should The preliminary chlorination proceed (with and without UV). As a studies reported herein indicate that beginning the following selected refer chlorination of well buffered drinking ences are offered: Frycka (1972). Gould water with PAR present, cannot be (972), Bober and Dagon (975), Gould expected to control associated carcino and Weber (1976), Williams et al. genic hazards. Even after extraordi (1977), Sievers et al. (1977). Dore et narily harsh chlorination (> 10 times al. (1978), Elia et al. (1978) and practical treatment concentrations and Burleson et al. 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Wakeham, S. G. 1979. Aza arenes in recent lake sediments. Environ Woodward-Clyde, Consul tant s. 1976. mental Science and Technology Vol. Disposal of retorted oil shale from 13, No.9. September. the Paraho oil shale project. Prepared for USDI, 2908 West Ward, J. C., G. A. Margheim, and G. O. Seventh Avenue, Denver, Colorado. G. Lof. 1971. Water pollution 80204. December. (I, p) potential of spent oil shale residues. EPA Water Pollution Yamasaki, E., and B. N. Ames. 1977. Control Research Series. (I) Concentration of mutagens from Ward, J. C. and S. E. Reinecke. 1972. urine by adsorption with nonpolar Water pollution of snowfall on resin XAD-2: Cigarette smokers have spent oil shale residues. U.S. mutagenic urine. Bureau of Mines. Laramie, Wyoming. June. (1) Yen, T. F. 1976. Science and tech- nology of oil shale. Ann Arbor Weast, R. C. (ed.). 1976-77. Handbook Science Publishers, 230 Colling o f c hem i s try and ph Y sic s • 5 7 t h wood, P.O. Box 1425, Ann Arbor, Edition. Michigan 48106. 96 Yen, T. F., and G. V. Chilingarian. Young, D. K., and T. F. Yen. 1977. The 1976. Developments in petroleum nature of straight-chain aliphatic science #5 oil shale. Elsevier structures in Green River kerogen. Scientific Publishing Co. Geochim. Cosmochim. Acta. Vol. 41, No. 10, p. 1411. Yen, T. F., C. S. Wen, J. T. Kwan, and E. Chew. 1977. The role of Zane, A. 1968. Separation of some asphaltenes in shale oil. AICHE polynuclear aromatic hydrocarbons Fuel Division symposium on Oil Sand by gas-solid chromatography on and Oil Shale. Vol. 22, No.3. graphitized carbon black. J. June. Chromatog. 38, p. 130. 97 APPENDICES Appendix A Supporting Data 99 ~m+:¢%; AKYLTHIOPHENE BENZOTHIOPHENE 2,2-DIMETHYL-I-THIAlNDAN 2-ETHYL-3,4,S-TRIMETHYL 2-METHY-BENZO [b] THIOPHENE THIOPHENE ~~~ 3.4,6, 7-TETRAMETHYL- 9-THIA-I.2-BENZOfLUORENE 3-ETHYL-6, B-DIMETHYLNAPtfTliO- DIBENZO [bd] THIOPHENE [1.2. b] THIOPHENE ARYLTHIAALKANE~ 2-METHYLTHIENO 3.4,5-TRIMETHYL- 2-(1-THIAETHYLl (2-METHYLTHIABUTYL) [3, 2, b] THIOPHENE THIOPHENE BENZENE EXAMPLES OF AROMATIC SULFUR COMPOUNDS IN PETROLEUM An average structure of coal Figure A-l. Examples of aromatic compounds found in petroleum coal (Orr, 1977) and an average structure of coal (Kwan and Yen, 1979). ,100 I I J Table A-I. Identification of organics found in shale oils (Clark et al., 1978; Fruchter et al., 1977). Detennina tion of n alkanes in a mixed petroleum crude, shale oil and COED syncrude. Concentration (mg/g) COMPOUNDS ID£NTIFIED IN SHALE Oil BY GC/MS Compound Mixed Shale COAL NEUTRAL COMPOUNDS petroleums oil CRUDE A N-ALKANES BRANCHED ALKENES N-ALKENES ALKYU:.,RANS CII 6.11 7.55 0.34 CYCLOHDCANE ALKYL TH lOP HENE S CI2 6.06 6.65 4.41 ALKYLCYCLOHEXANES PRISTANE BRANCHED ALKANES PHYTANE CI3 6.31 6.20 2.98 CI4 6.18 4.80 1.30 AROMATIC COMPOUNDS CI S 4.92 3.30 1.85 INDENE ACENAPHTHENE CHRYSENE ...... CI6 4.65 4.50 3.14 ALKYLINDENES FLUORENE METHYLCHRYSENES 0 C 3.86 8.60 NAPHTHALENE ALKYLFLUORENES CHOLANTHRENE ...... I7 2.51 ALKYLANI SOLE PHENANTHRENElANTHRACENE BENZOFLUORANTHENES CI8 6.03 8.80 3.64 BIPHENYL ALKYLPHENANTHRENES BENZOPYRENES CI9 3.')5 5.60 1.82 ACENAPHTHYLENE FLUORANTHENE ALKYLNAPHTHALENES PYRENE C20 3.83 4.80 1.85 ACIDIC COMPOUNDS C21 3.~3 5.70 2.40 C 3.52 4.50 1.73 ALKYLPHENOLS THIONAPHTHOLS 22 NAPHTHOL THIOPHENOLS C23 3.51 5.00 2.60 ALKYLNAPHTHOLS C 24 2.73 3.60 1.98 BASIC COMPOUNDS C 2.19 3.90, 1.99 2S PYR1DINE ALKYLACRI DINES C26 1.95 3.45 2.09 ALKYLPYRIDINES INDOLE C21 1.94 3.35 2.22 QUINOLINE ALKYLI NDOLES C28 1.28 2,90 1.77 ALKYLQU I NOLI NE S CARBAZOLE ACRIDINE ALKYLCARBAZOLES C29 1.06 3.20 1.55 C30 0.89 1.00 0.96 C31 0.86 0.20 0.86 C32 0.94 0.10 0.86 C33 0.43 0.65 0.24 C34 0.47 0.40 0.23 C3S 0.38 0.17 C36 0.22 0.15 0.11 I " Table A-2. Comparison of PAH content of various crude and syncrude oils. TOTAL ANALYSIS OF HYDROCARBON FRACTION OF ATllABASCA OIL POLYNUCLEAR AROMATIC HYDROCARBONS IN PETROLEUM MATElllALS °/. South Louisiana Crude 011 Kuwait Crude 011 NO. 2 Fuel 011 Bunker C Fuel 011 Fraction Carbon H: a. extended proee{!ure; b. straightforward procedure. (Pancirov et al., 1978) l-' 0 (Selucky et a1., 1977) N Oil Polyou~lear aromatic hydrocarbons in eoal l1qu1ds. Compound uB Il "Cn Compound Ita n t·C" ppb ppb Clearfield. \I. Va. Kentucky Kentucky Pa.. Clearfield Ireland W. Va. HOO\estead Liquefaction KanoT Liquefaction Mine Liquefaction Feed Coal Product Feed Coal Product Feed Coal Product Benz{a)anthracene Pyrene 19 ------ppm ------Pyrene 0.8 2040 0.6 2280 1.9 1.5 Benzo(a)pyrere 29 106 Triphenylene 5 - Fluoranthene 1.2 0.5 NO 8.1 4.3 0.4 BaA 5.8 0.2 1.3 0.5 9.3 0.1, Ilenzo(e)pyrene 370 831 Chrysene 1 - Chryaene 6.6 1.1 12.9 2.7 9.9 1.8 Triphenylene 0.4 0.3 2.6 1.1 1.2 0.1 BaP 6.2 1.3 1.6 1.6 19.2 2.9 Benzo(ghi)pery1ene 48 f1uoranthene 3 - BoP 3.5 5.0 1.6 1.1 9.3 2.9 Coronene 28 61 Perylene - 666 NO - nOt detected~ From Panc1rov et al. (1978). (Guerin, 1977) Table A-3. Comparison of PAH methyl isomers in Synthoil and Prudhoe Bay (Jones in Coomes) 1978). Methyl Groups 0 1 2 3 4 5 6 1 8 9 10 Anthrllcenes/ BH 1.00 1.82 2.38 3.00 2.41 1.91 3.06 2.22 1.10 1.18 1.71 Phenanthrencs SY 1.00 1.11 2.21 2.04 1.71 1.0lt 0.56 0.29 0.13 0.04 0.02 PR 1.00 1.98 1.41 0.15 0.92 0.10 0.39 0.14 0.01 0.04 0.02 Pyrnes/ S1I 1.00 3.08 1.. 08 5.86 5.42 9.92 13.9 12.5 1l.2 11.9 Fluoranthenes/ BY 1.00 0.51 0.28 0.51 0.39 0.30 0.17 0.10 0.06 0.03 llenzfluroenes PR 1.00 3.69 4.66 9~06 1.72 4.19 2.15 1.89 Benzanthracenea/ 811 l.00 1./11 3.29 1.01 8.92 9.03 9.08 1.44 1.25 6.15 5.46 Chrysenes SY 1.00 3.2lt 2.64 2.21 2.18 1.49 1.13 0.60 0.24 0.04 PR 1.00 1.51 3.68 4.11. 3.38 3.11 2.68 1.51 I-' 0 w Cholanthrenes 511 1.00 2./16 3.35 4.1.1 4.51• 1.. 51 3.50 3.30 1.98 1.16 0.10 SY 1.00 0.95 1.24 1.20 1.15 0.71 0.37 0.17 0.03 PR 1.00 2.82 4.05 4.23 5.05 3.73 1.59 0.82 Benzpyrenes/ SH 1.00 1.17 2.96 3.5'. 1.27 5.73 6.35 5.21 4.58 3.46 2.58 nenzfluoranthese/ SY 1.00 2.25 2.86 3.30 5.50 4.29 2.S4 0.86 0.23 Perylenes PR 1.00 3.93 8.61 1.54 20.1 11.63 11.66 5.66 Indenopyrenes/ SII 1.00 1. 50 2.21 2.10 2.11 2.13 2.04 1.19 Benz(ghi)perylenes SY 1.00 0.90 0.53 0.62 0.72 0.34 PY 1.00 3.18 2.33 1.73 1.16 Dibenzanthracenes/ SIl 1. 00 It .60 6.44 6.61 6.69 6.60 6.16 5.04 Picenes SY 1.00 2.51 3.89 3./16 2.11 1.06 0.49 PR 1.00 1.42 2.36 5.69 3.61 2.35 0.47 Table A-4. PAR content of product and waste samples from coal conver sion plants. Analyses of samples collected at solvent-refined coal plant:. Concentration ppm Raw Solvent Ught Wash Process Mineral Particulate Process Refined Oil Solvent Sol vent Residue Filter Water Coal PNA FRACTION xylene 1300 o-ethylbenzene 9800 1700 m/p-ethylbenzene 700 C)-benzene 3900 1500 C4-benzene 500 Indane 4300 13000 85 methyl1ndane 510 2500 15 25 methylindane 180 1400 methyl1ndane 240 2300 55 dimethyl1ndane <5 40 25 tetra11n 330 4100 <0.1 110 dimethyl tetral1n <5 1500 0.5 35 6-methyltetral1n 110 3200 50 naph thalene 1630 32000 100 1500 I 3 2 -methy Inaph thalene 690 32000 3800 740 8 16 I-methylnaphthal ene 110 12000 930 180 5 4 dimethylnaph thalene 80 13000 11200 0.3 260 6 110 dime. thylnaphthal ene 70 700 1700 60 20 dimethy Inaph tha lene 4000 4200 150 d imethy 1 naphthalene 10 160 650 2 <2 10 2-isopropy Inaph thalene 40 50 0.7 <1 <0.5 l-isopropyInaph t halene 210 1400 2 15 20 C4-naphthalene 5 50 <1 4 cyclohexylbenzene 410 5 biphenyl 80 10000 5900 0.2 270 75 acenaphthYlene 2 500 3400 <0.1 45 60 dimethyl biphenyl 15 35 2100 0.5 30 130 dimethyLbiphenyl 21 30 560 0.2 20 7 40 dlbenzofuran 8 400 5800 0.6 60 9 160 xanthene 10 30 840 0.1 20 5 40 dibenzothiophene 3 50 4200 1.5 70 30 180 methy ldibenzothlophene 15 320 <0.1 8 4 60 dime thy Idibenzothiophene IS 1200 <0.05 20 13 130 thioxanthene 2 3300 0.\ 5 3 120 fluorene 15 250 6600 0.3 80 27 200 9-methyl fluorene 15 HO 3100 0.3 40 It 150 i-methyl fluorene 10 10 3000 0,2 50 18 100 an thracenel phenanthrene 25 130 23000 1.1 500 300 1500 methy 1 phenan t hrene 6 15 6200 0.3 100 50 400 l-methylphenanthrene 6 3900 0.2 50 30 300 C2-an thracene 6 25 500 <0.05 10 1 30 fluoranthene 15 35 10500 0.4 200 180 700 d ihydropyrene 6 25 1200 <0.05 10 I 30 pyrene 20 40 11200 0.6 200 280 900 NEuTRAL FRACTION (n-a I k~n.s) n-octane 16000 900 2.3 n-nonane 8700 2700 n-decane 9800 5000 n-undecane 3900 8300 50 0.3 90 4 n-dodecane 1400 21000 80 0.3 550 10 n-t r idecane 410 14000 30 0.4 9100 8 4 n-tetradecane 170 11000 340 0.3 210 7 12 n-penradecane 60 4000 1000 0.2 80 12 18 n-hexadec.ane 10 400 2000 0.2 50 8 50 n-heptade.:ane 10 120 3100 0.02 20 35 n-o(' tadecane 40 no 10 18 n-nonadecane 500 800 16 22 )0 n-eiC'osane 930 14 20 n-heneicosane 600 14 3S n-doco$ane 670 16 S5 n-tricosane 980 14 35 n-te t ral..:"osane 900 14 4S n-pen tacosane 740 10 4J n-hexacosane 450 8 ~o n-heptacosane 300 6 25 n-oc tacosane 150 5 28 o-nonacosane 90 18 n-triacontane 60 22 n-hen rriacontane 40 15 n-dotriacon tane 10 II n-tri tri~lcont:lne 5 7 From Fruchter et al. (1971). 104 ,.1 II 'J Table A-5. Summary of PAH content of coal derived synthetic oils (TRW, 1916). Range of values Total syncrude H Coal Liquid SRC Process from benzene from COED coal Products, Dis- solvents soluble tars pro- process t illat ion a. startap duced in the syn- b. distilled range solvent thane gasifica- products a. < 2000C (Creos ti tion process 200-3500C b. 200-350oC Oil) with differ- c. 3500-4500 c. 350-5000C b. Regele ent feed coals and hydro- (%, weight) solvent, (%, volume) genated coal de- d. distillation rived bottoms (% , weight ) Alkanef; etc 43 ,49b ,40c, 20d Paraf ins :; Mono Aromatics ~~~~~~~~ ene 1.9 - 4.1 Phenols 2.8 - 13.1 7.9a,2.0b,l.5c Alkylbenzenes 17a,13b,3.0c Biphenyl 2.2a,4.8 Di Aromatics 39 ,4 8b , 30c , 5 3d and hydrogenated derivatives Naphthalenes 11.6 - 19.0 O.6a,3.7b,27c 14.0a,8.9b (methylated) Indans/lndenes 5.0 - 10.5 5.7 Indenes Naphthols & Indanols 0.9 - 11.4 Indans & Tetralines 6.4a,31b,O.5c Tri Aromatics 6.6b,25c Phenyl naphthalenes 3.5 - 9.8 Acenaphenes 11.1 - 15.8 9.2 Fluorenes 1.2 - 10 .1 5.5a,3.2b Anthracenes/Phenanthrenes 9.0 - 14.8 0.5 20a,13b Acenaphthals 2.0 - 4.9 Table A-5. Cont inued. Range of va lues Total sync rude H-Coal L1qUld 8RC Process from benzene from COED coal Products, Dis solvents soluble tars pro process tillation a. startap duced in the syn b. distilled range solvent thane gasifica products a. < 2000C (Creosti tion process 200-3500C b. 200-3500C Oil) with differ- c. 3500-4500 c. 350-5000C b. Regele ent feed coals and hydro (%, we ight) solvent, (%, volume) genated coal de d. distillation rived bottoms (%, weight) Phenanthrols 0.9 - 2.7 ..... Acenaphthalenes 5.9,2.2b,23c,6.6d o 0\ Acenaphthene 9.7a,4.3b Tetracyclic Aromatics Benzanthatenes, chrysene 3.5 - 7.6 1.8,6.8c lOc (Pericondensed) Pyrene, Benzphenanthrenes 1.4 - 4.1 0.8c,8.2d 5c 4.4a,3.2b (Catacondensed) Fluoranthrene 6.4a,3.7b Pentacyclic Aromatics not detected 10 8b Trace Larger & or heterocyclic + + + + Table A-6. Estimated PAR content of soils and sediments. Concentration of PAH found in forest soil. Nea.r Lake Cons ranee PAll (~g Oak Spruce Mixed Beech Woods Woods Woods Woods Woods Woods Benzo(a)pyrene 2.5 4.0 1.5 1.5 2.5 1.5 Benzo (ghi) perylene 10 70 20 10 20 10 Benzo(b) fluoranthene and Benzo(j) fluorant:hene 30 110 50 35 25 25 From Harrison et al. (1975) . PAH in sand filter deposits and river water solids. Location Rapid Rapid PAll (mg kg-I) Sand Sand Filter a River Solids ~!i~:~ b Schussen C Fluoranthene 10.0 1.0 2.0 2.6 20.0 12.0 2.0 11.0 Pyrena 0.2 1.2 1.4 8.0 5.6 1.1 7.9 Chrysene 0.5 1.6 Benzo(a) anthracene 0.4 0.9 1.2 3.2 0.4 2.6 Benzo (b) fluoranthene 0.3)0.4 2.7 6.7 1.2 4.9 1.3 Benzo(j) fluoranthene 0.5 ~::) 0.8 2.0 4.6 1.4 6.2 Benzo(k) fluoranthene 1.0 0.5 0.6 1.3 1.8 2.4 0.4 3.3 Benzo(a)pyrene 0.05 0.2 0.3 0.6 2.0 0.5 0.1 0.4 Benzo (ghi) pe ryl ene 0.4 1.3 1.6 1.4 2.4 4.8 0.4 3.5 Indeno (1,2, 3-cd) pyrena 0.5 0.6 1.7 1.2 4.3 0.6 3.6 From Harrison et al. (1975) . a Coarse settled solids. b Centrifuged particles. of river water. Typical RaP levels in marine sediments. Locati.on Benzo(a)pyrene Concentration (Wg kg- I dry we) Greenland 0.2 Italy Highly 15-45 1000-3000 (Bay of Naples) industrialized 7.5 { 13 area 2-65 10-530 Near volcanic 55 260-960 pollution { 120 1.4 Island affected by 100-560 pollution french Mediterranean Coast 14 400 16 1500 48 75 { 58 82 400 34 20 Estuary 15 15 not detected From Harrison et a1. (l97S) 107 I I I , J Table A-7. Estimated PAH content of soils and sediments (Giger and Blumer. 1974). Fraction Fink hlau Lalllma.. Tentative identificationa 2 168 294 Biphenyl. Acenaphthene 3 182 Tetrahydrophenanthrene. Tetrahydroanthracene 4 as Fraction 3 II 180 236 Fluorene. Acenaphthylene. Biphenylene. Benzoindene 3 as 4 4 166 306 As II, also Dinaphthenenaphthalenes (1) II 178 262 Phenanthrene 2 weak 3 178 290 Phenanthrene 4 178 276+ Phenanthrene 5 178 318 Phenanthrene, Anthracene 6 178 318 Phenanthrene, Anthracene 2 weak 3 190 330 lIIaphthenephenanthrene 4 190 344 lIIaphthenephenanthrene 2 weak 3 230 328 Dinaphthenephenanthrene 4 202 Pyrene ,..... 4 230 328 Dinaphthenephenanthrene o 5 202 Pyrene/Fluoranthene 00 5 230 328 Dinaphthenephenanthrene 6 202 342 Pyrene/Flnoran thene IV 216 230 Benzofluorene 5 242 284 . Trinaphthenephenanthrene 6 :::28 Chrysene, Tripbenylene. Benzanthracene IV 228 312 Chrysene. Triphenylene. Benzanthracene 3 184 338 Dibenzothiophene. lIIaphtbothiophene 3 254 Tetranaphthenephenanthrene 4 184 338 Dibenzotbiophene. lIIaphthothiophene IV 240 lIIaphthenechrysene 4 280 Pentanaphthenephenanthrene IV 252 322 Dinaphthenologs of Tetracyclic Aromatics V 252 336 Benzo (0 Jpyrene. Benzo [e ]pyrene, Perylene. Benzo- ftuoranthene IV 278 320 Trinaphthenologs of Tetracyclic Aromatics VI 278 348 Picene, Dibenzantbracene, Dibenzophenanthrene VI 276 346 Benzolghi Iperylene, Anthanthrene, Indenopyrene VII 276 346 Benzo [ghi )perylene, : •• lthanthrene, Indenopyrene VII 302 344 DibenzoBuoranthene VIII 302 344 Dibenzoftuoranthene VII 300 342 Coronene VIn 326 Dinaphthenedibenz~4Juoranthene. lIIaphthenecoronene aUsted are identifications which arc most consistent with spectra (UV, VIS, MS), chromatographic mobility, and relative volatility. Many series extend beyond the scan limit (350 amu). No last mass is listed if a single peak predominates (as in the first eluates of each major series) or where severe overlap between series occurs. Table A-8. Estimated PAR content of soils and sediments. Polynuclear aromatic hydrocarbons in sediments. West Falmouth West Falmouth a a Downslope Upslope Scott Lake ------ppb ------Fluoranthene 13 .8 32 Pyrene <0.24 15.6 19 Methylpyrene <0.30 4.3 <1.7 Benz (a) anthracene 1.1 1.2 6 Chrysene 1.3 6.0 19 Triphenylene 0.28 2.1 8 Benzo(a)pyrene 2.6 5.5 11 Benzo(e)pyrene 1.3 6.6 22 Perylene 1.0 <5.3 17 From Farrington (1978). aCorrected for loss on drying. Distribution of PARs in Rhondda Fawr sediments (sampling date: Nov. 20,1975). Compound 1 2 3 4 5 6 7 8 9 llg PAR per g sediment (dry weight basis) Anthracene 12.4 5.3 11.2 7.8 7.5 12.8 0.6 17.6 1.8 Fluoranthene 13 .4 12.4 11.0 6.5 10.2 10.4 0.6 13.8 1.6 Pyrene 10.9 8.7 6.1 5.1 8.8 11.3 0.7 21.3 1.9 2,3-Benzofluorene 3.6 3.0 2.1 1.8 2.0 3.2 0.2 7.1 0.6 Chrysene (triphenylene) 15.2 25.9 17.8 35.5 56.8 14.9 1.1 24.1 2.5 3,4-Benzpyrene 9.7 11.9 3.9 7.2 10.2 29.3 2.7 6.0 5.0 1, 2, 3,4-Dibenzanthracene 2.2 6.1 0.6 5.4 7.3 0.4 1.1 Benzo(ghi)perylene 3.6 6.5 1.4 4.2 6.0 2.9 0.6 1.3 Coronene llg PAR per g sediment (wet weight basis) Anthracene 8.4 3.9 8.7 5.9 4.9 9.4 0.6 12.8 1.3 Fluoranthene 9.1 9.2 8.5 5.0 6.6 7.6 0.5 10.1 1.1 Pyrene 7.4 6.5 4.7 3.9 5.7 8.3 0.6 15.5 1.4 2,3-Benzofluorene 2.4 2.2 1.6 1.3 1.3 2.3 0.2 5.2 0.4 Chrysene (triphenylene) 10.3 19.2 13.8 27.2 36.8 11.0 0.9 17.5 1.8 3,4-Benzpyrene 6.6 8.8 3.0 5.5 6.6 21.6 2.4 4.4 3.6 1, 2, 3,4-Dibenzanthracene 1.5 4.6 0.4 4.1 4.7 0.4 0.8 Benzo(ghi)perylene 2.4 4.8 1.1 3.2 3.9 2.1 0.5 0.9 Coronene From John and Nickless (1977) • 109 Table A-9. Estimated PAH content of air emissions and ambient air particulate concentrations. Seasonal Effects on PAH-size Distribution at Range in Composition of Coke Oven York Site. Toronto, Ont. Effluent Samples. (Pg PAH/g particulate) Sampling Compound RIl period" Totalconcn Polynuclear aromatic compounds Range,/018 Chrysene 1.19 S 11.6 ± 0.5 Fluoranthene 1-45 W 17.5 0.8 Pyrene 1-34 Benz(a)anthracene 1.09 S 11.3 ± 0.5 BcnZ(Clacridine <2, <1 W 22.2 ± 0.4 Benz[a]anthracene 2-22 8enzo(a)pyrene 1.0) S 12.6 ± 0.7 Chrysene 1-20 W 17.1 ± 0.9 Bcnz[alanthrone <2. <1 8enzo(h)flu ora nthe ne 0.99 S 11.2 ± 0.5 Bcnzo[a]pyrene 3-25 W 17.4 ± 0.8 Benzo!c']pyrcne 0-19 Perylene 0.9) S 7.1±0.3 Total cyclohexane 0.1-7.5 mg W 10.1 ± 0.5 soluble Benzo(ghi)perylene 0.85 S 20.2 ± 1.0 W 31.1 ± 1.5 Searl et al., 1970 Coronene 0.40 S 8.2 ± 0.5 ...... W 12.3 ± 0.7 ...... Anthanthrene 0.78 S 1.8 ± 0.1 0 W 2.6 ± 0.1 8enzanthrone 0.67 S 30.5 ± 1.8 W 39.1 ± 2.3 Perinaphthanone 0.37 S 26.5 ± 1.6 W 15.9± 1.0 .. S. York (24/06172-28/01!l2). W. York (31/01/72-31/03/12). Rn. distance traveled by compound wIth ,espect to benzO(a)pyrene. Pierce and Katz, 1975 Quantitative results for the basic fraction (air ~articulates). First Determination Second Determination b Results of PAR Analysis of concenlration. (ppm weight) (~~m weight) Some Airborne Particulate n!l/m' Com~ound Average Sam~le t Sam~le Sam~le Sample 2 Matter. 8/17- 8/2·1- RRTQ compound 18/76 25/76 Methylquinoline 14 L5 l3 L4 l.32 0.4 0.6 Acridine and f1uoranthene benzoquinolines 33 26 25 20 26 pyrene 1.42 0.2 0.5 Phenanthridine L2 9.4 L4 LL L2 benz(aJanthracene l.81 1.6 2.4 Benz[x]acridine L8 13 25 L6 LS chrysene/triphenylene 2.00 1.6 3.0 Benzo[x]phen8nthridine 35 25 28 24 28 2.58 3.0 4.4 Dibenzo[x]quinoline II B.O 8.6 6.6 S.6 benzoic J pyrene 8 benzo[a 1pyrene 2.60 1.6 2.9 Dibenz[x]acridine B.8 13 26 L3 3.63 1.3 1.1 benzor gil; Jperylene From Cautreels and Cauwenberghe (L977). a RRT = retention time relative to C,.. b Concentra tions corrected for recoveries. aValue is in error owing to an artifact. Daisey and Leyko, 1979 Table A-I0. Estimated PAR content of air emissions and ambient air particulate concentrations (Guerin, 1977). Concentration. ng/qm Naphthalene 8.3 2-Methylnaphthalene 5.0 l-Methylnaphthalene 5.2 Biphenyl 10.3 1.6- and/or 1.3-0imethylnaphthalene T 2.6-Dimethylnaphthalene T 1.5- and/or 2.3-0imethylnapthalene T 9.10-Dihydroanthracene 12.6 Phenanthrene 17.6 2-Methylanthracene 9.1 l-Methylphenanthrene <24.8 Fluoranthene <13.4 Pyrene <19.0 1,2-Benzofluorene 36.8 2,3-Benzofluorene 11.8 l-Methy 1 pyrene T Picene T TOTAL 0.2 ppm T. trace 111 Table A-1!. Estimated PAR content of air emissions and ambient air particulate concentrations (Katz et al., 1978). Comparative Seasonal Concentration Levels of PAH's in AIr ot OntarIo Cities April 1975-March 1976 [Location: Toronto (Bathurst at 401): Site No. 340071 Apr~-Jun. 1975 Jul.-S.pt. 1975 Ocl.-P..,. 1975 Jan.-Mar. 191a l 0QI1000 m' "gig ng/1000 m "gill no:/1000 m' WII "9/1000 m> I'!//II AIr p ..... AI< p.m. AI. p.m. AI< p.m. Benzo(a)pyrene 189 8.8 1047 11.0 1874 20.2 720 9.2 Benzo(ejp)'rene 440 4.9 519 5.4 1294 15.6 781 10.0 Benzo(bllluoranthene 866 9.1 798 8.4 1387 16.8 783 10.1 Benzo(kllluoranthene 428 4.8 571 6.0 916 11.1 508 6.5 Perylene 102 1.1 123 1.3 193 2.3 108 1.4 Dibenz(det,mno)ctvysane 46 0.5 44 0.5 234 2.8 34 0.4 Benzo(ghilpef)'lene 5849 65.3 7131 74.8 10528 127.2 4413 56.7 Naptho(l.2.3,4,det)chr)tsene 270 3.0 362 3.8 538 6.5 228 2.9 Benzo(rst)pentaphene 58 0.7 60 0.6 150 1.8 67 0.9 Dibenzo(b.det)chf)'sene 313 3.6 183 1.9 446 5.4 213 2.7 Comparative Seasonal Concentration Levels ot PAH's In Air ot Ontario Cities April 1975-March 1976 [Location: Toronto (Kennedy at Lawrence); Site No. 33003) Apt...... un. 1175 Jul.-Sept. 1975 Oct.-D.... 197$ """.-Ma,. 197. "V/1000 m' "gig OQIl000 m> "gig ngll000m3 Wg ngl1000 m3 "gig Air p.m. AI< p.m. AIr p.m. AI< p ..... Benzo(a)pyrene 657 8.7 408 6.2 729 11.7 814 5.9 Benzo(ejpyrene 478 6.3 375 5.7 400 6.6 791 5.8 Benzo(b )fluoranlhene 890 11.8 693 10.6 1259 20.7 1829 13.4 Benzo(k)lluoranthene 328 4.3 285 4.4 597 9.8 519 3.8 Pef)'lene 99 1.3 57 0.9 136 2.2 51 0.4 Dibenz(def.mnolchf)'sene 65 0.9 38 0.8 102 1.7 162 1.2 Benzo(ghi)pef)'lene 5077 67.1 3303 50.5 4693 77.3 9814 71.6 Naptho( l,2.3.4.del)chf)'sene 410 5.4 201 3.1 300 4.9 2762 20.2 Benzo(rst)pentaphene 89 1.2 27 0.4 90 1.5· 259 1.9 Dibenzo(b,del)chf)'sene 210 2.8 109 1.7 229 3.8 490 3.6 Comparative Seasonal Concentration Levels of PAH's in Air ot Ontario Cities April 1975-March 1976 [Location: Hamilton: Site No. 29025) Apr.-June 1975 Jul.-Sep" 1975 OCt.-Dec. 1975 Jan.-Mar. 1916 ...,g/1000 ...,3 ng/1000...,:1 3 "gig "gIg 'ng/1000 ...,:1 "gig nO'I1000 m "gig Ak p.m. AI, p.m. Air p.m. Air p.m. Benzo(a)pyrene 1404 9.6 2351 16.9 3498 50.6 1934 23.1 Benzo(e)pyrene 606 4.2 1407 10.1 3771 54.4 1607 19.2 Benzo(b)fluoranthene 813 5.6 2626 18.9 7841 113.1 2297 27.S Benlo(k)fluoranlhene 419 2.9 1425 10.3 5145 74.2 443 5.3 Pef)'lene 141 1.0 283 2.0 403 5.8 347 4.2 Oibenz(def.mno)chrysene 70 0.5 128 0.9 369 5.3 150 1.8 Benzo(ghi)perylene 5809 39.9 7183 51.1 7532 108.7 6418 76.7 Naptho( 1.2.3. 4.del)chf)'sene 184 1.3 1017 7.3 2027 29.2 903 10.8 Benlo(rst)pentaphene 74 0.5 247 1.8 434 6.3 281 3.4 Oibenzo(b.del)chrysene 331 2.3 915 6,6 1132 16.3 704 8.4 Comparative Seasonal Concentration Levels of PAH's in Air of Ontario Cities April 1975-March 1976 (Local/on: Soulhern Sarnia; Site No. 140611 Apr. ...Jun. 1975 Jul.-Sept. 1975 Oct.-Dec:. 19n Jan.-Mar. 197. ng11000...,3 3 3 ~g/g ng/1000m ~g/g ng11000...,3 ~O/g no/1000 m "gig AI, p.m. AI, p..... AI, p.m. AI, p.m. Benzo(alpyrene 338 5,5 114 2.4 596 11.4 190 7.0 Benzo(e)pyrene 118 1.9 52 1.1 603 11.5 64 2.4 Benzo(b)fluoranthene 371 6.0 243 5.2 938 17.9 289 10.6 Benzo(klfluoranthene 81 1.3 70 1.5 439 8.4 104 3.8 Perylene 27 0.4 13 0.3 87 1.7 19 0.7 Oibenz(del.mno)chrysene 23 0.4 8 0.2 44 0.8 7 0.3 Benzo(ghi)perylene 1038 16.8 1049 22.5 2700 51.7 1158 42.6 Naptho( 1.2.3,4.def)chrysene 823 13,3 61 1.3 434 8.3 129 4.7 Benzo(fstlpentaphene 422 6.8 15 0.3 69 1.3 23 0.8 Dibenzo(b.del)chrysene 508 8.2 81 1.7 213 4.1 107 3.9 112 Table A-ll. Continued. Comparative Seasonal Concentration Levels of PAH'sln Air of Ontario Cities April 1975-March 1976 [Locallon: Sudbury; Site No. 77016] Apt.-June 1'7$ Jul.-Sept. 197$ Oct~-DN:. ,'75 J.n.-M,at~ 197a ngl1000,.;s "glo ngl1000,.;s "gig ngl1000,.;s "glo ng/1QQQ m' ..aIO Air p.m. AIr p.m. AIr p ..... Air p ..... Benzo(a)pyrene 175 5.4 111 2.6 342 15.3 444 19.0 Benzo(eJpyrene 23 0.7 45 1.1 255 11.4 317 13.6 Benzo(b)fluo,antnene 255 7.8 173 4.1 417 18.7 650 27.8 Benzo(k)tluoranlh_ 57 1.7 74 1.8 197 8.S 271 11.8 Perylene 17 0.5 17 0.4 41 1.8 50 2.1 Dibenz(def.mno)chtysell& 8 0.2 9 0.2 37 1.7 32 1.4 8enzo(ghlJperylene 779 23.9 1104 26.3 2321 104.0 3009 128.7 Naplho(l.2.3.4,def)chtysene 510 15.6 73 1.7 99 4.4 230 9.8 Benzo(rst)penlaphene 40 1.2 10 0.2 17 0.8 36 1.5 Dibenzo{b.def~ 149 4.6 47 1.1 S4 2.4 130 5.8 Total Concentrations of 10 PAH's 11'1 Air of Ontario CIties April 1975-March 1976 T_ TorOf'lto H"""HOft s.m,. Sudbury 51t.34007 Sit. 331,'103 511.21025 _0 $U.14011 5n.7701• 3 3 hgl1000,.;s ..aIo ..gI1000 m ..aIo ng/1000 m ng/1000 m:l I'glo ft9I1000 m 1 AIt- p.m. Air p.ni. Air p.m. Air p.m. Air -,p.m. Apr- . ..June 9161 102.4 8303 109.8 9851 67.8 3749 60.6 2013 61.6 Jul.-Sept. 9838 113.7 5496 84.1 11582 126.S 1706 36.5 1663 39.5 Oct.-Dec. 17 360 209.7 8535 140.2 32152 463.9 6123 117.1 3780 169.3 Jan.-Mat. 7855 100.8 17491 127.8 15084 180.4 2090 76.8 5169 221.1 Mean 11 053 131.6 995.6 115.5 18667 209.6 3417 72.7 3156 122.9 Comparative Concentration Levels of PAH's 11'1 U.S. and Other Cities "'w Yortc City A .. u.s. ""'wetp Gh...t Mn.,. (22) "'.... (23) (24) (1Q) (1Q) ngl1000,.;s PM ngl1000 m' I'V/ O ngl1000 ",' 1'0/ 0 'pg/g compound Air Air pa'" Air part. p .... Benzo(a)pyrene 1150-1300 5700 51 5200 60 46 Benzo{e)pyrene 1400 5000 51 Benzo{blfluoranthene 800 2300-7400 83 (Det,olt) 7700 90 68 8enzo(1 • Antwerp CMcentfation includes anthanthtette. 113 J Table A-12. Estimated PAH content of aquatic organisms and food. 9 a Polynm.. lt1ilf <1romaE tc hydnh.:a.rbolli>' In flnfl.-;h. Polynuclear 1U'!)1II8cic hydrocarbons east coast illU&8els (10- gIg dry welght ). Narragansett, Blue H111 Falls, 8oBton. Fire Island, Compound Rhode laland Haine Hasa. New York ------~------ppb. 10,/(;[ wel ght ~------Naphthalene 9.8 8.2 4.2 2.6 ...:0.3 0.5 <0.3 Hethylnaphthalenes 9.1 8.2 25 7.2 ·0.6 <0.5 <2 9 8 Polynuclear arOmatic hydrocarbons in shel Utah. Polynuclear aromatic hydrocarbons oystera (10- gIg dry we1gh( ). UYSlt!r Oyster Clam Clam Crab Crab Inlet. St. Augustine. Pass Christian. BIloxi. CoClpound (Chlrh,:olcilguC. Va.) (L.I. Sound) (Va.} (L.r. Sound) {Chesapeake} (Raritan) Florida HIss. Miss. ------ppb. wet weiSht Naphthalene 1.8 2.0 8.6 Methyl naphthalenes 4.8 18 Pyr~nt! 0.5 56 1.0 12 <0.2 Dimethylnaphtholenes. 11.0 9.0 8S Htl-pyrenu ;:-0. I II <0.2 2.5 <0.2 1.6 Phenan threne 8.4 29 ]) 60 BaA 0.02 8 0.3 1 <1.5 2 He t hy 1 phenanthrenes 8.9 45 26 170 Chry~cne 0,3 7.0 <0.1 1.6 <1.2 2 Dlmethylphenanthrenea 49 _0 29, rr l. Jlh~ny 1~nt:: O. ) 15.1 <0.1 3.3 Polynuclear dromatic hydrocarbons in selected food samples. Fresh ~:~d G~~:: Hamburgers& Oranges Fresh Spinach Lettuce Peanuts ----=-="'- String Beans ------ppb. lofet weight ------ <0. } <0. j <0.3 <0.2 0.2 <0.9 <0.6 <0.2 <0.1 <0.3 <0.1 <0.3 <0.02 0.9 <0.02 <0.4: 0.4 "Composite sample of cooked hamburgers. From Pancirov et al. (1978) Table A-l3. Estimated PAR content of wastewaters and river waters. PAH in wastewater samples. Domestic Factory Domestic Sewage PAR (ngll-I ) Effluents Effluents Effluents (high percentage industry) Fluoranthene 2416 2198 273 3420 2660 Pyrene 1763 1957 3120 2560 Benzo(a)anthracene 319 167 191 1360 343 Benzo(b) fluoranthene 202 114 36 870 525 Benzo(j) fluoranthene 205 45 37 1740 1I00 Benzo(k) fluoranthene 193 32 31 460 336 Benzo(a)pyrene 74 100 38 100 368 Benzo(ghi)perylene 219 73 40 480 120 Indeno (1,2" 3-cd) pyrene 238 57 2Z 930 476 From Harrison et al. Wt75). PAR in domestic sewage during dry and wet weather. Concentration in Concentration in Sewage During Sewage OUI:' iog Dry Weather Heavy Rain Fluoranthene 352 16,350 Pyrena 254 16,050 Senzo(a) anthracene 25 10,360 Benzo(b) fluoranthene 39 9,910 Benzo (j) Huotan thene 57 10,790 Benzo(k) fluoranthene 22 4.180 Benzo (.) pyreoe 1,840 Benzo (ghi}perylene 4 3,840 lndeno (1.2 , 3-ccl) pyrene 17 4,980 From Harrison et 01. (1975). Polynuclear aromatic compounds in wastewater effluents. Nil - not detected (detection limit in bracket). From Pane irov et al. (1978). 115 J II 'I Table A-14. Estimated PAR content of wastewaters and river waters. PAH levels in Thames River water. -1 Location PAH (ng 1 ) Kew Albert Tower Bridge Bridge Bridge Fluoranthene 140 200 360 Benzo(k)fluoranthene 80 40 120 Benzo(a)pyrene 130 160 350 Perylene ·40 70 130 Indeno(1,2,3-cd)pyrene 50 110 210 Benzo(ghi)perylene 60 110 160 From Harrison et al. (1975). PAH levels in German rivers. -1 PAH (ng 1 ) River Gersprenz River Danube River Main River Aach River at Hunster at Ulm at Seligenstadt at Stockach Schussen Fluoranthene 38.5 71.3 94 61 107 21.3 128 192 694 474 379 761 358 Benzo(a)anthracene 18.8 4.3 11 14 7.4 7.0 14.4 16.2 385 199 101 128 57 Chrysene 11.8 26.4 38.2 Benzo(b)fluoranthene 10.4 13.2 24.2 23.9 12.2 19.9 32.1 67.0 362 177 76 332 41 Benzo(j)fluoranthene 4.6 14.7 10.1 23.4 14.2 21.5 35.7 75.5 337 394 144 420 53 Benzo(k)fluoranthene 9.6 4.8 7.7 14.1 4.2 6.4 10.6 21.6 130 136 132 173 33 Benzo(a)pyrene 9.6 0.6 1.3 1.1 2.4 6.5 43 16 4 5 10 Benzo(ghi)perylene 12.9 1.6 9.5 9.5 8.0 13.2 21.2 25.9 84 105 42 46 46 Indeno(I,2,3-cd)pyrene 12 5.4 9.5 16.4 12.5 19.5 32.0 23.7 217 116 144 188 45 From Harrison et al. (1975) . Table A-IS. Estimated PAR content of wastewaters and river waters (Guerin, 1977). Mi11iQrams eer Liter {epm} Synthane Gasification Solvent Refined Coal Simulated In-situ Constituent Condensate Raw Process Water Shale Retort Bl Product Water Napthalene 0.2 5 0.1 2-methylnapthalene 1.3 2 0.3 l-methylnapthalene <0.1 -a 0.1 2.6-dimethylnapthalene cO. 1 <0.1 1.3 + 1.6-dimethylnapthalene 0.1 0.2 1.5 + 2.3-dimethylnapthalene cO.l 0.1 1.2-dimethylnapthalene cO.l cO.l Oimethylnapthalenes 2.3 2-isopropylnapthalene 0.7 l-isopropylnapthalene 2 Biphenyl cO.l 0.2 cO.l Acenapthalene cO. 1 Acenapthene lRb cO.l 0imethylbiphenyls 0.7 Fluorene cO.l 0.3 0.2 9.10-dihydroanthracene cO.l cO.l 9-methylfluorene 0.3 I-methyl fluorene NO c 0.2 0.2 Anthracene/phenanthrene NO 1.1 0.3 2-methylanthracene NO 0.2 I-methyl phenanthrene NO 0.2 0.1 aNot determined b Trace cNot detected 117 .I Table A-16. Comparison of BaP content of selected materials (Guerin, 1977). Haterials .1ateria 1s Crude Oi Is Mi see 11 aneous Petroleum Creosote 200 Libya 1.3 Venezua 1" 1. 6 Coal Tar 1800. 5000 3,000 Persian Gulf 0.04 Arabian 1.5 Coal Tar Pitch 10,000 Shale Derived 3 Raw Shale .015 Crude Oi 1 3.1 Processed Shale .03 Hydro treated 0.7 8i tumonus Coal <.001 Coal Derived 3 Reference Envionmental Materials Catalytic Hydrogenation 1.6. 41 Waters Pyrolysis 4.1 Uncontaminated ground water <0.00001 Petrol4:lJm Products Drinking water <0.00003 Gasoline 0.4 Contaminated by industrial effluent 0.01 Coomercial 0.46. 0.03, 0.55 Heavily contaminated by coking, oil shale, Catalytically Reformed 6.2 oil-gas processing 0.5-1.0 Natiom·lide Composite Premium 0.48 Miscellaneous Nationwide Composite Regular 0.21 Foods <0.001 I'!otor Oil, new 0.03 Earths upper crust 0.1-1.0 Motor Oil, used 2.4. 6.0 4 Blosynthesized per weight dried material. Diesel Fuel . 0.03, 0.07 .05 wheat dnd rye 0.01-0.02 No. 2 Heating Oil 0.01-0.05 .03 Asphalt 0.1-27 2 Petro lellm Pitch 2000 Table A-17. Comparison of BaP content of selected materials (Coomes, 1976) • Substrate Material E:enzo(a)pyrene Natural Hateria1s (parts per billion) Coconut oil 43.7 Peanut oil 1.9 Oysters (Norfolk, Va.) 10 to 20 (based on dry weight) Forest soil 4 to 8 Farm field near Moscow 79 Oak 1eaves 300 max Petroleums and Petroleum Products Libyan crude oil 1 ,320 Cracked residuum (API Smpl 59) 50,000 Cracked sidestream (API Smpl 2) 2,000 West Texas paraffin distillate 3,000 Asphalt 1 x 104 to 1 x 105 Oil Shale Related Materials TOSCO II retorted shale 13 - 100 GCR retorted shale 15 Raw shale oil (Colorado) 30,000 - 40,000 Crude shale oil (TOSCO II) 3,130 Hydrotreated shale oil (0.25%N) 6,900 Hydrotreated shale oil (0.05%N) 690 --Coals High volatile bituminous 4,200 Low volatile bituminous 3,150 Lignite 1 ,200 Coal tar 3 x 106 to 8 x 106 119 Table A-18. Comparison of BaP content of selected materials. BaP levels in industrial effluents. Concentration Industry of B~ (llgl - ) Shale oil After dephenolization I 2 II 2 III 312 Coke by-products After biochemical treatment 12-16 Gasworks After filtration through coke beds 20 After depheno1ization 130-290 Oil refineries Coking of residues after direct distillation of oil 0.48-5.0 Catalytic cracking of kerosene 0.14 gas oil fraction at 450°C 0.ll-0.19 0.05-0.29 Catalytic cracking 0.07-0.ll Thermal cracking, 700-8000 C 0.09-0.23 0.10-3.0 Pyrolysis of ethane ethylene o fractions, 700-800 C 3.6 After settling ponds of various refineriesg up to 0.22 From Harrison et al. (1975). 120 Table A-19. Comparison of BaP content of selected materials. BaP Concentration Source (l1g kg -1) Greenland Plankton 5 Italy Plankton 6-21 French Channel Coast Plankton 400 Greenland Algae (sample at 40 m) 60 Greenland Algae (sample at seabed) 60 Italy Algae 2 Greenland Cod fish 15 Greenland Mollusk 60 Greenland Musse 1: shell 18 body 55 Italy Mussel: she 11 11 body 130 and 540 Italy Hollusk 2 Italy Sardine 65 _. ------From Harrison et :11. (1975). Benzo[al- Benz[aJ- pyrene anthracene Foodstuff (ppb) (ppb) Literature Cited Fresh vegetables" 2.85--24.5 0.3-43.6 24,25 Vegetable oils OA-1.4 0.8-1.1 27, 189, 190 Coconut oil 43.7 98.0 28, 29, 191 Margarine 0.4-0.5 1.4-3.0 192 _Mayonnaise 0.4 2.2 192 Coffee 0.3-1.3 1.3-3.0 193, 194 Tea 3.9 2.9-4.6 193 Grain" 0.19-4.13 0040-6.85 32, 195, 196 Oysters and mussels 1.5-9.0 197, 198 Smoked ham 3.2 2.8 26, 45, 199 Smoked fish b 0.83 1.9 40,40:,199,200 Smoked bonito 37 189 201 Cooked sausage 12.5--18.8 17.S-26.2 199,202,203 Singed meat 35-99 28-79 204 BroilE'd meat 0.17-0.63 0.2-oA 44, 200, 205 Char('oal-broiled steak a 8.0 4.5 44, 205 BroilE'd mackerel 0.9 2.9 51 Barbecued beef 3.3 13.2 199 Barbecued ribs 10.5 3.6 44 4 Dibenz[a,hJanthracene has heen dete('ted in charcoal-broiled meat (0.2 ppb), gra.in (0.1-0.61 ppb), and fresh vegetables (0.04-1.71 pph). b A number of Russian studies (206, 208) reported higher levels, up to 8,.5 ppb of benzo[alpyrene in smoked fish. From Searle (1976) 121 ..... ~ OIL SHALE MINERAL RIGHT OWNERSHIP PICEANCE CREEK BASIN, COLORADO PATENTED/FEE LAND ______ FEDERAL LANDS 0 JWh.n locat•• within Withdrawal Ar ••} MAXIMUM THICKNESS (IN FEET) OF CONTINUOUS OIL SHALE SECTION AY!;RAGING AT L£AST ZS GALLON OF OIL P£R TON {F,om SuMIn•• 11-1. 73Sn_.-IIP' r-""Ti~"lrrITt-lg*-t-t-!';;:;;';;r-U~":"~;;~~b_,-:CURIIENTSHAL£ WITHDRAWAL'SOUNDARIES OF______THE 'FEDERAL OIL_ ACKNOWLBlGMI!NT ~.-iI-~--+---~""--;--+-;-""".-C'H';-f:;-t~;::~...:'f'-,A±-r""l.;7.';r--; Ma., aba',ac1.d and ,.dwc:H from Ot".'''.' a .. ppli.d by C."..tOft ~,.. tn,., o.n.... r. M.,..r.1 rlg"t OWft.. ahtp o. I... 1ft.", 100 "r•• "'.y not ... r• .,...... d. due 101ft. ",ap·. l ...aU Kakt. Figure A-2. Specific oil shale develop areas (Kilburn et al., 1974). 122 , I J - . • • .... N - LV • a 0 ~a III ... lilt .. f!J r:P 0 aD 0 cfl, r!I' [(D 0 _~ __.;;o;.t CIL IIW.I ~ IIIIIKT CIIINIMIW' Gil 0 • tl 0 0 '. • UINTA BASIN UTAH - COLORADO o •• ' II .._ .i" II'~ D .,!I [J ...~ 0 [J _1rrUI0II...... ""*' rI'·"p D .J3I. _ fJIEl'llA'lCIIL ...... 1.., .... _,...... l..UIID 'I'l '0 O ...... ,.. .. ·L .... _ ...... ~CL_ ~~ .:-...... "0 ...... [J o o D:="U:-u. CC DD DO rP urAl! Figure A-3. Specific oil sha.le develop areas (Slawson, 1979). a Table A-20. Comparison of 3 to 5 ring PAR ~n selected material. ppbb Shales 1 - 102 Coals 103 Oils 10 - 103 Coal Oils 103 - 107 Shale Oils 103 - 104 + Asphalt 103 - 105 Coal Tar and Petroleum Pitches 106 - 107 Coke Oven Emissions 107 (Searl et al., 1970) Soils 1 - 103 Air Particulates (cities) 102 - 105 River Sediments < 1 - 103 River Waters 10-3 - 10-1 Solubility (5 - 3 ring PAR) 10-2 - 1 Industrial Effluens 10-2 102 Shale Related Wastewater 1 - 103 Potable waters < 10-2 Sewage 10-3 - 10 2 Terrestrial and Aquatic Organisms 10-2 - 10 2 (and Food) Tobacco/Marijuana Smoke (~ 1 ~g/IOO cigarettes) (Lee et al., 1976) aData from Tables A-2 - A-19 and A-2l and A-22. bppb except as indicated Note: underlined data judged most reflective. 124 Figure A-4. Isoerodent map, R, for Colorado (Fletcher et al., 1977). 125 ". 113 "' '" Figure A-S. Isoerodent map, R, for Utah (Fletcher et al., 1977). 126 Table A-21. Factors influencing solubility of PAR in water. . Sorption dependence on sorbate properties. Compo.,nc! Pyrene 12 135 84 150 0.56 Me tnoJ(ycn lor 6.3 120 BO 120 0.67 Naphthalene 4460 31,700 1.3 2.3 0.57 2-Me chy Inaph thalene 3220 25,400 B.5 lJ 0.65 Anthracene 7.57 73 26 35 0.74 9-Methylanchracene 24.4 261 65 117 0.56 Phenanthrene 130 1.290 23 37 0.62 Tetracene 0.037 0.5 650 BOO O.Bl Hexachlorobiphenyl 0 _.048 0.95 1200 2200 0.55 Benzene 410,000 1,780,000 0.083 0.13 0.61 From Kariekhoff et &1. (1979). Variation of aqueous solubility w1th rellperatuu (oC). Solubility on Temperature Correlation l. Benzene (0.0247t3 0.6838c2 + O.3166t: + 18J3)xlO3 0.9443 2. Naphthalene (0.0189,2 .0.2499< + lJ .66) d03 0.9987 3. Fluorene 0.0185c3 + 0.4543c2 + 22. 7t)t 543 0.9999 4. Phenanthrene 0.0025t3 + 0.8059t2 + 5.413t • 324 0.9992 5. !-Methylpnenanthrene 0.0080t3 - a.DOitZ + 6.8016c +• 55.4 0.994 6. Pyrene -a.OOllt) + 0.2007c2 "" LOSH + 50.2 0.9997 7. Fluoranthene 0.0072t3 - 0.1047c2 + 4.322t 50.4 0.9988 8. Anthra<:ene 0.0013t3 - 0.0097t2 + 0.B861t •+ 8.21 0.9998 9. 2-Methylanthracene 0.0011t3 0.0306t2 + 0.8L80t + 2.79 0.9988 10. l, 2-'Sen~anthracene 0.0003t3 - 0.0031t2 + O.l897t+ 1.74 0.9991 11. Chrysene 0.0024t2 + 0.Ol44t + 0.609 0.9982 From May and Wasik (978). aThese equations and correlation coefficients were obtained from versus temperatlJre data to the Polynomicai Regression (2° or 3°) program Hewlett-Packard 98JOA ea Lculator. Soiubility of some PAH In water at 25°C. PAH Naphtholl\!n\! 12.500 Phcnanthrenl:! l.600 Anthr-:.!;.. "':!'nl:! 15 Pyrt)n~ 175 n u.1t'anthene 265 ChrY1:lene 6 Ben%o (.l) anthracene 10 Naphthacene 1.5 from Harri.son et .11. (1975). 127 J Table A-21. Continued. The aqu~uus solubllili~:; oi some aromatic hydrociJrbons a:> J~lermLned by several investigators. ==--_-_---_==--==:=.==C__ ------"'_--__=-=-=-=_=-======------So 1 ub i 11 [les (mg/kg) ------:..------ HoI. ------This Work ------Davis Mackay (. Shut Schwarz Wauchope & Getzen Others Compound o o ",. 25°C 29°C 29°C 25°C 2S C 25°C 2S C (1942) (1977) (1977) (1972) ----- Benzene 78.1 1791 10 1780 (9) • 1755 (10) • 1755 (14) • 1796 (20) Naphtha I t!ne 128.2 31.69 .23 31.7 .2 ]0. ] ± .3 ]1.2 34.4 (4) Fluoren~ 166.2 1.685 .005 1.98 .04 1.90 Anthracene 178.2 .0446 .OOO2 e .0570 1" .003 .0570 , .005 .07) , .005 .041 ± .000) .075 .075 (20) Phenanthrent! 178.2 1.002 .Olle 1.220 .01 ) 1.600 .050 1.290 , .070 I. 151 , .015 1.180 .994 (24) 2-He thy I anthracene 192.3 .0213 .OOle I-Met hy I pht'nanrhrene 1':12.3 .269 .oo)e Fluoranthene 202.3 .206 .002 .264 .002 .240 .020 .260 .020 .265 .240 (24) Pyrene I 202.3 .132 .001 .162 .001 .165 .007 .135 .005 .129 , .002 .148 1,2-Ben:tdllthra('ene I 22S.3 .0094 .0001 .0122 .0001 .011 .001 .014 .0002 .010 (20) Chrysene 12S.3 .001S .0001 .0022 .0eUl .0015 .0004 .002 .0002 .006 (20) ------FrOID Hay and Was lk (1978) . ...... N (Xl Table A-22. PAH content of petroleum products. Some polycyclic aromatic hydrocarbons in petroleum products. QJ ,:::: QJ r-I Gasolines QJr-I No. 2 Heating Oils Motor Oils Ul Ul QJ a QJ ;:I llg/ml (ppm) ...... trz.. llg/g (ppm) llg/ml (ppm) QJ p ::4 A B C D llg/gm (ppm) A B C D New Used Anthracene 0.04 2.9 4.2 1.0 6.7 2.4 Phenanthrene ND ND ND ND ND ND Methylanthracene - <0.01 9.3 6.6 20.7 15.2 20.7 Benz (a) anthracene 1.0 11.5 ND 0.54 <0.01 0.13 0.03 0.03 0.06 0.02 ND 2.2 l-' Pyrene 2.0 10.6 0.15 5.1 0.16 0.37 ND 3.0 0.58 0.45 1.3 11.6 N \D Fluoranthene 1.8 20.8 0.06 3.2 0.09 0.57 0.47 3.2 ND 3.6 Chrysene 0.57 4.9 ND 0.54 ND 0.45 0.50 0.51 0.37 0.81 Triphenylene ND 3.3 ND 0.76 0.23 1.2 Benzo(a)pyrene 0.46 6.2 0.03 0.55 ",0.01 0.07 0.04 0.01 0.05 0.01 ND 2.4 Benzo(e)pyrene 0.37 2.0 0.03 0.85 <0.01 0.18 0.02 0.02 0.02 <0.01 0.67 2.7 Benzo(ghi)pyrene 0.83 6.4 0.04 1.40 <0.01 0.03 0.07 0.02 0.01 0.01 0'.28 1.8 Coronene' 0.22 0.53 0.01 0.34 ND 0.57 From Guerin (1977). Table A-23. Recoveries of monocyclic aromatic hydrocarbons with XAD resins (Gustafson and Paleos in Faust and Hunter (eas.), 1971 and Webb. 1975). Typical Properties of Various Adsorbents Porosity Surface Area Ave. Pore 2 Resin ml/ml m /g DiaID. K STYRENE-DVB ADSORBENTS XAD-l 0.352 100 200 XAD-2 0.430 313 91 XAD-5 0.434 415 68 EXP-500 0.387 525 45 XAD-4 0.552 860 51 METHACRYLATE-BASED ADSORBENTS XAD-7 0.532 445 82 XAD-8 0.513 212 160 ACTIVATED CARBON CAL(12 x 4q 0.685 1045 38 Percent Recovery frofll 50 J.lg/l Samples COl1POUND XAD Resin a a 7 24 S 2 2S a 24 4 4S C'ICI b I I I '3 I I bis-Ch1oro isopropyl ether c 74 77 176 76 77 71 80 77 92 i 1 i :>ym"'1'etri'\('h nrn'>tha:te 35 58 59 . 66 61 68 69 ! 72 72 82 I : n-HCx.acecilnc 3 c c 8 3 18 14 ! c 11 )inco1 0i?h~ ! ! 1 T 'rh"l",n<" 64 66 I 78 77 79 81 82 80 1 80 87 I I I 83 £-Ni troto1uenc 53 75 I 77 79 82 81 81 83 j 91 I I I ! 2-!<:ethy1 nGp::..a;halene 63 61 77 72 75 80 81 77 177 ! 86 I i , I I j 1-1.1cthy1 naphthe.1ene 64 62 80 75 76 82 80 77 79 86 I I I I Benzothiazo1e ! 40 80 53 75 ! 74 73 77 82 ~ 82 96 I ! i i I I I Phc!'.ol I 30 29 32 i 33 41 38 ~() I 19 119 I I 11-: I ! ! i 33 58 I 47 60 69 68 I 50 .z-Creso1 I I 50 144 I 49 i I Ace:taphthene 72 68 20 81 99 ! 85 84 81 I 81 I 91 I I I I I I Dibonzofura:l 73 I 70 95 83 93 86 85 82 84 92 I I 1 I I Averages excluding -I 51 69 70 i2 74 75 76 80 n-He:<~deca.'1e 65 I 1 /71 I I ! ! i a - puxture of equal dry we~ghts of each res~n. b - Sample directly extracted with b;o SO-ml portions. c - Peak ~~suitaj)le for accurate quantitation. 130 Appendix B Summary of Organic Chemistry Extraction and Identification Regimes Reported in the Literature 131 Table B-1. Summary of selected oil shale investigations of organics. Identification Methods Samples and/or GC Columns Procedure Keywords and Other Comments Source Analyzed and Conditions Chong et al. Oil shale 50' SE-30 Extracted with benzene and methanol 76 thermally SCOT LC IRA-904 anion, A-IS catio~. FeCl -clay 0 0 3 degraded with 100 -275 @ IRA-904 anion, silica gel, SA molecular SO/min sieve CO-H 20 Cummins et al. Raw shales 50' SE-30 4.7 kg stirred in 6 ~ benzene 1/2 days + 72 and 74 L in situ capillary column 10 min ultrasonic ~ 7.5% organics extracted ./ simulation LC alumina of pentane solubles columns LC silical gel and SA molecular sieve ~ alkanes Gallegos Green River 200' x 0.02" Crushed 2-3 mm, soxhlet extraction for 73 shale Dexsil coated one week capillary GC/MS 50:50 benzene:methanol TIM ? Chromatography Jacobson et al. Raw. shales 1/8" od 10' SS Pyrolysis procedure. retorting study 74 Utah 150/200 mesh Wyoming Poropak Q Colorado He 50-1800 C Kwan et al. Spent and raw GC/MS and HPLC Spent shale ground to <100 mesh soxhlet 77 shales + extracted 48 hrs benzene. roto evaporation LC-alumina benzene-methanol fractions Maase et al. Processed 10 m glass capil Soxhlet extraction 3 days with benzene then 79 and shales lary column with methanol extraction ~ Ames test Dickson et al. SP2100 Flash evaporation and Kuderna Danish o 0 79 90-250 C @ 5 /min TLC ,[ Table B-1. Continued. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Robinson and Cook Oil shale, raw IR Crushed, C6H12 soxhlet 24 hrs L/L ultra 71 sonic, flash evaporation (10 torr) TAR problem molecular sieves other work with pentane Robinson and Cook Raw shale Not reported <8 mesh + <100 mesh 24 hr. soxhlet with 73 Wyoming cyclohexane, elution chromatography and molecular sieves +++ t:; Saxby in Shale kerogen Not reported Soxhlet extraction benzene:methanol w Yen 76 Acid/Basic fractionation Chapter 6 TAR and moisture problems Identification C40HSO Schmidt-Collerus Spent shale 50' Corasil SCOT Benzene, 6 day soxhlet extraction 74 100o-300oC Flash evaporation/Kuderna Danish TLC identification/separation Show PAH mobility with polar solvents Thomas and Lorenz Raw shales Not reported Centrifical separation macro character 70 istics C, N. S, Fe, H with/without TAR problem Yen Shale bitumen Not reported Benzene soxhlet extraction, fluorescence, 76 kerogen GC, HPLC, UV macro element characterization kerogen model, geological origin? , much more J Table B-2. Selected investigations of products and wastes derived from shales, tar sand, coal. and high boiling crude oil distillates. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Bunger Tar Sand NMR, MS, IR Review of methods of analysis! Problems 77 Bitumens with flash evaporation macro character ization C, H, N, S inorganics! Callen et al. Oils (related) NMR, IR LC: n-Pentane, benzene, THF 77 Pyridine, macro characterization 0, N, S, C Heteroatom concentrations ..... w +:- Clark et al. Shale oil 3% Dexsil packed Benzene ~ Pyridine extraction 77 COED 400 column Flash evaporation problems LC Florisil, Sync rude Alumina, Sephadex DMSO, Cyclohexane, H 0 2 fractions Fruchter et al. Shale oil 6' 3% SP2100 Isooctane/HCl/NaOH DMSO fractionations 77 solvent refined 1200 -2S00 C Irradiation of samples for standard also coal materials inorganics Greinke and Coal and GC, MS, UV Distillation of petroleum pitch Lewis petroleum 1/8" x 10' SS collected volatiles soxhlet extracted 75 pitch 3% Dexsil 300 with cyclohexane volatiles on Chromo sorb G 3-5 ring PAH content estimated Guerin Crude oils USBM-API Comparison of PAR from energy sources, 77 Coal oils procedure combustion products, conversion products Shale oils and other processing wastes + I, q Table B-Z. Continued. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Ho et al. Shale Oil 1/8" x ZO' Centrifuge separation water/oil/emulsion 79 150 ton 3% Dexsil 400 Acid/Base LL extractions Laramie Retort on 100/1Z0 mesh LC Sephadex LH-ZO, Silicic Acid, Chromosorb 750 Basic Alumina Neutral Aza-arenes suggested Jones et a1. Oils from coal GC/MS 3% Dexsi1 400 LC Sephadex LH-20 elution of PAH with Z t 0 0 77 and shale 70-3Z0 C @ 4 /min THF and Z t ethanol Jones in Shale oil and 6' 1% OV-101 LC Silica Gel Coomes related fuels 100-340o @ 4 °/min Petroleum ether and CH C1 methanol Z 2 78 fractions Pellizzari Energy related 100 m glass SCOT Liquid and solid effluents from oil shale, 0 78 wastes and OV-101 ZO-240 C coal gasification and coal liquefaction o effluents @ 4 /min; 50 m processes, coal fired power plants and oil glass SCOT, others refineries ++1 Rubin et a1. Crude oils Frac tiona t ion L/L Acid/Base extractions 76 from coal for biological LC florisil of neutral fraction testing eluted with hexane, benzene, ether, methanol Schiller and Oils, Tar 1/8" x 10 I ss Mi~ed tar with Z-3 g AIZ03(N) LC Alumina Mathiason Sand and Coal 5% SE-30 on CC13H, tetrahydrafuran/hexane/toluene/ 77 derived Chromo sorb W chloroform THF/ethanol fractions Table B-2. Continued. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Condifions Schweighardt Coal derived Liquid nitrogen saponification and Thomas products N-Pentane/benzene/THF 78 Selucky et al. Bitumen HPLC LC 77 N-Pentane/Benzene molecular sieve (SA) thiourea Sharkey et al. Coal. ashes "high resolution Analysis of PAR in coal. coal ash, fly ash, 76 Shale oils MS" and other fuel and emission samples 0 6 Ferroalloy 300 C 10- torr Uden et al. TOSCO II GC/IR L/L Acid Base extractions 79 Shale Oil 100' x 0.03" substituted pyridines and quinolines Acids and Bases SCOT FFAP and phenols identified on Chromo sorb R " , Table B-3. Selected investigations of air concentrations of PAR. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Cautreels and Aerosol 3 m Soxhlet extraction 4 hrs benzene. 4 hrs Cauwenberghe extracts 4% Dexsil-300 methanol redissolved in ether. washed in o 0 77 120-280 C @ 4 /min water Acid/Base fractions Daisey and Leyko Air filters 3.18 mm x 3.66 m Soxhlet extraction with cyclohexane 79 SS with 6% Dexsil TLC acetylated cellulose; 300 on 80/100 propanol-acetone-water (2:1:1) Chromosorb W (HP) ..... w ...... Rill et al. Air filters 10' x 2 mm glass Soxhlet extraction with methanol re 77 packing coated with dissolved in cyclohexane Carbowax 20 o 100-240 @ 4 /min Lee and Novotny Air filters 19 m x 0.26 mm Column study 76 glass capillary 180 cm x 0.32 cm od stainless steel column SE-52 3% Dexsil 300 on 80/100 mesh Chromosorb W Natusch and Air filters 1/4" od x 6 t glass Dimethyl sulfoxide soxhlet extraction Tomkins 1.5-3% SP2100 n-pentane, n-heptane isooctane, n-hexane 78 80/100 mesh + fractions others Pierce and Ka tz Aerosols Not reported Benzene soxhlet extraction TLC pre 75 separation polycyclic Quinones identified I I J Table B-3. Continued. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Pitts et· a1. Air filters TLC solvent toluene: 78 CH Cl :Methanol 25:1:1 2 2 Silica gel plates deadsorption in methanol + Ames test t-' W 00 1. II IJ Table B-4. Continued. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions KWan et al. Shale retort IR, UV, GC L/L extractions with ether for 2 weeks 77 water RPLC Acid/Neutral/Basic fractions May et al. Water with XAD-2 resin Study of PAR water solubilities 78 PAR stan extraction Naphthalene ~ Chrysene dards Spath Ohio River GC 1/811 X 6' SS Background study and results of chlorina 72 water 10% silicone tion of PAIls Naphthalene - Pyrene grease on Gas Chrom Q Stepan and Water with 2 mm x 3.5 m XAD-2 and 7 extraction efficiency study Smith knowns glass column variable flowrate, pH, temperature 77 3% SE-30 Webb Water with XAD resins Comparison of isolation methods for ~ C 6 75 knowns urethane foam alkanes and 1 to 4 ring PAIl solvent extrac tion , I j Table B-4. Selected investigations concerning PAH water concentrations. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Acheson et al. Synthetic and TLC GLC Ultra-Turrax resin ~ CH2Cl2 76 river water extraction efficiency study variables suspended solids, initial con centration Adams et al. Water with Chromo sorb 101 Comparison of sorbent resins properties 77 knowns and 102 and efficiencies for C6 - C13 alkanes and XAD 2 and 4 1 to 4 ring PAH Tenex - GC and Poropak Chriswell et al. Water with GC 3 mID x 1.S m Study of XAD-2 and carbon adsorption 77 known PAH SS column packed recovery of trace organics from water with 5% OV-l on 100/120 mesh Chromo sorb WAW 75-2500 C @ SO/min Dunlap et al. Groundwater XAD-2 resin Sampling and extraction study of ground 77 extraction waters EPA Industrial L/L extraction Sampling and analysis procedures for 77 wastewater CH Cl H/HO screening of industrial for priority 2 2 pollutants Junk et al. Water XAD-2 resin Study of removal of trace organics from 74 extraction water J Table B-S. Selected investigations of PAH content in other environmental samples. Identification Methods Samples Source and/or GC Columns Procedure Keywords and Other Comments Analyzed and Conditions Brown et al. Marine sediments 30 m x 0.2S mm Benzene/methanol soxhlet extractions; LC 7S Glass capillary on silica gel SE-S4 WCOT col. Farrington Near offshore Glass capillary "EPA mussel watch" pyrene and chrysene 7S sediments identified Giger and Blumer Sediments UV, MS, GC Soxhlet extractions methanol and benzene 74 LC-Sephadex LH-20, Silica gel, Alumina removal of H20, S; UV estimation of PAH contents through coronene John and Nickless Sediments 4 mm x 3' with 5% Na2S04 water removal, soxhlet extraction 77 Dexsil 300 on 60/S0 CH2Cl2 LC x 2 then TLC mesh Chromo sorb W Lao et al. Sludges, tar, 0.12S" X 12' SS Cyclohexane soxhlet extraction 24 hrs; 75 soot. air packed with 6% or separatory funnel 24 hrs CH Cl 2 Dexsil 300, 400, or 2 410 on SO/100 mesh Chromo sorb W HP Lee and Hi te.s Carbon black 11 m x 0.26 rom Soxhlet extraction CH Cl for IS hrs 2 2 76 Glass capillary SE-S2 14 Pancirov et al. Wastewater l/S" x 10' 2% SE-30 C as a standard CH2Cl2 soxhlet extraction 7S refinery on Chromo sorb G LC on alumina elutions isooctane to DMSO sediments He 40 ml/min 175-3000 @ 4°/min Appendix C Characterization of Selected Polzczclic Aromatic Hzdrocarbons Table C-l. Characterization of selected polycyclic aromatic hydrocarbons. Formula Boiling Solubility and Formula and and Carcinogenicit.y Name and Molecular Structure Melting Physical Mutagenic! ty Weight Point Description ------Benzothiophene H S 221 w 1 +(H) CS 6 a1 v l34.20 QJ 22 rst 5 biphenyl C H 255 w 1 l2 IO a1 5 154.21 eth 5 0-0 b. v 4.4-dimethy1- C14H15N3 w 1 Carcinogen (T) aminoazobentene Q-N=N-Q al v 225.30 117 eth 5 J (CH 3 zN indene H C9 S 116.16 QJ indole CaH7N N 117.15 CD~ I H naphthalene CloHa 218 w i Inactive (CC). a1 5 ° (C) 128.17 , ..6 81 eth v co ace v bz v OH naphthol C H O w Carcinogen (T) 10 i a a1 s 144.17 168 eth 5 cD~ fi 142 Table C-l. Continued. Formula Boiling Solubility Carcinogenicity and Formula and and Name Molecular Struc ture Melting Physical and Mutagenicity Weight Point Description naphthylamine ClOH9N 306 w s Carcinogen (T) al s 143.19 113 eth s 05~ ~ phenyl ether C H O 12 10 170.21 0-0-0 quinoline H N C9 7 129.16 co~ NA: thiophthene C6H4S 2 140.23 LDS acenaphthene C H 12 10 295 w i al <1 154.21 116 bz & rst 00o 0 sol ilc~naphthylene C H 1 1Z 8 265 w al ';/ 152.20 92 eth ';/ 00~ ~ bz v acridine C13HgN 345 bz ';/ nd 179.22 ~N h III ceo (sub) anthracene C H I4 1O 340 w i (sub) r.91: 0" 178.24 (XX)h A ~ H I carbazole Cl2H9N 355 -(C); OM 167.21 o:DI h 248 143 Table C-l. Continued. Formula Boiling Solubill ty Care! nogenic i ty and Formula and and Name and Molecular Structure: Melting Physical MutageniC' i ty Weight Point Description C H C? (T) 9,10-dimethyl- 16 14 anthracene 206.29 c¢o::::::,.. ::::::,.. CH, fluorene C li 299 w i -(C); OM 13 lO al cr 166.24 116 bz & rat 0c0 5 0 9,10-anthra- C H 0 14 S 2 II quinone 208.23 OJ) II 0 2-amino fluorene C H N 13 ll 0::0/NH2 lSI. 24 I I .d dibenzothiophene 4-azafluorene H N C12 9 167.21 coo::::::,.. N""':: phenanthrene C H i Disputed (CC), 14 lO 340 w rst: S Carcinogen (T) 178.24 , ::::-... 101 - (C), OM, ? (H) 09~I ~ 144 Table C-l. Continued. Formula Boiling Solubility Carcinogenicity and Formula and and and ~arne Molecular Structure Mel ting Physical Mutagenicity Weight Point Description poenanthridine C13 H9N 349 w cr al v 179.22 106 eth v ace s cB~I : bz 5 C H +(M) fluoranthene 16 lO 202.26 05):1 Ih azabenz(a) Carcinogen (T) anthracene s +(C) benz(e) acenaphthylene Il-H benzo(a) Slight (CC); carbazole +(C) 1.2- benz<> carbazole 3,4-dihydro 163 145 Table C-l. Continued. Formula Boiling Solubility Carcinogt2nici ty and Formula and and ~ame and Molecular Struc ture Melting Physical Xutagcnicity Weight Point Dt;;!scription 1-H benzo(c)- C!6"llN carbazole 217.27 , ~ ~ I N I .b ooc9I H 1-" benzo C H N Slight (ee) 1S lO Z [g] y carboline N~ I I ~ 218.26 N .b ce8I H ocnzo(def)- C H 5 14 8 ~ dio'=!:nzo- , thiophene 208.28 m~I .b benzo(a) - d ibl"nzo thiophene 4-1{ cyclo pe(]ta(defl pJa..:tlllnthrene 15-H cyc!openta(a)- C H 17 12 phenanthrene 216.29 146 Table C-l. Continued. Formula BOiling SOlubility Carcinogt2nic i ty and Formula and and Name and Molecular Structure Melting Physical Mutag8nicity Weight Point Description fluoranthene C H w i 16 lO 375 a1 s 202.26 111 bz s '1 o pa org ~ ~ h nd. or pL 0:8H I phenanthro- C H NS Slight (CC) 15 lO (2.1-d)- thiazole 236.32 roc~, ~ s ~I b thianthrene benz(c) -(C) acridine 7-H benz(d.e) Carcinogen (T) aotllr;.H:cn-7-one benzo (a)- C H 1S 12 435 bz s +(H) anthracene w 1 +(OHC) 228.30 162 rst s (sub) ye br plates 147 Table C-l. Continued. Formula BOiling Solubility Ca rcinQgenic ity and Formula and and nnd ~ame Molecular Structure Melting PhYSical Mutagt:'nicity Weight Point Description benzo(c)- w i Moderate (cel Cl8Hl2 phenanthrene al a +(OHL) 228.30 68 chrysene 448 w i Dispu ted (ee) rst 0 +(OHC) 225 7,12_dimethyl_ +M benz(a) anthracene n;lphthacene Inactive (eel pyrene e H 393 w i Inactive (eel l6 l0 1Yh a1 s -(+) (OHc)-H 202.26 156 eth s (sub) pa yeI I b b 69 p1 triphenylene C H 425 w Inactive (eel l8 l2 a1 s 228.30 199 bz v needles 148 Table C-l. Continued. Formula Boiling Solubili ty Carcinogenic 1 ty and Formula and and and ~ame Molecular Structure Melting Physical Mu tagenic i ty Weigh~ Point Description methyl- C H N 16 ll azapyrene 217.27 2-aminopyrene +M azabenzo Slight (ee) (a) pyrene benzo (c) Moderate (ee) chrysene Weak +(C) b~nzo(b) Inactive (ec); chry~ene -(e) benzo(g) Modera te (CC); chrysene +(C) 149 Table C-l. Continued. Formula Boiling Solubility Carcinog~nic i ty and Formula and and Name and Molecular Structure Melting Physical Mutag~nici ty Weight Point Description benzo{a)- w i +++(H) . C20HI2 pyreoe +++(OHC) ; 252.32 176.6 +(C); +M benzo(e)_ +(H) ; pyrene ;;eak +(C) (+)(OHC); +M d1benz(a,b) acridine dibcnz (a, j) Slight (GG) acridine _(ft); -(el dibenz(a, h) Slight (GC) dibenz(a,c) bz s Disput"d (eel ;1nthracene +(OHG); wc~k 205 +(C); +M 150 Table C-l. Continued. Formula Boiling Solubility Carcinogenic i ty and Formula and and Name and Molecular Struc cure Melting Physica 1 Mutagenicity Weight Point Description ------~------dlbenz(a,h) w i Carcinogen anthracene a1 a (M & B) 269 ace s ++(OHC); bz s +(C); +M dibenz(c, h) Slight (CC); acridine t(OHC); +(C) dibenz(a, i) w i Moderate (CC) ; anthracene a1 0 weak +(C) 269 ace: s bz s dih~nz(b.g) Inactive (eel; phenanthrene -(e) dibenz{c, g) Inactive (eel; phenanthrene -?(e) pentaphene w i Inactive (ee); a1 a -(C) 257 eth oJ bz s 151 Table C-l. Continued. Formula BOiling Solubility Ca rcinogenic i ty and Formula and and ~ame and Molecular Structure Melting Physical Mutagenicity Weight Point Description perylene C H ",375 w i -(H); +II 20 12 aft" 252.32 278 itha bz s sold br yel pl picene C H 519 w i Inactive (CC) 22 l4 al (1 278.36 368 bz (1 bi. Ur pentacene Inactive (eC) benz(j) aceanthryiene b~nzo (0- 511gh t (Ce) CI9H II NS benzo (2, 3)- thieno- 285.37 quinol ine benzo(h)" Slight (CC) Cl9H II NS b,>nzo(2,3) tltl~no(),2-b) 285. 37 qui.noline 152 Table C-l. Continued. Formula BOiling Solubili ty Carcinogenh: i ty and Formula and and Name and Molecular Structure Melting Physical Mutagt:nicity Weight Point Description benzo (b)- w i CZOEl12 +r(EI) ; fluoranthene bz a +r(OHC) 252.32 168 benzo(ghi) -(C) fluoranthene benzo (k)- -(H); f 1 uoranthene weak +(C) benzo (1) Carcinogen (T); fluoranthene +(C) 7-H benzo(a) Slight (Ce) pyrido-[J, Z-gJ carbazole LJ-H benzo (a) Moderate (eC) pyrido-[3,2-i] carbazole 268.32 153 Table C-l. Continued. Formula Boiling SolubiE ty Carcinogenici ty and Formula and and Name and Molecular Structure Melting Physical MutagBnicity Weight Point DescrIption 7-H benzo(e) Moderate (ee) pyrido-[Z,3-g] carbazole 7-H benzo(e) Slight (eG) l'yrido-[3,2-g] carbazole 7-H benze (g) Moderate (eG) pyrido-[2, 3-a] carbazole 7-H benzo(g) High (GG); pyrido-[3,2-aJ +(C) ..'arbazole eye lopenta (cd) pyrene 13-H dibenzo(a,O Slight (eG) carbazole 154 Table C-l. Continued. Formula BOiling Solubility Carcinogenicity and Formula and and ~ame and Molecular Structure Mel ting Physical Mutagenicity Weight Point Description 7-H dibenzo(c,g)- CZOH13N High (CC); carbazole 210 w i +(C) 267.33 @O.2 (sub) al s 175 bz s pa yl fluoreno- Slight (eCl w i C C(H&B) 180 5-oxo- 5 H High (CCl benzo(e) isochromeno (4, 3-b) indole 5-oxo-5 R C!9R!!OZli Slight (eCl benzo(gl- i50C' hromeno 285.30 (4, 3-b) indole 8-oxo-8 H CI8HLON202 Slight (CC) isochromeno (3' ,4' ;4,5l- 286.29 155 .... ~ Table C-l. Continued. Formula Boiling Solubility Carcinogenic! ty and Formula and and Name and Molecular Struc ture Helting Physical Mutagenicity Weight Point Description 6.12 dimethyl Carcinogen benzo(b) (ee); +(e) thionaphtheno-- (2,3-0- thionaphthene 6, 12-dimethyl Care inogen benzo(b) (CC); +(C) thionaphtheno- (3.2-0- thionaphthene pyrido (2, 3-a) Slight (CC) thieno(2,3-1) carbazole benzo(j) +l-(H) ;+l-(OHC) fluor,anthene lndeno +(H) l,2 t 3-cd pyrene anthanthrene [nat eive (ee); -(e) 156 Table C-l. Continued. Formula Boiling Solubility Carcinogenicity and Formula and and i4ame and Molecular Structure Melting Physical Mutagenicity Weight Point Description anthra( I, 2-a)- e H Inactive (ee) 26 l6 anthracene 328.42 benzo(b) Inactive (ee) pentaphene dibenzo(a,i) High (ee); pyrene ++(OHe) ; +(e) benzo(ghi) Moderate (CC); perylene -(+) (OHC) dibenz(a,j) Inac tive (CC) nllphth~lcene 157 Table C-l. Continued. Formula Boiling Solubility Care i nogenic i ty and Formula and and ~ame and Molecular Structure Melting Physical Hu tagenici ty Weight Point Description dibenzo (de,qr) Inactive (ee) napllthacene dibenzo(fg,op) Inactive (ee) naphthacene 4, ll-diaza Moderate (ee) benzo(b,def) chrysene l,11 diaza Moderate (eCl berrzo (rstl pentnphene dibenzo(a, h) High (eC); pyrene ++(OHC) ; +(el 158 Table C-l. Continued. Formula Boiling Solubility Carci nogenici ty and Formula and and Name and Molecular Structure Melting Physical Mutagenici ty Weight Point Description C H Inac tive (eC) dibenzo (b. k)- 26 16 chrysene 328.42 dibenzo (def,p) High (ee) chrysene dibenzo(a,e) High (ee) pyrene naphtho (2, 3-a) Moderate (ee) pyre>n~ naphtho(!,2-b) Inactive (ee) triphenylene 159 Table C-l. Continued. Formula Soiling Solubility Carcinogenic j ty and Formula and and Name and Molecular Structure Melting Physical Mutagenicity Weight Point Description tricyc 10 Moderate (ee) quinazoline coronene 525 w i bz " 440 yel nd Key to Appendix C Boiling and melting points (degrees centigrade), solubility and physical description from Handbook of Chemistry and Physic" 57th edition (lieast, R.C. ed., 1976-1977). ae - acetone e - ether pa - pale - soluble a1 - alcohol fir fluoresct!nt pi plates sl or I.J - slightly bz - bt:!nzt!ne i - insoluble rst rest of the five sub - sublim.:1.tes br - brown nd - net2'dles solvents not io- ye - yellow dividually specif ied v very T or TRII = TRII (1976) H Harrison et al. (1975) C and/or CC = Chemical Carcinogens (Searle, 1976) M & B = Morrison and Boyd (1973) + Care inogen (+) Co-carcinogen - or 0 inac tive M mutagt;n OHC Origins of Human Cancer (Hiatt et aI., 1977) 160