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INDEX A Acid digestion bomb 483 oil shale analysis 484-85/ Activation parameters for oil formation 324/ Age, Queensland tertiary oil shales 116 Aldehydes, as geochemical markers 30 Aleksinac oil shale acids 42,43/ aliphatic lactones 47 H-alkanes, composition 38, 39/ aromatic hydrocarbons 42 bitumen composition 38/ constituents, physiological activity 52, 56 cyclic alkanes, composition 40 cyclic 7-lactones 49 fatty acid methyl esters 47 geolipids 37-58 isoprenoid alkanes 40/ ketones 49 triterpane fraction 41 Aleksinac, Yugoslavia, oil shale—See also Aleksinac oil shale 37-58 Algonquin Arch 145 n-Alkane distribution 5, If H-Alkanes, composition, Aleksinac oil shale 38, 39/ Alkylnaphthalenes, mass spectra 80 Ankerite decomposition 517-22 Anthony-Howard's equation 284-87 Antrim shale, upper 147 Apatite, biogenic 90 Aromatic aliphatic index 78 Aromatic aliphatic ratio, kerogens 134 Aromaticity, role in pyrolysis 311 Arsenic, bioaccumulation 423 Artificial evolution of kerogen 9 Ash, low-temperature, mineral concentrations 499 Ash determination, Parr oxygen bombs 482/ Ashing of oil shales 480 Australia deposit information 274/ deposit summary 271 Australian oil shales analysis 487/ chemical and retorting properties 317-34 gas evolution profiles 331, 333 weight loss characteristics 281/
B Bighorn basin, hydrocarbons Biogenic apatite Biological markers—See Biomarkers Biomarkers cross-correlation coefficients
219 90
451
Biomarkers—Continued definition 433 in Green River shale oil 433-56 presence 440 source material and effects 440 Bitumen composition, Aleksinac oil shale 38/ Bitumens in Brazilian oil shales 22-24 Black oil shales, in Kentucky 159-61 Black shale, lower 149 Black shale sequence 149 Boundaries, in geochemistry 13-14 Brazil deposit information 274/ deposit summary 271 Brazilian Irati Formation, organites 16 Brazilian oil shales 13-36 ash content variation 389/ bitumens 22-24 elemental composition 20-22 information system 33 kerogens 24 molecular composition 22 occurrence 17-20, 18/ pristane/phytane index 28 reserves 19/ weight loss characteristics 281/ Brazilian Vale do Paraiba oil shale 20 Brown oil shale, Condor deposit 109 Bulk mineralogy, and elemental composition 497 Byfield deposit, mineral composition of oil shale seams 110/
C Calcite 90 decomposition 551 in formation of silicates 515 thermogravimetry 536 Calcite decomposition 517-22 reversible 523-25 Calcite rate parameters, comparison 523/ Calcium carbonate effects on combustion 91 Calorific value, Israeli oil shales 91 Ca-bon determination 488-90 Carbon hydrogen, analysis 386 Carbon preference index 27 Carbonates decomposition 540, 551 removal 540 Carboniferous oil shales 70 Char, reaction rate 548 Char combustion, effect on mineral species 543-56 Characterization, analytical techniques 477-92 Charge-assisted vibrational displacement mechanism 33
559 Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
GEOCHEMISTRY AND CHEMISTRY OF OIL SHALES
560
Chen-Nuttall equation 283 kinetic parameters 289/ China deposit information 274/ deposit summary 271 Chinese oil shales, weight loss characteristics 281/ Claisse fluxer analysis, shale analysis 482/ Claisse fusion device, procedure 479 Clay minerals 90 in shales 1 Cleveland shale, mineral carbon content 164 Coal, comparison of elemental concentrations 424/ Coal evolution, inadequacy of pyrolysis 9, 10/ Coalified wood, C-NMR spectra, from Upper Devonian black shale \90f Coats-Redfern equation 284 kinetic parameters 289/ Coldwater shale 152 Colony sink float, mineralogy 392/ Colorado oil shales analysis of inorganic constituents 481 / ashing effects on element determination ... 486/ bulk multielement analysis 497/ elemental analyses of kerogen 399/ mineral reactions comparison 513-28 weight loss characteristics 281/ Combustion, calcium carbonate effects 91 Combustion rate 551 effects of water soluble minerals 553 Comparative organic geochemistry of European oil shales 59-84 Condor deposit brown oil shale 109 mineral composition of oil shale seams 110/ Condor shale activation parameters for oil formation ... 324/ properties 319/ Cracking 338 Crude oil, shale oil differences 11 Crustal subsidence 147 Cyclic alkanes, composition, Aleksinac oil shale 40 Cyclic 7-lactones, Aleksinac oil shale 49 ,3
Devonian oil shales— Continued mineralogic composition 172/ in northwestern Michigan 147, 148/ stratigraphic interpretations 145-55 thickness ; 154 Devonian period, sedimentary rock accumulation 154 Diabase intrusion in the I rati Formation ... 28-30 Diphenylethylenediamine 22 Dolomite 242 decomposition 551 Green River formation 235 thermogravimetry 536 Duaringa mineral composition of oil shale seams 110/ mineralogy 106-12 Duaringa Basin, deposit geology 104 Duaringa condor deposit, oxide content 108/ Duaringa shale activation parameters for oil formation ... 324/ properties 319/
E
Eastern Kentucky oil shales 159-80 economic zones 164 Fischer assay relationships 168-71 hydrogen content 167 location 160/" molybdenum concentration 175/ nickel concentration 175/ nitrogen content 167 organic elemental analysis 166/ sulfur content 167 vanadium concentration 175/ zinc concentration 175/* Eastern oil shales, Fischer assay yields 169 Eastern paleoshoreline, kerogen 183 Eastern vs. western oil shales, Fischer assay yields 171/ E f e oil shale, trace elements 95/ Efe phosphorite, trace elements 95/ Ellsworth shale 149 Eocene Green River formation 229 Epimerization 32/* of optically active centers 31 Epimers ration index, in materia prima 28 D European oil shales chromatographic analyses of extractable Decarbonation reactions, metamorphic bitumens 68/ petrology 473 comparative organic geochemistry 59-84 Depositional environment, Queensland tertiary extractable bitumens 66/ oil shales 116 Fischer assay 71/ Devonian, upper, black shales 181-98 geochemical analysis 65-69 coalified wood, C-NMR spectra 190/ location 61/ elemental compositions 187 organic carbon 66/ kerogen aromaticity 196 reflectance and fluorescence data 63/ location 187/ mean aromaticity for kerogen 191, 193/ Extractable metal-organic complexes from Julia Creek shale 413/ mean losses on ignition 187/ 390/ natural gas 182 Extracted kerogen vs. sinkfloatvalues NMR data 189-96 total carbon contents 187/ F Van Krevelen diagram 188/ Ferric chloride-clay chromatography 458-59 Devonian-Mississippian black shales 139 Ferric chloride-clay complexation Devonian oil shales method 457-66 distribution and regional correlation 139-58 l3
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
561
INDEX Ferric chloride-clay complexation method—Continued nitrogen content of fossil oils 462/ separation ability 462/ separation scheme 461 Findlay Arch 145 Fingerprint pyrograms, of torbanite 76f Fingerprints, of kerogens 75 Foerstia 145, 146/ Fossil deposits, trace metalloids, molecular forms 424-25 Fossil fuels, removal of nitrogen-containing components 457-66 Fossil oils, fractionation, metal chlorides-clay chromatography 463/ Fourier-transform IR spectroscopy 502 Functional markers method 24, 25/
H 'H NMR solid-echo signal 'H NMR theimal scan data, analysis Halogen determination, by ion chromatography Hannibal/Saverton shales Heat influences Hillsborough Basin deposit geology mineralogy Hopanoic acids Huron shale, mineral carbon content Hydrochloric acid Hydrogen determination Hydrogen index Hydrogen loss of kerogen "Hyphenated" analytical techniques
355/ 364 488/ 149 28-30 103-4 106-12 42 164 502 488-90 9 9 425
G Geochemical purposes of oil shales 14/ Geochemistry, definition 14 Gosuite lake 226 Green River dolomite 235 Green River formation Eocene 229 extraction 426 illite concentration 235 inorganic geochemistry of Mahogany zone oil shale 249-68 Mahogany zone 228/ 256-65 element composition 234/ elemental analysis 253/, 254/ oxide composition 234/ Green River lakes 226 Green River oil shales analysis 306/ average pristene content 446 biomarkers 433 56 bulk mineralogy 498/ carbonate separation 531, 532/ characteristics 225-38 creation 225-48 elemental analysis 2/ high-pressure pyrolysis 335-52 'H-NMR spectroscopic analysis 506/ IR aliphatic bands 3/ location 226, 227/ Mahogany zone 498/ particle size distribution 509-10 mineral suite 235 molar balances from pyrolysis 308/ NMR analysis of oils 307/ oil generation procedure 436-38 oil yield histograms 231/ organic-mineral matter interactions ... 493-512 pyrolysis effects, indigenous mineral matter 529-42 mineral matrix effects 538/ products 6/ 307/ silicate mineral content 243 silicate separation 531, 532/" trace elements 95/ treated multielemental analysis 500/ thermogravimetry results 538
Igneous petrology interpretation of spent shales 473-74 oxygen fugacity 469 Illite concentration, Green River formation 235 Illite-producing reaction 242 Immature rocks, definition 28 Indigenous mineral matter, effects of Green River oil shale pyrolysis 529-42 Inorganic arsenic compounds, from Green River formation 423-32 Ion chromatography, nonmetals determination 487-88 IR aliphatic bands, kerogens 4/ IR band assignments 504/ IR spectra, aliphatic bands of kerogens 3 Irati Formation diabase intrusion 28-30 functionalization 26 inorganic matrix 22 location 17 sulfur content 21 use of thermal alteration index 27 Isoprenoid acids 42 Isoprenoid alkanes, Aleksinac oil shale 40/ Israel deposit information 274/ deposit summary 271 Israeli oil shales 85-96 calorific value 91 components 85 current reserves 85 differential thermal analysis 92/ Ghareb formation 87/ kerogen 90 IR spectra 93-95, 94/ location 86/" major elements and mineralogy 88-91 weight loss characteristics 281/ J Jet fuels, H-alkane content Julia Creek shale extractable metal-organic complexes 'H NMR thermal scanning data
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
371 413/ 365, 368
GEOCHEMISTRY AND
562 Julia Creek shale—Continued petroporphyrins absorption spectra
CHEMISTRY OF OIL SHALES
M 411-22 416/*
Mahogany bed 250 Mahogany oil shale—See Green River formation, Mahogany zone K Mahogany zone 250 Kankakee Arch 145 element composition 234/ Kerogen-carbonate/ silicate interfacial oxide composition 234/ layer 501 Marau Formation, reserves 19 Kerogen cross-links 402 Marcellus formation Kerogen decomposition, pyrite effects 530 middle Devonian 120 Kerogen extraction, solvent polarity thermal maturation 130/ effects 320/ total organic carbon 124 Kerogens Martin Eale, patent 59 aliphatic bands of IR spectra 3 Mass transfer coefficient 548 aromatic to aliphatic ratio 134 Materia actuale 15 artificial evolution and hydrogen loss 9 Materia prima, epimers ratio index 28 in Brazilian oil shales 24 Mature rocks, definition 28 classification 132 Meade Peak formation comparison of elemental isopachs 207/ concentrations 424/ organic-carbon deposition 208, 209/ composition 407 thickness 206 decomposition rate 278 Meade Peak member definition 1 lanthanum distribution 215/ depolymerized toluene solubles, field phosphorite deposits 211 ionization mass spectra 406/ silver distribution 2\0f IR aliphatic bands 4f vanadium distribution 214/ isolation 69 Meade Peak phosphatic shale member, Israeli oil shales 90 location 199 phenolic acid depolymerization, Melilite 474 products 401/ Meromictic lakes 238 pyrolysis/gas chromatography 5, 7/ Messel shales, IR aliphatic bands 3/ Queensland tertiary oil shales 114/ Metal chlorides-clay chromatography, reduction 398 fractionation by fossil oils 463/ reductive alkylation 400,402 Metamorphic petrology thermal history 126, 128/ decarbonation reactions 473 toluene solubles, spectra 405/ interpretation of spent shales 471,473 type I 3, 132 oxygen fugacity 469 type II 3, 132 Methylarsonic acids, gas chromatography/ mass type III 132 spectrometry 426 Ketones, Aleksinac oil shale 49 Middle Devonian Marcellus formation 120 Kettle Point formation Mineral catalysis 549-55 location 119 Mineral-matter dissolution 495 thermal maturation 130/ Mineral reaction rates 514 total organic carbon 124 Mineral reactions, comparison for Colorado Kjeldahl procedure 489 oil shales 513-28 Kukersite 398 Mineral species, effect of char IR aliphatic bands 3/ combustion 543-56 Mineralogical phases 90 L Mineralogy, bulk, and elemental 7-Lactones 47 composition 497 cyclic, Aleksinac oil shale 49 Molecular hydrogen Lacustrine, ion chromatogram 82/ effect on carbonate minerals 312 Lake Uinta role in pyrolysis 312 calcite formation 245 Morocco chemical history 238-46 deposit information 274/ depositional models 250 deposit summary 271 saline mineral suite 245 Moroccan oil shales, weight loss stratification 240/ characteristics 281/ Leachate water, elemental analysis 553/ N Lexington Dome 159 Lower black shale 149 Nagoorin shale activation parameters for oil formation ... 324/ Lower Toarcian shales, Paris Basin, elemental properties 319/ analysis 2/ Narrows Graben Low-temperature ash, mineral mineralogy 106-12 concentrations 499
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
563
INDEX
Petroleum, comparison of elemental Narrows Graben—Continued concentrations 424/ seam classification 107/ Narrows Graben deposit, composite 102/ Petrology the science 467 Nitrogen components, isolation 459 of spent shale 467-76 Nitrogen determination 488-90, 490/ of spent shales, possible models 469,471 classical method 489 Nonmarine/ marine species, fingerprint 81/ Petroporphyrins demetallation 421 Nonmetals determination, ion derivation 411 chromatography 487-88 from Julia Creek shale, absorption Normative mineral calculation, definition 468 spectra 416/ O shale from Julia Creek 411-22 Ohio shale, stratigraphic trends of carbon 167 Phenol acid depolymerization, western U.S. oil shale kerogen 397-410 Oil coking 338 29 Oil evolution, high pressure effects 348 Phenol index Phenol-p-toluene sulfonic acid Oil shales depolymerization 399-400 comparison of elemental concentrations... 424/ 402-7 definition, economic 1 Phenol-tosyl acid depolymerization geochemical purposes \4f Phenylarsonic acids, gas chromatography/mass spectrometry 426 geochemistry 1-11 Oil yield, pressure effects 350 Phosphoria formation deposition 204,206 Ontario black shales intertonguing 204 geology 120-22 paleogeographic setting 200-204 Paleozoic 119-38 petroleum generation 216-21 Ontario shales, Van Krevelen diagram 133/ Sublett basin 201/ Optically active centers, epimerization 31 200 Organic fractions, mass balance 6/ Phosphorites in eastern Idaho 212 Organic geochemistry, comparative, of European location 216 oil shales 59-84 in northeastern Utah 212 Organic-mineral matter interactions, in Green Permian Phosphoria formation River oil shale 493-512 oil shales 211-12 Organites 15 Phylloerythrin fractions, fast atom Brazilian Irati Formation 16 bombardment spectra 417,420/ Brazilian reserves 17/ Phytane 38 Organoarsenic, from Green River 421 formation 423-32 Porphyrin fractions, demetallation Preashing 486 Organoarsonic acids, biogeochemical 38 origin 430 Pristane Pristane/phytane index Oxygen fugacity 471 Brazilian oil shales 28 P data 73 Processing, mineral reaction rates 514 Paleoshoreline, eastern, kerogen 183 Pyrite 22 Paleozoic black shales of Ontario 119-38 effect on kerogen decomposition 530 Parachute Creek member, oil shales 244f thermogravimetry 536 Paraho shale oil, distillation 372 Pyrite determination 491/ Paraho vacuum distillate, C NMR 529 spectra 375/ Pyrobitumen Pyrolysates 134 Paraho vacuum distillate fractions, n-alkane Pyrolysis yields 383/ apparatus 337/ 437/ Paris Basin, Lower Toarcian shales, elemental effects 5 analysis 2f in hydrogen atmosphere, molecular Paris Basin shale, pyrolysis products 6/ mechanism 301-16 Park City formation, deposition 206 kerogen aromaticity 302 Parr acid digestion bomb, dissolution kerogen decomposition 282 of shales 483 kinetic expressions 282-83 Parr oxygen bombs 478-79 mechanistic scheme 304/ for ash determination 481,482/ multiple heating rate data 293-96 Pennsylvanian Tensleep Sandstone 219, 22Qf in nitrogen atmosphere, molecular Permian Phosphoria formation oil mechanism 301-16 shales 199-224 of oil shales 1-11 phosphorite 211-12 oil yield at near-atmospheric pressure 338 thicknesses 206-8 porosity reduction 336 Permian rocks reaction rate constants 296 intertonguing relations 205/ of shale oil crude 371-85 nomenclature 205/ ,3
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
GEOCHEMISTRY AND CHEMISTRY OF OIL SHALES
564
Sink float colony, mineralogy 392/ fraction collection 386 predetermined specific gravity 386, 387/ 288, 293 procedures 385-96 vs. extracted kerogen values 390/ 288 weight percent determination 388 288 22, 23/ 282 Solid phase extraction method Solvent polarity effects, kerogen 371-85 extraction 320/ 5, If 269-300 Spent shales chemical data 470/ petrology 467-76 353-70 possible models 469, 471 474 Sporinite 70 Steranes 40 Q destruction 348 Queensland oil shales, location 98/ Stuart deposit, oxide content 108/ Queensland tertiary lamosites 106 Stuart shale Queensland tertiary oil shales 97-118 activation parameters for oil formation ... 324/ age 116 mineral composition of oil shale seams 110/ atomic ratios 114/ properties 319/ Byfield oil shale—See Byfield oil shale Sublett basin 202 deposit geology 100-106 of Phosphoria formation 201/ depositional environment 116 Sulfur content, Irati formation 21 Duaringa Basin—See Duaringa Basin Sulfur determination, by ion elemental analyses 114/ chromatography 488/ Hillsborough Basin—See Hillsborough Basin Sunbury shale 152 kerogen content 113/ carbon-hydrogen contents 168 kerogens 112, 114/ mineral carbon content 164 location of basins 99/ stratigraphic trends of carbon 167 Narrows Graben deposit geology, See Sweden Narrows Graben deposit deposit information 274/ shale oils 114/ deposit summary 272 Van Krevelen diagram 113/ Swedish oil shales, weight loss characteristics 281/ R
Pyrolysis—Continued single heating rate data Anthony-Howard vs. Coats-Redfern equations Coats-Redfern vs. Chen-Nuttall equations one-region vs. two-region treatments two-step mechanism of vacuum distillates Pyrolysis/gas chromatography, kerogens Pyrolysis kinetics Pyrolysis studies, by 'H NMR thermal scanning Pyroxenes, desilication
Reaction rate constants 296 Recarbonation 523 surface phenomenon 525 Residence time, determination 348 Resource assessment, criteria 141 Retort member 221 lanthanum distribution 215/ silver distribution 210/ vanadium distribution 215/ Retort phosphatic shale member, location 199 Retorted oil shale—See Spent shale Retorting—See Pyrolysis Reversible calcite decomposition 523-25 Rock-Eval pyrolysis of Toarcian shales 4f Rundle shale, ash content variation 389/
S Self-purging reactor, oil yield decrease Senile rocks, definition Shale analysis, Claisse fluxer analysis Shale oils n-alkane distribution crude oil differences removal of nitrogen-containing components vacuum distillates, C NMR Siderite Silicates, formation from calcite l3
343 28 482/ 7/ 11 457-66 376/ 109 515
T 2,6,10,14-Tetramethy lhexadecane 38 2,6,10,14-Tetramethy lpentadecane 38 Theoretical organic geochemistry 30-33 Thermal alteration index 27 Thermal influences 28-30 Thermal maturation indicators 130/ Thermogravimetric analysis for kinetic data analysis 546 of untreated shales 533-38 Thermogravimetry, calcite 536 Three Lick Bed 161 of Ohio shale, stratigraphic trends of carbon 167 Toarcian shales IR aliphatic bands 3/ Rock-Eval pyrolysis 4f Torbanite fingerprint pyrograms 76f IR aliphatic bands 3/ Trace element geochemistry, economic implications 176 Trace metalloids, in fossil deposits, molecular forms 424-25 Treated Green River oil shale, thermogravimetry results 538 Tremembe formation, functionalization 26
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
565
INDEX Triterpanes identification destruction Type I kerogens Type II kerogens Type III kerogens
41 348 3, 132 3, 132 132
Van Krevelen diagram Ontario shales Upper Devonian black shales
U Uinta basin oil shales, weight loss characteristics Uinta Lake calcite formation chemical history depositional models saline mineral suite stratification United States deposit information deposit summary Untreated shales, thermogravimetric analysis Upper Antrim shale Upper Devonian black shales coalified wood, C-NMR spectra elemental compositions kerogen aromaticity location mean aromaticity for kerogen mean losses on ignition natural gas NMR data total carbon contents Van Krevelen diagram l3
Upper Jurassic Kimmeridge clays, Blackstone band Upper Ordovician Whitby formation
281/ 226 245 238-46 250 245 240/" 274/ 272 533-38 147 181-98 190/ 187 196 187/ 191, 193/ 198/ 182 189-96 187/ 188/
70 122
133/ 188/
W Weight percent determination by sink float 388 Western U.S. oil shale kerogen phenol acid depolymerization 397-410 reduction 397-410 Western vs. eastern oil shales, Fischer assay yields 171/ Whitby formation Fischer assay 124 thermal maturation 130/ total organic carbon analyses 123 upper Ordovician 122 Whitby kerogen pyrolysates, gas chromatograms 135/
Y Yugoslavia deposit information deposit summary Yugoslavian oil shales, weight loss characteristics
Miknis and McKay; Geochemistry and Chemistry of Oil Shales ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
274/ 272 281/
