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Home , Chemical ionization

STP1019-EB/Apr. 1989

Subject Index

A

Alkylbenzene Benzene, chemical -proton chemical ionization-proton exchange exchange analysis, 40-43 analysis, 42, 44-45 Biomarker analysis, chromatography/ Kendrick analysis, 188-189 , 3 metastable spectra, 107-108 Biomarkers, 59-60 n-Alkylbenzenes Buddingtonite, pyrolysis of, 141- GC/MS analysis, 108-109 142 Arabian Heavy asphaltenes, 108- 109 C n-Alkylbenzothiophenes, 4, 108, 115 GC/MS analysis ~oC combinations, Kendrick masses, 182, background, 94-95 185-186 hydrocarbon and sulfur carbon types, CH34S combinations, Kendrick masses, 95, 97-103 182, 185-186 magnified view, 101, 104 Chemical ionization (CI) (see also pyrolysis GC/MS and, 95 chemical ionization; homologs, singlek doublet, and Isobutane chemical ionization) multiplet, 105, 108 coal-derived , 145 mass spectra, major isomers, 112- metalloporphyrins, 84-92 115 reagent gas pressure, 138 metastable spectra, 107-108 role in SFC-MS, 21 molecular and fragment ions, 108, SFC-MS interfaces and flow restrictors, 111 9 Alkylindans, chemical ionization-proton sterane analysis, mass spectrometry, 49 exchange analysis, 42, 44-45 Chemical ionization-proton exchange Alkyltetralins, chemical ionization-proton (CIPE), 3 exchange analysis, 42, 44-45 jet fuel analysis, 38-45 Ammonia, oil shale pyrolysis, 133- peak identification, 45 142 CHY software program, ! 85, 188 Ammonia chemical ionization Coal-derived liquids geoporphyrin analysis, 92 chemical ionization-proton exchange metalloporphyrins, 3, 84-85 analysis, 40-43 mass spectra, 86 low-voltage mass spectrometry, 144-153 porphyrin mass spectrometry, 88-92 SFC-MS analyses, 10-21 Arabian heavy asphaltenes Coal extracts n-akylbenzenes, 108-109 LVHRMS-direct insertion probe, 116- n-aklylbenzothiophenes, 95-115 125 Aromatics, hydrotreatment effect, 156- molten-caustic treatment, 117 157 preparation, ! 17 ASTM Test Methods raw versus molten-caustic-treated, D 2425-83, 25 126-131 D 2786-86, 25, 33-37, 164-166, 168 Coal tar, SFC-MS analyses, 7-8, 10-11 Autoscaling, multivariate analysis, Collisionally activated dissociation (CAD) 148 metalloporphyrins, 85

197 Copyright9 by ASTM International www.astm.org 198 FOSSILFUEL MASS SPECTROMETRY

Computer programming (see Hardware; GC/MS fossil fuel analysis Software programs) evaluation and reliability, 170 Contamination, tandem mass experimental systems, 162-163 spectrometry, 56, 58 future research, 170-171 Crude oil, sterane traces in, 47-58 hydrocarbon carbon number assignment, 165 D main principles of, 163-170 molecular ion search, 165-166 Deuterium exchange, chemical ionization- need for, 160-162 proton exchange analysis, 40- n-paraffin identification, 163-165 43 quantitation and sorting, 167-170 Diesel fuel structure assignment, 166-167 SFE-MS analysis, 10-21 type analysis, 164 CI mass spectra, 10, 13 human expert comparisons, 170-171 Dipyrrole fragments, pyrrole formation, schematic, 161 89-92 Direct fluid injection (DFI) mass spectrometry, 10, 12-15 SFC-MS interfaces and flow restrictors, Factor analysis 9 Factor I spectra, 152, 156 Direct-insertion-probe technique, Factor II spectra, 152, 156 LVHRMS hydrotreatment data, 148, 151-153 Bevier coal extracts, 123-125 Factor spectrum coal-derived materials, 116-125 hydrotreatment data, 148, 152-155 Direct-probe inlet mass spectrometry, 16- time/temperature trends, 153, 155 17 (FAB), 1 DS-55 software system, 119-120 Field ionization (FI), coal-derived liquids, 145 Flame ionization detection CIPE analysis and, 38 ECNCI and, 27 sterane analysis, 49 chromatography, 5-6 methane-enhanced, 50-5 l Fourier transform infrared Electron impact spectra (FTIR), 134 CIPE analysis and, 39 daughter spectra, 62, 64 G full-scan, 62-63 (EI) Gas chromatography (GC) geoporphyrin analysis, 92 apparatus, 3-m DuraBond system, 26 metalloporphyrin, 3, 84-92 component discrimination, 27-31 mass spectra, 86 flame ionization detection, 27 porphyrin mass spectrometry, 87- fossil fuel analysis, 159-171 88 mass spectrometry (GC/MS) (see Gas SFC-MS interfaces and flow restrictors, chromatography/mass 9 spectrometry) sterane analysis, sample introduction methods, 27-28 daughter mass spectra, 51-52 sterane analysis, 48-49 mass spectra, 49 Gas chromatography/mass spectrometry Electron ionization mass spectrometry (GC/MS) (EIMS), 134 n-alkylbenzothiophenes/n-alkylbenzenes, Expert systems, 159-171 95-115 comparisons with other analytical apparatus used, 26-27 methods, 171 ASTM comparisons, 33-37 future research trends, 170-171 biomarkers, 60 INDEX 199

CIPE analysis and, 39 coal-derived liquids, 145 comparisons with MS/MS, 2 IF-THEN-Else rules, 162 computer hardware and software, 27 Indans, chemical ionization-proton expert systems, 160-162 exchange analysis, 40-43 fuel variations, 34-37 Injection techniques HTA sample introduction methods, 27- area ratio accuracies, 31 31 gas chromatography, 28-31 hydrocarbon analysis, 3 Integrated Two-Stage Liquefaction (ITSL) injection port temperature versus area coal-derived liquids, 144-146 ratios, 27-30 schematic, 145-146 ion summation chromatograms, 27- Ion current instability, direct-insertion- 28 probe techniques, 120-121 jet fuel analysis, 24-37 Ionization techniques, 1-3 limits of detection, 31, 33-34 Isobutane chemical ionization short column and simulated distillation, ammonia determination, 137-138 25-27 ammonia from oil shale pyrolysis, 133- software programs for, 159-171 142 splitless versus on-column injection, 30- ammonia volume versus concentration, 31 149 sterane analysis, 52-53 isobutane fragment monitoring, 138- Geoporphyrins 140 defined, 84-85 quadruple analyzer transmission, EI and ammonia CI analysis, 90 138 reagent gas pressure, 138 H secondary (SEM) gain, 138 Hardware (computer), Hewlett Packard- Interface Buss (HPIB), 135 J Heuristics, expert systems, 161-162 HFR interface, SFC-MS analysis, 15 Jet fuel analysis High Resolution Mass Spectral analysis, CIPE method, 38-45 Kendric masses and, 172-193 coal-derived, 40-43 Hydroaromatics, hydrotreatment effect, GS/MS hydrocarbon-type analysis, 24- 156-157 37 Hydrocarbon carbon number assignment, 165-166 K homologs, coal extracts, 119-120 LVHRM-direct-insertion-probe Kendrick masses, 4 techniques, 124 ~2C mass, 174-175 Hydrocarbon-type analysis (HTA), 3 defect, 175 fuel variations, 34-37 factor, 175 jet fuels, GS/MS, 24-37 high-resolution mass spectrometry and, sample introduction methods, 27- 172-193 28 root mean square errors, 189 versus ASTM test methods, 33-37 Knowledge engineering, 162 Hydronium ion, ammonia determination, 140 L Hydrotreatment effect, 4 average mass spectra, 148-150 Laser desorption, 1-2 coal-derived liquids, 144-153 chromatography/mass sample identification, 145-146 spectrometry (LC/MS), Hydroxy-polynuclear aromatic 145 hydrocarbons, 20-21 LISP language, 162 200 FOSSILFUEL MASS SPECTROMETRY

Low-voltage high-resolution mass Molten-caustic-treated coal extracts, spectrometry (LVHRMS), 4 LVHRM-direct-insertion-probe direct-insertion-probe technique techniques formula class distributions, 123 Bevier coal extracts,. 123-124 summary of compound types, 122- mole percent determinations, 126-131 123 Monoaromatics, hydrocarbon carbon Low-voltage, high-resolution mass numbers, 165-166 spectrometry Monooxygenated compounds, LVHRM- direct-insertion probe and coal-derived direct-insertion-probe techniques, materials, 116-125 124 Low-voltage mass spectrometry MS/MS (see ) coal-derived liquids, 144-153 Multiple reaction monitoring multivariate analysis and, 4 crude oil extracts used, 60-61, 65 schematic diagram, 147 sterane responses, 65, 67-70 triterpenes, 65, 75-78 M Multivariate analysis, standardization, 148

MAP, n-alkylbenzenes analysis, 95, 97-103 N Marine diesel fuel, SFC-MS analysis, 10, 12 -containing polycyclic aromatic Mass spectrometry (MS) (see also Tandem hydrocarbon (NPAC) mass spectrometry (MS/MS)) LVHRM-direct-insertion-probe n-alkylbenzothiophenes and n- techniques, 124-125 alkylbenzenes, 95-115 mass spectra from, 16, 18-19, 21 apparatus, MAT TSQ45, 26 SFC-MS analysis, 16-17 chemical ionization-proton exchange Nominal mass Z series (NMZ) and, 38-45 first array combinations, 182, 184 coal-derived liquids, 145 rectangular array concept, 174-182 gas chromatography (see Gas unassigned peaks, 175, 180-183 chromatography/mass N-paraffins, expert system identification, spectrometry (GC/MS)) 163-165 jet fuel analysis, 24-37 low-voltage high-resolution (see Low- O voltage high-resolution mass spectrometry (LVHRMS)) Octaethylporphyrin, EI and ammonia CI metalloporphyrins, 84-85 analysis, 86-92 overview, 1 Oil-oil correlation, multiple reaction software programs for, 159-171 monitoring, 65-83 sterane analysis, normal MS, 49-51 Oil shale (see Shale oil) supercritical fluid chromatography (see On-column injection, gas chromatography, Supercritical fluid 30-31 chromatography/mass One-ring aromatic neutrals, Kendric mass spectrometry (SFC/MS)) rectangular array, 175-182 Medium-resolution SIR, 62, 65 On-line mass spectrometry, ammonia Metalloporphyrins from oil shale pyrolysis, 133-142 chemical ionization, 84-92 Organosulfur compounds (see Sulfur) electron ionization, 84-92 Metastable ions, multiple reaction P monitoring, 60-64 Methane chemical ionization, PCI, sterane analysis metalloporphyrins, 84-85 daughter mass spectra, 52-53 Methylene, repeating unit concept, 173 MS/MS, 49 Microbore SFC-MS, 15-21 Petroleum analysis, high-resolution mass hydroxy-PAC fractions, 20-21 spectrometry and, 172-193 Molecular ions, 165-166 desorption ionization, 2 INDEX 201

Polar modifiers, supercritical fluid Shale oil, chromatography and, 7-9 pyrolysis, 4, 133-134 Polynuclear aromatic hydrocarbons sterane traces in, 47-58 (PNAs) Short column GC/MS, 25-27 hydrotreatment effect, 156-157 SIGMA software system, 148, 151 MS/MS analysis, 2 Simulated distillation, GC/MS, 25-27 Pressure programming, SFC-MS analysis, Software for fuel analysis 15-16 CHY program, 185, 188 PROB software program, 185, 188 DS-55 system, 119-120 Programming for fuel analysis (see HP 3497A thermocouple conditioning Software programs) and digitizing system, 135 Prophyrins, SFC-MS analyses, 10-21 HRMS data analysis, 182, 185 Pyridine dialyzate, direct-insertion-probe IBM CAPMC4 Chromatography techniques, 121-123 Applications Program, 27 Pyrolysis mass spectrometry data with, 4 Buddingtonite, 141-142 PROB program, 185, 188 GC/MS READTAP program, 182, 185 n-alkylbenzothiophenes, 95 RETROFIT program, 118-120 Arabian Heavy asphaltenes, 105-106 SIGMA system, 148 metastable spectra, 107-108 SPECTR program, 182, 185 sulfur in, 105 XFER program, 182, 185 oil shale, 4, 133-134 probe analysis Pyrrole formation, mono and tripyrrolic confirmation, 56-57 fragments, 89-92 sterane analysis, 49 tandem mass spectrometry, 53-57 Q Sorting carbon numbers and isomers, 169- Quadruple analyzer transmission, 170 isobutane chemical ionization, hydrocarbon mixtures, 167-170 138 isomer summing, 169 Quantitation, hydrocarbon mixtures, 167- Specific Z series (SPZ), 174-182 170 one-ring aromatic neutrals, 175-181, 193 R SPECTR software program, 182, 185 Splitless injection techniques, 29-31 READTAP software program, 182, 185 SS retort, ammonia determination, 135- Reconstructed ion current (RIC) 136 hydrocarbon-type analysis, 31, Stability index (SI) 33-34, 167-168 defined, 85 Rectangular array doubly charged ions in EI, 88-89 ion formulas, 172-193 electron ionization and, 3-4 second array combinations, 189-192 fragmentation under Ammonia CI, 88- Retort, ammonia determination 89 SS retort, 135-136 metalloporphyrin reactivity, 85 steam retort, 140-142 pyrrole formation, 89-92 RETROFIT software program, 118-120 Steam retort, ammonia determination, 140-142 Steranes biomarkers, 59-60 Secondary electron multiplier (SEM) gain, carbon number distribution, 58 138 marine oil, 65, 67-70 Secondary ion mass spectrometry (SIMS), molecular formulas and standard 1 weights, 48 Selected' ion recording (SIR), 60-62, 65 multiple reaction monitoring Separation techniques, overview, 1-2 peak identifications, 65-66 202 FOSSILFUEL MASS SPECTROMETRY

tandem mass spectrometry T abundance measurements, 55- 56 Tandem mass spectrometry (MS/MS) crude and shale oils, 47- contamination and chemical interface, 58 56, 58 parent spectra, 53-55 metalloporphyrins, 85 terrestrial oil, 67, 71-74 overview, 2 Structure assignments, hydrocarbon solid probe configuration, 56-57 mixtures, 166-167 sterane analysis Sulfur CAD daughter spectra, 51 n-alkylbenzenes and, 95, 97-103 El-CAD daughter spectra, 51-52 coal extract removal, 119-125 sterane traces, 3, 47-58 LVHRM-direct-insertion-probe Tetralins, chemical ionization-proton techniques, 123-125 exchange analysis, 40-43 Supercritical fluid chromatography (SFC), , 2 203 Trimethylamine, isobutane chemical flame ionization detector, 5-6 ionization, 140 Supercritical fluid chromatography/mass Triple quadrupole mass spectrometry spectrometry (SFC/MS), 3, 5- (TQMS) 21 ammonia determination, 134-135 direct fluid injection (DFI) and, 10- nitric oxide, 136-137 15 Tri-sector geometry, multiple reaction experimental procedure, 6-7 monitoring, 61-62 fossil fuel analysis, 10-1 l Triterpene hydroxy-containing polynuclear biomarkers, 59-60 aromatic compounds~20- marine oil, 65, 76-78 21 multiple reaction monitoring, 65, 67 interfaces and flow restrictors, 9 terrestrial oil, 79-83 microbore techniques, 15-2 l nitrogen-containing polycyclic aromatic U hydrocarbon (NPAC), 16- 19 Ultraviolet absorption detection, 5-6 polar fluid and column development, 7- 9 V polar sediments from marine diesel fuels, 10, 13 Variance Diagram Technique, pressure programming, 15-16 hydrotreatment data, 152-154 split injection techniques, 15 Supercritical fluid extraction (SFE) X fossil fuels, 10, 13-15 mass spectrometry and, 6-7 XFER software program, 182, 185