'U A U.S. Environmental Protection Agency Industrial Environmental Research ii •» Office of Research and Development Laboratory Research Triangle Park, North Carolina 27711 EPA-600/7-77-149 December 1977 ORGANIC EMISSIONS FROM AUTOMOBILE INTERIORS Interagency Energy-Environment Research and Development Program Report z z z 7 ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into seven series. These seven broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The seven series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy—Environment Research and Development This report has been assigned to the INTERAGENCY ENERGY—ENVIRONMENT RESEARCH AND DEVELOPMENT series. Reports in this series result from the effort funded under the 17—ageucy Federal Energy/Environment Research and Development Program. These studies relate to EPA’s mission to protect the public health and welfare from adverse effects of pollutants associated with energy systems. The goal of the Program is to assure the rapid development of domestic energy supplies in an environmentally——compatible manner by providing the necessary environmental data and control technology. Investigations include analyses of the transport of energy—related pollutants and their health and ecological effects; assessments of, and development of, control technologies for energy systems; and integrated assessments of a wide range of energy—related environmental issues. REVIEW NOTICE This report has been reviewed by the participating Federal Agencies, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Government, nor does mention of trade names or commercial products constitute endorsement or recommen- dation for use. This document is available to the public through the National Technical Information Service, Springfield, Virginia 22161. ------- EPA-600/7-77-1 49 December 1977 ORGANIC EMISSIONS FROM AUTOMOBILE INTERIORS by Ruth A. Zweidinger Research Triangle Institute P.O. Box 12194 Research Triangle Park, N.C. 27709 Contract No. 68-02-1325, Task 46 Program Element No. EHE624A EPA Project Officer: Joseph A. McSorley Industrial Environmental Research Laboratory Office of Energy, Minerals, and Industry Research Triangle Park, N.C. 27711 Prepared for U.S. ENVIRONMENTAL PROTECTION AGENCY Office of Research and Development Washington, D.C. 20460 ------- ABSTRACT This research program was initiated to evaluate the potential for exposure of the general population to organic emissions of automobile In- teriors and specifically to vinyl chloride monomer (VCM). This program was intended as a pilot study to evaluate (a) whether there exists a possible hazard due to VCN or other hazardous organics and (b) the test conditions and relevent parameters for further testing of a statistically significant sample of automobiles should that be undertaken subsequent to this study. Six subcompact automobiles (Ford Pinto, ANC Gremlin, GNC Vega, G 1C Chevette, N 1C Datsun 710 and VW Rabbit) were evaluated in this study for the emission of VCM and other organics into the passenger compartment. The quantitation of VCM was achieved using Lot No. 104 SKC charcoal cartridges interfaced with gas-liquid chromatography-mass spectrometry (GLC/MS) in the single ion mode. The interiors of the automobiles were thermostatically controlled at either 45 or 65°C for 3 hrs before sampling the car interior. Each automobile was sampled for VCN at both temperatures. Levels of VCN in the Ford Pinto, ANC Gremlin, GHC Vega and GMC Chevette were less than the detection limit of 50 ppb. With improved instrumental parameters a limit of detection of 2 ppb was attained. Under these conditions no VCN was detected in the GNC Chevette. VCN was detected in the VW Rabbit at 4±3 ppb when sampled at 65°C and less than 2 ppb at 45°C. The NNC Datsun 710 was found to produce VCN levels of 7±2 ppb and 3±1 ppb at 65° and 45°C, respectively. In accordance with E.P.A. proposed rules as set forth in the Federal Register, Vol. 42, p. 28154, 1977, these low levels must be regarded as unacceptable. 111 ------- Samples for qualitative GLC/HS analysis of each automobile for other organics were taken at 65°C using Tenax GC sorbent. This analysis produced a composited list of 147 organic compounds which were identified in the automobiles but not in the ambient air in the vicinity of the test. Another 36 compounds were tentatively identified. Inclusion in the latter group resulted when the compound was either in very small amounts or there were possible interferences. Of the compounds identified in automobile interiors, aniline, biphenyl, 1,2-dibromoethane (tentative identification), dichlorobenzene (tentative identification), dimethyiphenol isomers (some isomers are carcinogenic), isobutyl alcohol, maleic anhydride (tentative identification), naphthalene and 1,1,1-trichioroethane are listed as having carcinogenic or neoplastic effects according to the Registry of Toxic Effects of Chemical Substances , 1976 Edition. Beuzene, carbon tetrachloride, chloroform and phenol are also listed as carcinogenic or neoplastic; however, they were found in the back- ground as well as in the automobile interiors. Further investigation of these emissions seems warranted based upon these preliminary results; however, it will have to be initiated by that segment of the E.P.A. specifically responsible for automobile emissions. This report was submitted in fulfillment of Contract No. 68-02-1325 by Research Triangle Institute under sponsorship of the U. S. Environmental Protection Agency. This report covers the period Hay 15, 1976 to December 22, 1976, and work was completed as of April 1, 1977. iv ------- CONTENTS Abstract iii Acknowledgments 1. Introduction 1 2. Conclusions 3 3. Recommendations 5 4. Experimental Procedures 7 Sample Design Selection of Test Automobiles . . . . 7 Parameter Evaluation 7 Sampling for Qualitative Analysis . . . . . 9 Quality Control 9 Analytical Methods . . 1Q Vinyl Chloride Monomer 10 Gas Liquid Chromatography/Mass Spectroscopic——Qualitative Analysis of Organics 12 5. Results and Discussion 23 Quantitative Analysis 23 Qualitative Analysis of Organic Emissions 23 References 35 Appendix A 37 Sampling Port 38 Temperature Controls 38 Appendix B 43 Gas Liquid Chromatography—Mass Spectrometry Analysis of Organics in Automobile Interiors Appendix C 75 V ------- P IGURES Number Page 1 Mass spectrum of a chromatographic peak identified as vinyl chloride monomer from an environmental sample 11 2 Gas chromatography/mass spectrometric analysis — single ion mode (m/e = 62) of: (a) Air from the interior of a Datsun 710 automobile at 65°C (0.5 £ sample), (b) 50 ng standard of VCM 13 3 Calibration curve for vinyl chloride monomer 14 4 Thermal desorption inlet manifold 16 5 Thermal desorption chamber 17 6 Instrumental outlay of the gas chromatography/mass spectrometry/ computer system 18 A-i Side window on driver’s side 39 A—2 Automobile interior temperature control 40 B—i Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Vega (8/26/76) automobile 44 B—2 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Datsun (10/10/76) automobile 50 B-3 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Chevette (10/10/76) automobile 53 B—4 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Chevette (8/25/76) automobile 56 B—5 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Pinto (8/28/76) automobile 58 B—6 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Gremlin (8/26/76) automobile 65 vi ------- FIGURES (con.) Number B—7 Total ion current plot during gas liquid chromatography/mass spectrometry of air sample from the interior of a Rabbit (10/9/76) 3—8 Total ion current plot during gas liquid chromatography/mass spectrometry of a background air sample 1 8 2 20 3 24 4 25 B—i 47 B—2 51 B—3 54 B—4 57 B—5 61 B—6 66 3—7 70 B—8 73 76 Page 69 72 TABLES Measurement Matrix Operation Parameters for GLC—MS—COMP System Vinyl Chloride Monomer Found in Test Vehicles Organics Found in Automobile Interiors . . Organic Compounds Identif led from Figure B—i Organic Compounds Identified from Figure B—2 Organic Compounds Identif led from Figure B—3 Organic Compounds Identified from Figure B—4 Organic Compounds Identified from Figure B—5 Organic Compounds Identified from Figure B—6 Organic Compounds Identified from Figure B—7 Organic Compounds Identified from Figure 3—8 C—i Frequency—Prioritized List of Organics Found in Automobile Interiors vii ------- ACKNOWLEDGMENTS The valuable assistance of Hr. R. B. Keefe in executing the laboratory and sampling experimentation is gratefully appreciated. ?ls. D. Smith, N. Pardow and Dr. J. T. Bursey provided the interpretation of mass spectra and the analysis by high resolution gas-liquid chromatography/mass spectrometry/- computer in this research project; a sincere thanks for their support. The helpful suggestions of Dr. E. D. Pellizzari throughout the project are appreciated. The assistance of Dr. T. Hartwell with the statistical design of the experiment is gratefully acknowledged. The encouragement and support of Project Officer, J. A. HcSorley, of IERL-RTP is deeply appreciated. viii ------- SECTION 1 INTRODUCTION The possibility of toxic or carcinogenic organic compounds being volatilized into the interior of automobiles as a result of the extensive use of plastics has aroused concern. A number of toxic compounds have been postulated as arising from the pyrolysis of various plastics at 65°C, and these have been examined. However, even qualitative information on the identity of these compounds actually occurring in the automobile interiors is incomplete. Vinyl chloride monomer (VCN) would be expected to be a likely offender due to the abundance of polyvinyl chloride (PVC) in automobile interiors. Since VCN is a suspected carcino- gen in man 6 ’ a very careful assessment of its presence and amount in automobile interiors should be made using “worst case” conditions. The “worst case” would provide an upper limit on the exposure to the public, and an appropriately designed experiment should permit estimation of levels under less extreme conditions. The inclusion of qualitative information on other compounds in this study avoids omission of other hazardous compounds. Parameters which are likely to be relevant to the selection of “worst case” conditions are newness of the automobile, plastic-content- to-volume ratio, and temperature. The age of a test automobile is expected to affect the amount of residual VCN in the PVC components. Temperature and ventilation history may have a very substantial influence on the residual VCM; however, these parameters were not controllable for the period between the automobile’s manufacture and initiation of the study. If extremes of temperature history are available that information would certainly be useful, but not essential. Subcompact cars potentially represent the “worst case” for plastic-content-to-volume-of-interior 1 ------- ratio and consequently should accumulate the highest concentrations over a given interval. The last parameter for the “worst case” criteria is temperature. The volatilization of VCM would be expected to be diffusion controlled since it is a gas at normal ambient temperatures (boiling point: —13°C). The temperature dependence of the diffusion rate will depend upon the properties of the particular polymer. Numerous different formulations and applications of PVC from foams to solid sheets are found in automobile interiors; therefore, only actual measurement of the resulting VCN levels as a function of temperature and time will yield meaningful information. The experimental design used in this study was selected to maximize the information content for a manageable number of samples. The identi- fication of other organics emitted into the automobile passenger compart- ment was designed to probe the potential exposure to hazardous organic compounds. In this case, only qualitative information at the highest selected temperature was sought. 2 ------- SECTION 2 CONCLUSIONS Six subcompact automobiles (Ford Pinto, ANC Gremlin, GNC Vega, GMC Chevette, NNC Datsun 710 and VW Rabbit) were evaluated in this study for the emission of vinyl chloride monomer (VCM) and other organics into the passenger compartment. The quantitation of VCH was obtained using Lot 104 SKC charcoal cartridges interfaced with gas-liquid chromatography- mass spectometry (GLC/NS) in the single ion mode. The interiors of the automobiles were thermostatically controlled at either 45 or 65°C for 3 hrs before sampling the car interior. Each automobile was sampled for VCH at both temperatures. Levels of VCN in the Ford Pinto, MC Gremlin, GNC Vega and GMC Chevette were less than the detection limit of 50 ppb. With improved instrumental parameters a limit of detection of 2 ppb was obtained. Under these conditions no VCN was detected in the GMC Chevette. Vinyl chloride monomer was detected in the VW Rabbit at 4±3 ppb (± 3 refers to standard deviation of duplicate samples) when sampled at 65°C and less than 2 ppb at 45°C. The NNC Datsun 710 was found to produce VCN levels of 7±2 ppb and 3±1 ppb at 65° and 45°C, respectively. Since the analysis of VCN in the interiors of Ford Pinto, ANC Gremlin and GHC Vega was not repeated with the lower limit of detection, no comparison of their VCN levels with the other three automobiles can be made. In accordance with EPA proposed rules as set forth in the Federal Register, 8 these low levels must be regarded as unacceptable. An array of times as well as temperatures was originally proposed to indicate aging effects and one automobile in the study, the Chevette, was sampled at 1 month and 3 months of age. The VCN levels were below the limit of detection at both sampling times. Although the limit of 3 ------- detection changed between the two times, no inference may be drawn from the results except that the levels were below the limits of detection of 50 and 2 ppb at 1 and 3 months respectively. It should be pointed out that 50 ppb is regarded as the usual limit of detection of VCM analyses and that the levels found in the Rabbit and Datsun 710 would not normally have been detected. The selection of new compact automobiles sampled at elevated tempera- tures was based on the assumption that this would represent the “worst case” for accumulation of VCN in the passenger compartment. The results of this study probably represent an upper range for VCN exposure due to the use of polyvinyl chloride in automobile manufacture. Samples for qualitative GLC/NS analysis of each automobile for other organics were taken at 65°C using Tenax GC sorbent. This analysis produced a composited list of 147 organic compounds which were identified in the automobiles but not in the ambient air in the vicinity of the test. Another 36 compounds were tentatively identified. Inclusion in the latter group resulted when the compound was either in very small amounts or there were possible interferences. Of the compounds identified in automobile interiors, aniline, biphenyl, 1,2-dibromoethane (tentative identification), dichlorobenzene (tentative identification), dimethyl- phenol isomers (some isomers are carcinogenic), isobutyl alcohol, maleic anhydride (tentative identification), naphthalene and 1,l,l-trichloro- ethane are listed as having carcinogenic or neoplastic activity; however, they were found in the background as well as in the automobile interiors. 4 ------- SECTION 3 RECOMNENDATIONS Since the Environmental Protection Agency has set the goal of zero emission for vinyl chloride tnonomer 8 the low levels found in this study must be regarded as unacceptable. Further study of a larger, more statisti- cally significant sample is recommended before any action is taken. Several other compounds were found in the course of this study which (9) are listed as having carcinogenic or neoplastic effects. Further quanti- tative evaluation of these compounds should be included in any vinyl chloride evaluation which might be undertaken. ------- 6 ------- SECTION 4 EXPERIMENTAL PROCEDURE S SAMPLE DESIGN Selection of Test Automobiles Subcompact model cars, potentially represent the worst case of all models where the extent of plastic utilization to interior volumes is concerned. For this reason the subcompact was used for all tests. The selection of the manufacturers of the test automobiles is a more complex problem. The number of cars to be evaluated was limited to six; however, the number of manufacturers of subcompact cars substantially exceeds this number. Initially a random selection was proposed with the probability of selecting each manufacturer weighed according to their percentage of the total subcompact sales. This selection would represent a random sample of the subcompact car industry as a whole; however, the practical matter of obtaining automobiles suitable for this study narrowed the range of selection to those automobiles which represent the greatest portion of subcompact sales (i.e., Ford Pinto, ANC Gremlin, GFIC Vega, GMC Chevette, NNC Datsun 710 and VW Rabbit). Parameter Evaluation The evaluation of the VCM hazard requires knowledge of its concen- tration in the interior of a representative sample of automobiles. There are several parameters which would obviously affect the buildup of VCM. The most prominent among these are the temperature of the automobile interior and its age. The sampling matrix originally proposed for this study evaluated these parameters. The plan called for automobiles to be selected whose ages were known to be between 30 and 90 days. This selection would have insured that in a 60-day experiment the age dependence data for all of the cars would overlap. If for some reason the necessary make, model and age requirements were not met, the age requirement would be altered in one of I ------- the two following ways without substantial loss of information: (1) sample over a 90-day period selecting cars 30 to 120 days old, or (2) sample over a 60-day period selecting cars 60 to 120 days old. Assuming the sample contaied cars 30 to 90 days old, the sampling would be performed at 30-day intervals to obtain three time points for each automobile. Although the age criterion was broader than planned for cars in the study (30-120 days), the sample still represented a group of fairly new automobiles. The second controlled parameter, temperature, was to have been evaluated at three levels, 25°C, 45°C and 68°C. These were selected as representative of normal ambient (77°F), high ambient (113°F) and an extremely high, but possible temperature (154°F). A matrix of the temperature and age levels was selected which would evaluate both parameters while minimizing the number of analyses. The matrix of measurements which was originally planned is shown in Table 1. Table 1 MEASUREMENT MATRIX ys a t t+30days t+60days 25 45 68 X X X X X X a = age of car at beginning of study. 8 ------- Using this array, six automobiles may be evaluated for two para- meters at three levels each with only 36 analyses. Of course, because all three levels of temperature and age are not evaluated for each car, this implies that some information is lost on the interactions between these parameters. In the actual experiment the sampling array was truncated after the first period due to the very low to nondetectable amounts of VCM found. The maximum temperature which could be satisfactorily maintained was 65°C; therefore, this temperature was substituted for 68°C in Table 1. The detailed test procedure is in Appendix A. SAMPLING FOR QUALITATIVE ANALYSIS A detailed description of the sampling procedure is included in Appendix A. Samples from each automobile were collected at an interior tempera- ture of 65°C using Tenax GC cartridges (2.2 g sorbent each). Blanks of the purge gas were to be taken to pinpoint the car interior as the source and to access the background due to transportation and handling. Since the purge proved to be an impractical and uncertain method of lowering and/or establishing the background, the ambient air adjacent to the study site (outside of the Gremlin in a calm area) was sampled. The analysis was qualitative in nature; hence, background compounds were recognized on a present or absent basis. This qualitative basis does not permit the recognition of enrichment of compounds in the auto interior. The ambient air sample was typical for a nonindustrial urban area and was used as baseline for the entire study. QUALITY CONTROL The value of any analytical procedure is substantially influenced by the control data accumulated in the sampling and analysis process. This factor becomes more important as lower concentrations or more ubiquitous compounds are sought. Blanks (unsampled cartridges in the case of charcoal, ambient air in the case of Tenax) were prepared for each group of samples collected and subjected to the same rigors of transportation and storage as the samples. 9 ------- In order to control both the effects of recent ventilation and ambient levels of organic pollutants, it was proposed that the automobiles be purged with clean air (charcoal filtered) before each experiment. This purge would facilitate the evaluation of the GLC/MS analysis of the organic vapors arising from the plastic materials by removing the normal ambient air hydro- carbons. The purge proved to be impractical in several respects. First, because the volume which needed to be exchanged was large, a long cycle time would be required to dilute the interior compartment with “clean” air. Second, infiltration of air into the passenger compartment was significant and continued throughout the test. The cars were to be sealed after the purge for a set equilibration period determined in a one-car pilot experiment, perhaps 8-18 hours. In actual tests, the 65°C temperature could be maintained for only 4 to 5 hours during the hottest portion of the day; therefore, this period was used whether equilibrium was obtained or not. This approach provided no control over artifacts from ambient air, except that provided by control blanks. More significantly, no control could be obtained with an assembled automobile which would correct for the contamination of the interior by fuel vapors and auto exhaust. ANALYTI CAL METHODS Vinyl Chloride Monomer The quantitative analysis of VCM was accomplished using cartridge desorption interfaced to a capillary gas chromatograph/mass spectrometer. This system had been used with success previously in the single ion monitor mode for the quantitation of N-nitrosodimethylamine in complex mixtures. The same technique is applicable to the analysis of VCM. Two important factors are very favorable for the VCM analysis: chromatographic separation and a unique ion (Figure 1). Limits of detection with this method were controlled primarily by the sample volume collected on the cartridge. Originally Tenax GC was proposed as the collection medium. However, for good quantitation, the sample volume with the standard 2.2 g Tenax GC cartridge should not exceed 0.5 2. This does not leave a large margin for such factors as the effects of temperature on breakthrough volume. In view of this, another sorbent, activated charcoal (Lot 104 Charcoal S.K.C., Philadelphia, 10 ------- I I I I I I I I I II I III I III 1 II II III I I 111111 111111 I till II 11111 liii l iii tIll till iiitt titi ii 111111 liii titti tilt 11111111 11111111 iii i ti i iuti 6, 2 64 C H 2 = C H Cl ir,i m inn till i I I ‘ I I I I 4 1 1 I I 11111 I I I I I I I I i 10 20 30 40 ) 60 70 lIP 50 I lIP I U 2111 e i1li lIII,Ils1;i,II;,II ;lIlI llI rl2Is!1it I;I IIII1 Iltti:ilIl;itIl’I;I il :;ii:i, I I I I I I I I I I I I I I I I I I I I I 80 90 I 110 120 130 140 I 150 100 Figure 1. Nass spectrum of a chromatographic peak identified as vinyl chloride monomer from an environmental sample. 11 ------- Pa.), was used. A cartridge, 6 mm o.d. x 10.5 cm length, was filled with 150 mg of charcoal. The breakthrough volume of this cartridge is “3 2 at 25°C; hence, samples of 0.2 or 0.5 2 were well below the breakthrough volume or approximately 3 times that of Tenax. In the first group of analyses (7/28/76 to 8/2/76), the charcoal cartridges were desorbed directly in the capillary GLC/NS system. Although this procedure worked satisfactorily, as far as the production of useful data, the large amount of water accumulated on the charcoal caused excessive instrument deterioration. To avoid this problem, a method for removing the water was devised for the second group of samples. In this technique the charcoal cartridges were thermally desorbed and the sample passed through a 2 cm bed of calcium chloride to remove the water. The vinyl chloride was collected on a Tenax GC cartridge (2.2 g). The Tenax GC cartridge was then thermally desorbed into the GLC/MS system in the usual manner. The recovery from the charcoal to Tenax GC transfer was found to be 95%. All calibration standards in this phase were carried through the transfer procedure. Sample chromatograms of a standard and a sample from the Datsun 710 at 65°C are shown in Figure 2. The calibration curve for the samples analyzed 9/29/76 and 9/30/76 and the control samples are shown in Figure 3. The control samples were obtained by preparing 1.0 ppm and 0.5 ppm dilutions of VCN in a Tedlar bag, placing them in an oven at 65°C and sampling 0.2 2 using charcoal cartridges. These samples were transferred to Tenax GC cartridges and analyzed as described above. Gas-Liquid Chromatography/Nass Spectroscopic--Qualitative Analysis of Organics A system for the collection, concentration and analysis of a broad range of organic compounds at trace levels in ambient air was previously developed and was used in this study without further modification. The method is based upon collection on a Tenax GC cartridge and thermal de- sorption analysis. The thermal desorption technique which is a refinement (10) of Duel s solvent-free sample inlet system has been used at RTI to analyze organics in ambient air (EPA Contract No. 68-02-1228) as well as those in energy—related wastes and effluents (EPA Contract No. 68-03- 12 ------- CoJ iiiin: 91H OV—101 capillary 1enipcr itiire l’rograiii T liii I Ia 1 20°C p rograiiuned at 4°C/rn Iii 2 4 Time (mm.) Figure 2. Gas chromatography/mass spectrometric analysis — single ion mode (m/e = 62) of: (a) Air from the interior of a Datsun 710 auto- mobile at 65°C (0.5 2 sample), (b) 50 ng standard of VCM. >- U) U) c C 0 VCM VC M Chroinatographic coiidlr tons A >. U) C U) C C 0 ------- 150 ioo U ) CO a) C ’) V 50 0 — Average values of standards 0 — Values obtained ircm control experiments 100 200 300 400 0u bOO VCM in sample (ng) Figure 3. Calibration curve for vinyl chloride monomer. 14 ------- 2368). The system is designed so that the entire sample mixture can be introduced onto the GLC column. The inlet manifold (Figure 4) for introducing the sample into the instrumental systems consists of four main components: a desorption chamber (Figures 4 and 5); a six-port, two-position, high-temperature low—volume valve; a nickel capillary trap and a temperature controller. An aluminum sandwich serves as a thermal source. Two heating cartridges are used to heat the aluminum sandwich, and the temperature is monitored and controlled with a platinum sensor probe. The desorbed vapors pass into a six-port, two-position valve which is also encased in an aluminum heating bath. Temperature control is identical to the thermal desorption chamber. The temperature is monitored directly on a pyrometer. Control is ± 1°C. A nickel capillary constitutes one loop of the valve proper which is cooled with liquid nitrogen and serves as a trap for collecting and concentrating desorbed vapors prior to their introduction into the high- resolution GLC column. The vapors are released from the capillary trap by rapidly heating to 175°C. The multiport valve used on the inlet manifold was chosen for its polyimide stem to minimize the contact of desorbed trace vapors with reactive metal surfaces, therefore minimizing contamination and/or decomposition of sample constituents. In a typical thermal desorption cycle, a Tenax GC sampling cartridge containing volatile organics was placed in the preheated (>270°C) chamber, and helium gas was passed through the cartridge (>20 mi/mm) to purge the vapors into the liquid-nitrogen-cooled capillary trap. This condition constitutes the valve position A (Figure 4). After the thermal desorption step was completed, the six-port. valve was rotated to position B (Figure 4): the temperature on the capillary loop rose rapidly, whereupon the carrier gas carried the vapors onto the high resolution capillary column. For the identification of volatile organic compounds, the combined technique of gas-liquid chromatographyJmass spectrometry/computer (GC/ IS/- CONP) was employed. The instrumental outlay is shown in Figure Techniques previously developed by RTI for analysis of hazardous compounds were applied to this research program. 15 ------- COMPRESS1ON SPRING PURGE GAS TEMPERATURE CONTROLLER I— LVE POSITiON A (SAMPLE DESORPTION) SAMPLING ALUMINUM HEATI NO BAT H ALUMINUM HEATING BATH Six-PORT TWO POSITION VALVE — CARRIER GA S PURGE GAS TO GLC VENT GAS — 1 VALVE POSIflON B (SAMPLE INJECTION) TO GLC CAPILLARY HEATING AND COOLING BATH Ni CAPILLARY TRAP TO GLC VENT I I CARRIER I GAS I PURGE I GAS Thermal desorption inlet manifold. L._ ——-- ---i Figure 4. 16 ------- DESORPTION CHAMBER TO VALVE TEFLON INSERT COMPRESSION SPRING 4 PURGE GAS GLASS CARTRIDGE SAMPLER 13.0mm 10.5cm 1 15.0 cm 13.30 cm II O.56 Figure 5. Thermal desorption char:ber. ------- SEPARATOR CYPIIERNETICS TIME SHARED PDP/1O Ei ure 6. Instrumental outlay of the gas chromatography/mass spectrometry/ 00 SAMPLE INLET MAN TFOLD T computer system. ------- The previously described inlet manifold was used for recovering vapors trapped on Tenax GC cartridges, and it was interfaced to the GLC/ 1S/COMP system. The desorbed vapors were subsequently resolved by gas-liquid chroma- tography, and mass cracking patterns were automatically and continuously obtained throughout the GLC run with a Varian CH-7 mass spectrometer. Operating parameters, depicted in Table 2 for the GLC/NSJCONP system are suitable for the volatile organic fraction. Analysis profiles from automobile interiors are included in Appendix B, along with an unabridged list of identified compounds. The high resolution capillary columns are capable of resolving a multitude of compounds to allow their subsequent identification by MS/COMP techniques. The NS was first set to operate in the repetitive scanning mode. In this mode, the magnet is automatically scanned exponentially upward from preset low mass to high mass values. Although the scan range may be varied depending on the particular sample, typical values would be from m/e 28 to m/e 400. The scan is completed in approximately 5 seconds. At this time the instrument automatically resets itself to the low mass position in preparation for the next scan. The information is accumulated by an on-line 620/L computer on magnetic tapes. The reset period is approximately 2 seconds. Thus, a continuous scan cycle of 7 seconds per scan was maintained. Depending on specific sample requirements, this scan cycle can be shortened to as little as 5 seconds per cycle. With the magnet continuously scanning, the sample was injected, and automatic data acquisition was initiated. As each spectrum was acquired by the computer, each peak which exceeded a preset threshold was recognized and reduced by centroid time and peak intensity. This information was stored in the computer core while the scan was in progress. In addition, approximately 30 TIC values and an equal number of Hall probe signals were stored in core as they were acquired. During the 2 second period between scans, this spectral information, along with the spectrum number, was written sequentially on magnetic tape, and the computer was reset for the acquisition of the next spectrum. 19 ------- Table 2. OPERATING PARAMETERS FOR GLC-MS—COMP SYSTEM. Parameter Setting Inlet manifold desorption chamber 270°C valve 180°C capillary trap — minimum —195°C maximum +175°C GLC 200—700 ft SCOT glass capillary 20—30°C, 4/C° mm carrier (He) flow ‘\‘3 mi/mm transfer line to ms 210°C MS scan range m/e 20 - 300 scan rate, automatic—cyclic 1 sec/decade filament current 300 hA multiplier 6.0 6 ion source vacuum ‘\ 4 x 10 torr a 0 101 20 ------- This procedure was continued until the entire GC run was completed. By this time, there were from 300 to 1000 spectra on tape, which were then used for subsequent data processing. Depending on circumstances, either the tapes were then be processed immediately, or additional samples run and the results determined later. The mass spectral data was processed in the following manner. First, the original spectra were scanned, and TIC information extracted. This was done directly from the original tape immediately after data acquisition. Then the TIC intensities were plotted against the spectrum number on the Statos recorder. The information thus gained generally indicated whether or not the run was suitable for further processing, since it gave some idea of the number of unknowns in the sample and the resolution obtained using the particular GLC column conditions. The next stage of the processing involved the conversion of the spectral peak times to peak masses. To accomplish this, the spectra was read successively into the Varian computer core and then sent at high speed to the PDP/8 disc by means of the intercomputer interface. Depen- ding on the number of peaks in each spectrum, the disc capacity allowed the storage of 200-500 spectra. After the spectra containing time information were stored in the disc, the data was returned to the 620/L for mass conversion and re-stored on magnetic tape. The mass conversion was accomplished by use of the calibration table obtained previously. Normally, one set of calibration data was sufficient for an entire day’s processing since the characteristics of the Hall probe are such that the variation was less than 0.2 atomic mass units per day. For very long runs it was necessary to carry out several cycles of mass conversion using the PDP/8 disc to complete the data processing. Time required for the conversion process for 100 spectra was approximately 1 hour. After the spectra were obtained in mass-converted form, processing proceeded manually. In the manual mode, the full spectra of scans from the GC run were recorded on the Statos plotter. The TIC information available at this time was most useful for deciding which spectra to analyze. At the beginning of the run, where peaks were very sharp, nearly every spectrum was inspected individually. Later in the run, when the peaks were broader, only selected scans were analyzed. 21 ------- Resolved components were identified by comparing the mass cracking patterns of the unknown mass spectra to an eight major peak index of mass spectra.(]2) Searches for individual difficult unknowns, using the Cornell University STIRS and PMB systems were unnecessary. Unknowns may also be submitted to the EPA MSSS system for identification; however, this was not required. When feasible, the identifications may be confirmed by comparing the unknown’s cracking pattern and elution tempera- ture on two different columns (OV-l7 and OV-lOl SCOT capillaries) with authentic compounds; e.g. benzothiazole was compared to an authentic sample. Particular note was made of the boiling point of the identified compounds with the elution temperature and the order of elution of constituents in homologous series, since the OV-lOl SCOT capillary separates primarily on the basis of boiling point. 22 ------- SECTION 5 RESULTS AND DISCUSSION QUANTITATIVE ANALYSIS OF VINYL CHlORIDE NONONER Briefly, the test conditions were an initially ventilated compart- ment, closed and thermostatically maintained at either 45°C or 65°C for 3 hours before sampling. The results are shown in Table 3 with pertinent information on the automobiles. The quantitation was performed using charcoal cartridges for the collection of 0.2 or 0.5 £ air samples. The vinyl chloride was recovered by thermal desorption and analyzed by capillary GLC-uiS using single ion detection atm/e 62. This method is sensitive and selective. The instrumental operating parameters for the first test sequence (June 29 - July 2, 1976), which included all the domestic automobiles tested, did not permit the detection of VCM at levels below 50 ppb; however, the General Motors Chevette in this group was included in the second test sequence with the imported automobiles where the limit of detection had been lowered to 2 ppb. Again, VCN was not detected in the Chevette. QUALITATIVE ANALYSIS OF ORGANIC EMISSIONS The summarized list of the organics found in the six test automobile interiors is given in Table 4. The list has been prepared by removing compounds found in the background and collating the compounds found in each car to remove redundancies. The combined list was then organized according to structural characteristics for the convenience of evaluating toxicity. The list of hydrocarbons is long even with the background subtracted and probably represents a significant background due to gasoline evapora- tive emissions. The background sample was taken outside, next to the Gremlin, in a calm area (protected on two sides). 23 ------- Table 3. VINYL CHLORIDE MONOMER FOUND IN TEST VEHICLES. Manufacturer Model Description of Upholstery Temp. (°C) Date of Manufacture Sampled VCHa ppb Ford Pinto tan vinyl 45° 65° 6/76 7/30/76 7/29/76 <50 <50 AIIC Gremlin blue vinyl 45° 65° 4/76 8/20/76 7/30/76 <50 <50 GMC Vega tan vinyl 45° 65° 7/76 8/02/76 7/30/76 <50 <50 GMC Chevette dark blue vinyl 45° 65° 45° 65° 6/76 7/28/ 76 7/28/76 9/29/76 9/29-30/76 <50 <50 < 2 a < 2 a Nissen Motor Corp. Datsun 710 black vinyl 45° 65° 5/76 9/29-30/76 9/30/76 7 + + Volkswagen Rabbit black leatherette 45° 65° 7/76 9/29/76 9/29/76 4 < 2 a,c + 3 a,c aBlanks were all below the limit of detection (2 ppb). bTIte lowest standard which was analyzed was 40 ppb. The estimates here are obtained by extrapolation of the calibration curve. CAverage and standard deviation of duplicate determinations. ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS Compounds Notes Halogenated Compounds 1,2—dibromoethane (tent.) a ehlorobutane (tent.) b chlorocyclohexanol b chiorostyrene (tent.) b hexachioroethane (tent.) b chloroethylbenzene (tent.) b dichlorobenzene isomer c trichlorobenzene isomer d O gen Containing Compounds Aldehydes and Ketones propenal e,f propanal e,f 2—methyipropanal e 2—methyipropenal (tent.) e,f -butanal e,f 3—methylbutanal e —hexanal e,f hexanal isomer f 3—methylbutanal f n—heptanal e 2—butenal f ethylbutanal (tent.) methoxybenzaldehyde b methyl vinyl ketone e methyl ethyl ketone e 4 —methvl—2—pentanone f 2 —heptanone f octanone isomer (tent.) 25 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Oxygen Containing Compounds (con.) Aldehydes and Ketones (con.) cedranone (C 15 H 4 0) (tent. ?) c long chain propyl ketone c,d Alcohols 2—propanol e 2—methyl—2—propanol e , a, f 2—methyl—l—propanol e 1—butanol e,f 2—methyl—l—butanol (tent.) f undecenol (tent.) d dimethyiphenol isomers e,a,f,b ethylphenol isomer f cresol c,b,g di—t—butyl cresol b,d Ethers furari b,f dimethyl ether e,f diethyl ether e vinyl methyl ether (tent.) c,d ethyl vinyl ether c m—cresyl ethyl ether c,b diphenyl ether (tent.) c,d benzyl phenyl ether (tent.) c,d furfuryl methyl ether (tent.) b dimethyl—l,4—dioxane (tent.) b methyl anisole b butyl methyl ether d dihydropyran d anisole d 26 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Oxygen Containing ComDounds (con.) Ethers (con.) diphenoxybenzene g methoxyanthracene (tent.) b Other ethyl acetate f nialeic anhydride (tent.) b,g hexenyl hexenate (tent.) b phthalate g Nitrogen Containing Compounds N—methyl—2—butylamine (tent.) b diethylamine (tent.) b N-n—butylpiperidine (tent.) b butylaminodiphenylamine (tent.) d 2—amino—2--methyl—l—propanol g cyclohexylamine (tent.) c aniline g trimethylindoline (tent.) c phenylindole (tent.) c pyridine (tent.) b N—ethylpyridine (tent.) c phenylpyridine (tent.) c dimethyiquinoline d propene nitrile (tent.) a propane nitrile (tent.) b 3,3—dimethylcyclobutane carbon nitrile (tent.) g toluene diisocyanate (tent.) c Sulfur Contain4D Compounds carbon disulfide e,c,b diethyl sulfide e beuzothiazole e,d,g diisobutylthiophene (tent.) b d 27 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Sulfur Containing Compounds (con.) C 8 —alkyJ. thiophene (tent.) d Aromatic Hydrocarbons isopropylbenzene e, f n—propylbenzene e,a,f,c,b ,d 1,2, 4—trimethylbenzene e , a, f o—propylto luene e,a diethYlbe e isomer e ethy lbenzene a, f , c —xy1ene a,f 1,3,5—trimethylbenzene a —propylto1uene a C 4 —alkyl benzene isomers e,a,f,c,b,d C 5 —alkyl benzene isomers e,a,f,c,b,d diiuethylethylbenzene isomers e,a tetramethylbenzene isomer e 2 —ethy lto luene f biphenylene c C 6 —alkyl benzene isomers c,b,d dimethy idihydroindene or methyltetrahydronaphthalene c ,b ,d C 7 —alkyl benzene isomers c,b,d unsaturated C 6 —alkyl benzene isomers c unsaturated C 7 —alkyl benzene isomers c C 9 —alkyl benzene isomer c biphenyl c,b,g unsaturated C 8 —alkyl benzene isomer c trimethy lisopropylbenzene b phenylcyclohexene b C 3 —alkyl benZene d methyistyrene isomers c,b,d 28 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Aromatic Hydrocarbons (con.) dimethyistyrene a,d C.,—alkyl styrene isomers c diethyistyrene isomers b di—t—butylphenanthrene (tent.) B dimethylindane b ,d naphthalene e,c,b methyltetrahydronaphthalenes c dimethylnaphthalene c ,b , d, g dimethyldihydronaphthalenes c tetrahydronaphthalene b ethyltetrahydronaphthalene b C 4 —alkyl tetrahydronaphthalene b dimethyltetrahydronaphthalene d Other Hydrocarbons C 3 propene (tent.) b C 4 1—butene e,a,f,c,b,d 2—butene a,b,c n—butane a,f,c,d C 4 H 10 isomer C C 5 n—pentane a,f,b,d cyclopentene a pentyne b CH isomer c D 10 29 ------- Table 4. ORGA1’ ICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Other Hydrocarbons (con.) C 6 C 6 H 10 isomers e,a,b,d methylpentene a C 7 C 7 H 12 b methyl hexyne g methyl cyclohexene isomers a C 8 C 8 1 1 16 isomers e,f,b,d ethylcyclohexane a trimethylpentane isomer a C 8114 isomers a,b C 9 C 9 H 16 isomers e,f,c,b,d C 9 H 18 isomers e,f,c,b,d trimethylcyclohexane e 2, 3—dimethyiheptane e propylcyclohexane e , f ,b Cl 0 C 10 H 22 isomers e,a,b isomers e,f,c,b C 10 H 6 isomers e,f,b butylcyclohexane e,f,b,d terpinene isomers e,a,f,c,b,d C H isomer a 10 12 C H isomers e,f 10 20 30 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Notes Other Hydrocarbons (con.) Cli C 11 H 22 isomers e,a,f,c,b,d C 11 11 70 isomers a,f,c,b,d pentylcyclohexane e , f Cl 2 C 12 H 6 isomers e,f,c,b,d C 12 H 24 isomers e,f,c,b,d n—dodecane e,f triisobutylene f C 12 H 16 isomers c C 12 H 22 isomers b,d C 12 H 18 isomer b hexyicyclohexane e Cl 3 C 13 H 28 isomers e,f,c,b,d C 3 H 26 isomers e,a,f,c,b,d 2—methyidodecane e 3—methyldodecane e 3—methyldodecane e n—tridecane e C 13 H 24 isomers c,b,d dodecahydrofluorene (tent.) d Cl 4 C ,H isomers e,c,b,d l + 30 C H isomers e,c,b,d 14 28 CE isomers c,b 31 ------- Table 4. ORGANICS FOUND IN AUTOMOBILE INTERIORS (con.) Compounds Other Hydrocarbons (con.) C 14 (con.) C H isomers 14 24 C 14 H 22 isomers Cl 5 C 15 H 32 isomers C 15 H 30 isomers C 15 H 28 isomers C 15 H 26 isomers C 15 11 24 isomers C 15 H 22 isomers Cl 6 C 16 H 34 isomers c,b,d C 16 H 32 isomers c,b,d C 16 H 28 isomers b C 16 H 30 isomers b C 17 C 17 H 36 isomers Notes c C c,b,d d,c,b c,b C c ,b b Notes: b,c a = Compound found in 1976 Datsun — 9/24/76 b Compound found in 1976 Gremlin — 7/30/76 c = Compound found in 1976 Pinto — 7/29/76 d = Compound found in 1976 Vega — 8/5/76 e = Compound found in 1976 Rabbit — 9/22/76 f = Compound found in 1976 Chevette — 9/13/76 g = Compound found in 1976 Chevette — 7/28/76 32 ------- In the test procedure the automobiles were ventilated to outside air, closed up in the normal manner and the interior temperature thermostated at 65°C. After 3 hours, samples of the interior air were collected on Tenax cartridges and analyzed by GC/MS. Some identifications are reported as tentative. This usually means that the sample spectrum fits the reference compendium data for that identifi- cation, but is equivocal due to the presence of background, other unresolved components or an insufficient amount of the component. Empirical formulae are reported for many hydrocarbons with occasional further designation of branched or normal. The hydrocarbons reported as empirical formulae could be expanded only in a few instances to indicate that they were branched (the normal isomers appeared in the background). Structural elucidation beyond this point is complicated by two factors: (1) hydrocarbon isomers having the same empirical formula result in the same array of in/e values with relative intensities being the only distinguishing feature; and (2) compendia of mass spectra do not list all isomers, especially as the molecular weight and number of isomers increase. This situation is further complicated by incomplete chromatographic separation of hydrocarbons and several hydrocarbons giving rise to the same ions. Such overlap can seriously affect the relative intensities and can make this an unreliable parameter for structural identification. Greater mass spectral resolution does nothing to solve this problem since the ttinterferent? gives rise to the same ion(s). Quantitatation of the organics was not included in the scope of work. Although information on specific compounds may be retrieved for the Datsun, Rabbit and Chevette, this would be a project in itself. However, comparing the number and size of peaks in the Datsun chromatogram with the perfluoro- benzene external standard, shows the total concentration of organics to be about 1-10 pg/. . The other automobiles were not sufficiently different for this type of estimate not to apply to them. On the other end of the scale, approximately 1 ng/2 . or more would have to be present for an identification to be made. 33 ------- A frequency prioritized list of the same compounds is included in Appendix C to facilitate inspection of the most commonly found compounds. 34 ------- REFERENCE S 1. J. V. Pustinger, F. N. Hodgson, and W. B. Ross. Identification of Volatile Contaminants of Space Cabin Materials. Aerospace Medical Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio AMRL-TR-66-53. 1966. 2. J. V. Pustinger and F. N. Hodgson. Identification of Volatile Conta- minants of Space Cabin Materials. Aerospace Medical Research Labora- tory, Wright-Patterson Air Force Base, Dayton, Ohio. AMRL-TR-67-58. 1967. 3. J. V. Pustinger and F. N. Hodgson. Identification of Volatile Contami- nants of Space Cabin Materials. Aerospace Medical Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio. AMRL-TR-68-27. 1968. 4. J. V. Pustinger, F. N. Hodgson, and J. E. Strobel. Identification of Volatile Contaminants of Space Cabin Materials. Aerospace Medical Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio. ANRL-TR-69-l8. 1969. 5. J. V. Pustinger, F. N. Hodgson, J. E. Strobel, and R. L. Evers. Identi- fication of Volatile Contaminants of Space Cabin Materials. Aerospace Medical Research Laboratory, Wright-Patterson Air Force Base, Dayton, Ohio. ANRL-TR-69-71. 1969. 6. International Agency for Research on Cancer, Monograph 7, 291 (1974). 7. I. J. Selikoff and E. C. Hammond. “Toxicity of Vinyl Chloride - Poly- vinyl Chloride,” Ann. N. Y. Acad. Sci., 246, 1 (1975). 8. Federal Register, Vol. 42, p. 28154, 1977. 9. Registry of Toxic Effects of Chemical Substances , 1976 Edition. 10. C. L. Duel. Collection and Measurement of Atmospheric Trace Contami- nants. Aerojet Electrosystems Co. , Azusa, CA. Final Report Cont. NAS 1-8714, NASA Doc. No. 71-19636. 35 ------- 11. E. D. Pellizzari. Development of Method for Carcinogenic Vapor Analysis in Ambient Atmospheres. Research Triangle Institute Reports prepared for Office of Research and Development, U.S. Environmental Protection Agency, EPA-650/2-74-121, (NTIS No. PB 239770), Contract No. 68-02-1128, 162 pp., July 1974, and EPA- 600/2-75-076 (NTIS No. PB 250620), Contract No. 68-02-1128, 199 pp., November 1975, EPA 600/7-77-055 (NTIS No. PB 269582) Contract No. 68-02-1128, 228 p. June 1977. 12. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II (Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading, RG74PR, 13K, 1970. 36 ------- APPENDIX A SA\NPLING PROCEDURE 37 ------- APPENDIX A SANPLING PROCEDURE Two design criteria were essential to the sampling of the interior of each automobile. One was to be able to withdraw an air sample from the compartment without adversely affecting the breakthrough volume of the sorbent used in sampling. The other was to control the temperature of the compartment. The experimental arrangement which was used to meet these requirements is discussed below. SANPLING PORT A Plexiglas panel was designed to enable the sampling cartridges to be inserted into the automobile window. A grooved edge on the panel allowed it to fit snugly over the window glass, with the upper edge inserted into the groove normally accepting the window glass. The areas not covered by this panel were sealed using heavy weight aluminum foil supported with cardboard. The foil extended beyond the opening to cm and was pressed to conform to the window contours. This covering was held in place with duct tape applied at intervals along the perimeter. (see Figure A-l). Two ports were drilled in the panel: one 16 mm in diameter for the Tenax cartridge; the other 6 mm in diameter for the charcoal cartridge. When not in use these were filled with an aluminum foil plug. TENPERATURE CONTROLS The temperature of the automobile interior was positvely controlled using the arrangement shown schematically in Figure A-2. The temperature 38 ------- TEN AX TO SPACE H EATER AIR TEMP. P ROBE PORT CHARCOAL CARTRIDGE OPEN AREA COVERED WITH FOIL Fic ure A—i. Side window on driver’s side. ------- 0 THERMOMETER CHARCOAL OR TENAX FRONT SEAT FRONT SEAT TEMP CONTROLLER 0 THERM CM E T ER Figure A—.. Au:c’ bi1e ericr e-. era: re c ::r . ------- monitored at two points in the front and back of the compartment was found to be constant within ±2°C. The desired temperature was maintained for 3 hours before initiating the sample collection. The 200 to 500 ml samples collected on SKC charcoal were collected at 50 ml/min for 4 and 10 minutes, respectively. The Tenax GC samples were collected at 100- 300 mi/mm for 1 to 2 hours. Samples were collected using either a DuPont constant-flow personnel sampler (Pinto, Gremlin, Vega, and Chevette [ 1st sequence]) or an SKC personnel sampler (Chevette [ 2nd sequencel, Datsun and Rabbit). Air was pulled through a cartridge which protruded just inside the car when placed in the Plexiglas sampling port (see Figure A-i). The cartridge was attached to the sampler by a short rubber tube. The charcoal cartridge consisted of 150 mg of SKC Lot 104 charcoal packed between two 1 cm glass wool plugs inside a glass tube 6 mm o.d. The Tenax cartridge consisted of an 8 cm length of Tenax GC packed between two 1 cm glass wool plugs inside a glass tube 16 mm o.d. All cartridge samples were sealed in culture tubes and stored at or below —5°C until analyzed. The sampling arrangement used here minimized the effect of the elevated temperature of the automobile interior on the cartridge tempera- ture and consequently maintained the breakthrough volume. Since the cartridges were outside the car, they remained at ambient temperature until sampling was initiated. The low flow rates used for sampling minimized the temperature rise due to the temperature of the air sampled. 41 ------- 42 ------- APPENDIX B GAS LIQUID CHROMATOGRAPHY - MASS SPECTROMETRY ANALYSIS OF ORGANICS IN AUTOMOBILE INTERIORS 43 ------- 5 10 15 20 Ttine (mm) Figure B—i. Total ion current plot during gas liquid chromatography/mass spectrometry ol air sample from tiLe interior of a Vega (8/26/76) autoi .obile. A 100 m OV—101 SCU I7 Cal) ii thry column was te;c’1. See text for conditions. Sample volume 31.6 2. (con.) I 0 Is 10 :3, 25 30 ------- 105 I TenlperLltLlre (SC) 1 iru (ritn’ 200 45 II 140 1 30 It lo 181) 35 40 220 240 50 55 Fi tire B—i. (con.) ------- Ime (mlii) Figure B—i. (con.) ------- 2 30 3 57 4 62 5 43 6 66 7 66 5 70 9 74 10 31 11 83 12 34 15 36 13 83 15 90 46 94 17 97 13 98 19 132 20 104 21 111 22 112 23 114 24 119 25 420 26 122 27 121 28 126 29 123 30 129 31 130 32 134 33 135 34 136 35 137 36 133 37 129 38 141 39 142 40 144 41 145 42 146 43 lb 41 147 45 147 46 143 Table B—i. ORGANIC CO OTJNDS IDENTIFIED FROM FIGURE B-i. .7 - .3 49 30 51 45 53 34 43 55 57 53 59 60 61 62 63 64 03 00 67 68 69 70 71 73 74 75 76 77 78 79 30 SI 32 S3 34 85 36 37 83 39 90 91 150 C 9 -L 3 Ls.4oer 151 C.H, 0 Iscoer 153 anlsole 134 C H 13 Isor 155 C 0 H, Isorner 155 C_—be4zene 135 C 13 H, 0 iscrer 157 C H. 3 1so er 137 C 9 H, 5 lsc er 153 C 1 _ _ Iscrer 153 C H, 8 isooer 139 C. 3 H, 0 iscrer 150 ? ° ° 161 C , H_ 3 iso er 161 C, 0 H 0 iso er 162 4—propy1be zane 162 c, 0 :-i 15 Isc er 162 C,H, . 4 scoer 1ó2 C 10 3_., Isomer 163 phenol 163 C 3 —Senzene 164 C, 0 H,, Isomer 155 C 10 H 20 isomer 166 methyl styrena 157 C, - H., Isoner i_i —— 168 chiorostyrene (tent.) 163 C , 3 H 25 isomer 163 c 10 H 1 . isomer (tent.) 170 C 3 —ben:ene 171 C 10 H 2 , isomer 171 C 10 H 20 isomer 172 C 10 H 20 Isomer 173 dichlorobenzene (tent.) 173 C,—bem eoe 175 C 11 H, 2 isomer 175 C 11 H 2 , isomer 175 t—butthanol 175 C—Senzene 176 C—ben ene .4 176 C ,H.,. iSOmer 177 C 4 -b nzene 178 terptosne 173 179 dipropy1ben ene 179 C 11 H,, Isomer 130 C,—5enze e l ie a l i e ovde Chromato- Elution Chromato- Elution graphic Peak No. Temp. Compound graphic (°C) i Peak No. Temp. Compound (°C) butene C,H. Isomer 40 ISomer 4 C H., isomer 3.-— C 7 H, 1 isomer vinyl re:hvl ether (tent.) methyl b.iryl etr er C 6 . isomer C.H Isomer o 1.. CHC I 3 CH. isomer 0 isomer o 1.- CH ISczer 0 1.1.1—tc 1orcechane benz s .s C..H. - isomer C_H,. icmer C 7 H 14 Isomer C_H, - isomer 5.0 C 7 H 1 , isomer CH ,_i o mer ‘- - .3 C H - isomer 8 lo to1 ene C 3 H, 3 isomer C H - isomer S is C H, Iscoer 3 5._S C 3 H 13 Isomer C H. - Isomer 35.4 C 3 H 5 Isomer tetrach loroe thy lene hexa:hy1cycbo:r5.s 1Ox3r1e (3KG) C 9 H, 0 Isomer C_H. - Isomer S C 9 H 13 Isomer C 9 H 13 Isomer d ihy ropyr3ri e t by 15 en zeOe n/p — xv lens C 9 FL 0 Iscrer C_H isomer 3 C H. isomer 9 43 C 9 H 16 isomer Sryrene C 9 H, 3 (cy 1ooctste seme (tent.) 0X) IlC4 5 47 ------- Table B—i. (con.) Chromato- Elution Chromato- Elution graphic Peak No. Temp. Compound graphic (°C) Peak No. Temp. Compound (°C) 93 130 C 11 H 1so er 1.33 211 C 13 H , isa er 94 132 C 11 ,, iao er 139 311 C 13 H, 6 isoner 95 133 C, 1 3.. Isoner 140 211 C 13 R, 3 tso er 96 133 C 1 2 E, 5 isoner 141 211 C—beozene 97 133 C,— eozene 142 212 C H, isomer 4 13 6 98 184 C 1 .,H,. is3mer 143 214 dthethy1tetrahydronaphc a1e e 99 136 Isoprcpyi nechvi phenyl 144 215 C 6 -benzem chl3ride (rent.) 145 216 benzothiazo le 100 186 dj eth3xvbenzene 146 217 C 13 H, 6 iso ier 101 133 di ethv1styrene 147 218 C 6 H 11 beflZefle 102 188 C 1 H, 3 isomer 148 218 C 7 —benzerie 103 138 C ,IL, tso er 149 219 C •H, Isomer 104 138 C IL, isomer 150 219 C,, H lscoer 11 .. i. 30 105 190 C 11 3. isomer (branched) 151 220 C 13 H 26 isomer 106 192 C 5 —benzene 152 221 C 14 H 30 isomer 107 192 C 11 1L,, isomer 153 221 C 7 —be zerme 108 193 C 12 H.,, iso er 134 221 C 13 H, 5 isoer 109 193 C—ben:ene 155 221 dinethylirmdan 110 194 C 1 ,3 , isomer 156 223 undecermol (cenr.) 111 194 C 12 H ,. iscoer 157 224 C 13 H.. 3 Isorner 112 195 C 5 — en:ene 158 225 C 14 8 3 isomer 113 196 C 1 H, isomer 159 227 i—naphtha1ene 114 197 C.— snzene 160 228 C ,H, isomer ) 14 3 115 197 C 12 3, Isomer 161 229 C 15 H 30 Isomer 116 199 C 5 H 9 — enze e 162 229 C 7 —benzene 117 199 penrachlocoacerone (tent.) 163 230 3—mechylnapathalene 118 200 C 12 3,, isomer 164 230 dicechyltecrahydronaphchalene 119 200 C E .. isomer 165 230 C —be zene 12g. 7 120 200 C 12 L. 6 isomer 166 232 dlnethvlcecrahydronaphchalene 121 201 C 5 —b nzene 167 232 C 3 —benzene 122 202 C 13 H 26 Isomer 168 233 C 14 H 23 isomer 123 202 C 12 8,, isomer 169 234 C 15 H 0 Isomer 124 202 C 12 8, 6 isomer 170 234 C 7 —benzene 125 202 C 12 11, 4 isomer 171 234 C 14 H .. 5 isomer 126 203 C 12 3. , 6 isomer 172 234 C 1 H, 5 Isomer 127 204 C 13 H., 8 isomer 173 236 C 16 H 3 ., isomer 123 206 C 12 L, 4 isomer 174 239 C 15 H 32 isomer 129 206 trichlorobenzene 175 238 C 15 H 30 Isomer 130 206 C 6 —benze m e 176 238 C 16 M 34 isomer 131 207 methyltetrahydronaphthalene 177 239 C 14 H 30 isomer 132 208 C 12 H., 6 Isomer 178 239 C 15 H 30 Isomer 133 208 naphthalene 179 240 octamethyltrisiloxine 134 208 isomer 180 a C 15 H, 0 Isomer 135 209 C 6 —benzene 181 a’ dime yltsaphcha1.emte 136 210 C 13 11, 6 isomer 182 a C 16 H 34 isomer 137 210 nethyltetrahydronaphtha lene 183 di eChY1phCha1ate 48 ------- Table B—i. (con.) Chromato. Elution graphic Temp. Compound Peak No. (°C) Chromato- EltitioTi graphic Temp. Con pound Peak No. (°C) a iyLn p cna1 191 a Cg—t 1 2hefle (:e t.) 195 a - - isc er 192 a octa yLtri1 a e a dethvlqutholi 193 a dtphe v1et er ( e t.) 157 a UEtk OWLi 194 a icog ch. in pr y1 ke one 153 a C,.H, 1so er 195 a phenvi colyl ether 139 a isomer 196 a butyLa inodipheny1a ine (tent.) 190 a di—t—butylcresol a Isother .i i 49 ------- I I U i 0 A UN)0U II -- r .-T----———— 1 1 2) 40 60 80 100 120 140 T eapt.rmture_(‘ç) __- -- 4) 5 20 10 15 25 160 180 30 204) 40 220 Time (.lii) I I uri ’ I —2. Toi a I Ion ‘IIrrrnL 1)14)1 (IL IrI ng gas I Iqu Id ( ‘hronlolography/rnass spe( 1romct ry of a I r sample from tIi(’ I Ut or I or of a I)at.sun (10/10/76) auloinob I Ic. A 100 in OV— 101 SCOT rai I I I a ry ( O Itirnil was usc(I . See t OX t for (‘011(1 I I 10115 Samp I V vol (1100 1 8. 3 . — ------- Table B—2. ORGANIC CO ’tPOI.TNDS IDENTIFIED FROM FIGURE B—2. 03 , 1—but ene n—butane 2 —bu ten e CH Isomer 10 L ao tri1orofh orethane C..H, 0 isomer n—pen tone C.H. isomer ) aetone propeme nitrlle 113 - CS, ter—butonoj cvc!opentene C 6 H,. Isomer 2— e ry 17 ant ane C H. isomer 6 jO ber.zene cyclohexa ne 2—metbyihexane 2, 3—d methv1pentane 3—thv lhe ,cacie dImethv1 yc1opencar.e isomer trit y1pentana isomar C 7 H,, isomer C 7 H, 2 isooer n—heptane C 7 H 1 , isomer C 7 H 1 , isomer methy1cy lohexene isomer methyloyc lchex o ne C 5 H , 5 Isomer isomer 22A 31. 23 82 231 82 24 33 24 83 25 84 251 87 26 87- 27 83 28 89 29 90 291 91 30 92 301 92 31. 93 31A 94 32 95 33 97 34 93 35 98 36 100 361 101 37 102 371 103 38 104 39 106 391 108 40 111 401 113 41 114 411 117 42 117 421 117 43 119 431 120 44 121 441 121 45 122 46 123 47 125 43 126 431 126 49 127 50 1.23 51 1)0 52 1)2 C 5 H 13 isomer trimetytoycinpen aoe isomer Isomer C H, isomer S trlmethylpencone isomer toluene 2,5—d i chyihex one 2, 3—dithv lhexa ne 3—mechyiheptame C H, Isomer 1. C 9 H, 0 isomer 1,2—dibromoechame (teat.) C 3 H 15 isomer C 3 H 1 , isomer n—ccta ne C 3 H 16 Isomer C_H,, isomer P C 9 H 20 Isom,r silane c mtound (1Y C) C 9 H_ 0 Isomer ethv lcyc lohexaae C H..,., isomer 9 u C 9 H 13 isomer C Si. - isomer 9 .5 athv1ben ene ‘.1ene C 9 H, 0 soc er o —xy1 ne C 9 H 13 isomer 000ane C 9 H, 3 isomer isopropylbenrene C 10 H 72 isomer C 10 H 22 isomer C 10 H.. 0 isomer cerpineae isomer C 1 QH, 2 isoi er rt—p rop y lb ens ene —echyl t oluene 1, 3,5—crimethylbeasene 0 10 H,_ Isomer phenol (tent.) 0e thy It ol ueae C 13 H 20 isomer 1,2, 4 —tr1methylb’ z e n s n—de cane Chromato- Elution graphic Temp. Compound Peak No. (°C) Chromato- Elution graphic Temp. Compound Peak No. (°C) (teOt.) ÷ fteon 1 39 2 41 Lk 41 3 42 4 42 A 44 5 45 6 46 7 46 8 47 9 43 10 50 101 50 103 52 100 52 100 5) 11 54 12 56 121 57 13 58 131 59 133 59 132 60 13 61 14 61 141 62 148 63 14C 65 15 65 151 67 16 68 17 69 171 70 18 71 I Sa. 72 1,33 73 1.3C 73 19 74 191 75 20 76 201 76 2 1 78 2L A 79 22 50 3—me t hvlpan:ane C 6 H 15 .SOOCE — hexafluorobeazene (e ) C H. - I scmer 7 .0 C H,., isomer 6 C.H, Isomer 0 me th’. lpentene meyi cyclcpea:nne perfluorotoluene + C 7 H 1 S isomer (ei) 1,2—dichioroethane 51 ------- Table B—2. (con.) Chromal graphic Peak No. 0 ElUtiOn Temp. (°C) Compound Chxomato- Elution graphic Temp. Peak No. (°C) Compound 5A 323 53 1)3 133 135 C, , 0 1so er C.—aL y1 e1ze isc er - ,3—tri ethy1benzen 606 SOC 61 1 3 149 150 c 11 ,, isomr C,—aL yL eaze ’.e is r 4 n—undecarie 53A 135 C -a1 y1 berizene i3o er 62 152 C.— 1ky1 benze e i cer 53 53 55A 553 56 57 33 136 137 133 139 140 131 133 C 11 .. isocer ethv1styrene + C 11 H 2 , isocers C 10 L 0 isomer C 3 —alkyi benzene isonet k 7ropy1co1ueae n—bucylbenzene + propyltoluene o—propyltoluene 63 6i . 633 63C 63D 63E 153 153 156 156. 153 159 C,— 1ky1 benzene so er C11}423 isoner C 10 , isoner C 5 —slkyl benzene isouer C 10 12 soner di ethy1pheno1 + C,—alkyl benzeoe tsoer SSA 59 60 133 135 136 C 11 L, isoner di ethy1 ethylbenzene isoner dtethylstyrene or C 10 9, 0 isoner 63F 63C 63R 64 159 161 166 167 C 5 —alkyl beozene isorner C 12 l 2 , Lscer C 12 .,, isoner — ooecsne 60A 137 C—slkyl benzeie isoner 64A 173 C 13 b, 6 isocer 52 ------- i ’ i ’ jI It,oI, ;I . _ 40 It) 8)) I 00 I .0 14)) 160 180 1t iper.Itur& ( C ) — -- F —i - i— S II) [ 5 20 5 3(1 3 5 4’) I I int (In) i gti r R— rot a I luti (‘urrent p ot dun ng gas Ii quid (hromutogra )hy/mass sI)eeLI owe Lry oi air ;ninp It from the I nt.er br t ;i Chevette (10/10/7() automohi it. A tOo in OV— 101 SCOt’ cap ii I ary col own was tise(1 . Se. text k)r cond it i oils. a1U )1 e V( 101111. I. ‘3. ‘3 UI C ., ------- Table B—3. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—3. Chromato- Elution Chromato- Elutjon graphic Temp. Compound graphic Temp. Compound Peak No. (°C) Peak No. (°C) 2 .‘3 CO, CF..C1, 17C 91 C H 16 iao er 3 !.3 1 Sucar a 170 92 dL etht1cy1ohaxane isorner It .3 cat .aj &wde 13 93 r —haxa aj 33 4 n— ur ne 13A 94 C H 1 is er 3 37 tso e :a e 183 95 C H. isorner S 1.6 !.A 47 tri1orof1ur eth.ane 19 95 n—octane 43 43 1—pencane 19A 96 C_H, 6 isoner 4C 46 2—per.tene + fursa 20 100 hexanethylcyclotrisioxane (3KG) 5 49 n—oenra e 201 102 C H lso er — 9 in 51 49 pro 3na2. + c 5 a,, 3 tso er 203 103 ethyicyclohexane 53 50 pro a a1 2CC 103 C 9 H, 3 + C 9 H, 3 isocers SC 30 dich.orcaethane + C_L 0 lso er 21 105 2—hepta one 6 51 acetone 22 106 ethylbenzene 61 51 freon 113 (3KG) 221 107 C R. tsoaer 9 1.8 63 53 dinerhv l ether (tent.) 23 103 — c’:1ene SC 54 ter—b ,tano1 24 109 C 9 H, 0 isoner 7 35 2—nenhyl7encaae 25 110 C 9 H 0 isoner 71 56 crotcnaidehvde 251 111 C H 15 _soner 73 57 3—net i9entane 26 111 styrene 7C 57 C.H. - isoner 261 112 C H iscner 916 70 53 2—neth ’1prooanaj 263 112 o—xylane + C 9 H 15 isoner 9 . 59 he caf1uorobe:izeae (er) 27 113 a he?ta1dehvde 9 59 n— ne 271 114 C 9 H 13 isoner 91 63 ch1orofor 28 115 n—noaarie 53 61 aerh,1 ethyl katone 29 117 C 9 H 18 isocer 10 54 erf1uoroto1uene (er) 291 118 iso ropy1ben:etie 101 65 ethylcyclopencane 30 119 C 10 H,, Isoner 103 66 ethyl acetate (teat.) 30A 121 propvicyclohexane 11 67 n— utana1 31 122 tar9inene 1soc er 12 69 benzer.e 32 123 benz 1 ehyd 121 69 carbon tetrachiotide 321 124 n—proo-,lbenzeae 123 70 cyclonaxace 33 125 —athy1to1u ne 12C 71 1—butanol (cant.) 34 127 n—echyltoluene + C 10 H ..., isoner 13 72 2— ethy1hexane 341 127 C 10 H_ 3 isoner 14 73 3—butar.aj 35 3.28 C H,, jsoner 11 .... 15 76 n—heptaae 36 129 o—ethyltoluene + C 10 H,, Isoner 151 78 C 8 H 1 . isomer 361 130 C 10 H 16 isoner 16 79 2—aethyl—l—butanol (tent.) 37 131 occanone (ter.t.) + C 10 H. , 0 161 30 nethvlcyclohexane isoners 153 32 C 3 B, 3 isoner 38 132 1,2,4—crinechylbeazene + C 10 H 20 1SC 53 4—oe chyl—2—pentanoae isorers 160 84 hexanal isoner 381 133 C 10 H, 0 isoner liE 86 2,3—dlnechylhexane 39 133 n—decane 17 87 toluane 391 135 C 13 H_ 0 isoner 171 99 2, 4 —dtnethv lhexana 40 136 triisobutvleae 173 50 3—nec.’ ylhept ae 301 137 1,2, 3—trinethylbeozene 54 ------- Table B—3. (con.) Chromato- graphic Peak No. Elution Temp. (°C) Compound Chxomato- graphic Peak No. Elution Temp. (°C) Compound 303 137 —a1ky1 bei sn iaooe 513 154 C ,H,, isomer 31 133 C,,H,, isomer 4 52 155 C , H ,, isomer — 42 139 C. H,, isomer - 521 155 C,. H, isomer - ..21 140 butyloyclohemar.e C. 1 H ,, isomer 53 531 157 158 C, ,H, 5 isomer C_—alkvl enzetie 43 141 C H,, isomer 11 54 159 Dentv1c- c1ohexane . 34 142 C 12 H 26 isomer 541 160 C 1 ,H, :scmer 4 .A 142 C 1 H ,, isomer 55 151 C,—alkyl benzene 443 45 143 143 C.—alkvl benzene + C 11 H,, isomers acetop’nenone 53 55A 37 151 162 163 dimeth -,lphanol C 17 H, 6 isomer ethyl?nenol C—alkyl 5e zane 431 144 C 1 ,H 22 isomer isomer 46 145 C H isomer 11 24 58 164 C. H, isomer 37 38 39 147 148 149 C,—alks -1 benrene 0,_H, 6 isomers C, —a1 v1 benzene isomer C, 3 H_ 5 isomer 59 60 61 62 165 167 169 171 C _H , isomer C ,E,., isomer n—dodeoarie C 13 H, 3 4somer 50 150 C H., isomer 621 172 C 13 H 26 isomer 501 151 C 51 8 22 isomer 628 174 C, 3 H_ 5 isomer 303 131 0 11 H,, isomer 62C 175 0 12 H,, isomer 51 152 n—undecane 5L1 153 C. —a lkvl bemzeue isomer .4 55 ------- idkX) I I I I i i • )t)IUI .)UU() I l l I n f l I ; I 2 11 1111 ,i 0 lO l IC) a I — i\ .Ii !. , . i , , ,..IIlI )l ,ll1 l ,— —- n I / i’— ...j ! I I 41 — t o i ; — ioi 1 I 0 1 1 1 0 ç - . ‘J?O ‘Lempera r ure (°c) F — I — I ——---i -- - “T -- l 5 1(1 15 .0 25 10 1’) ‘*0 45 So Time (m m) V igtire R---4 . ‘lot at ion turr*nI pini (ltlri tig ga -; I 1(1(11(1 Fl lro lllatTography/lIlass sln’rtromet ry of air 5 1119) 1 1 root t Ito mt t I or oF a Cltt’ve t to (8/25/76) an totoob lit’ . A 100 in OV— 101 SUYI’ (it I 1 lttry column was IIS&’tI . So c 1 0 )01 lot- cOhidi I tolls. Saitiple vol time 6.42 2.. No It ’: a = In to r I cr011 10 dtte to watt,t’ U I 0 ’ ------- Table B—4. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—4. Chromato- Elutjon graphic Temp. Compound Pealc No. (°C) Chromato-Elution graphic Temp. Compound Peak No. (°C 1 133 3.3—di ey1’,35u car o— 41 19 C,—benzene tu:rt le 32 196 C 11 H_, iso er 2 113 43 193 C 5 —ber ze e 3 123 t 1uerta 44 199 d echy1 tyrene 4 133 exa: y1cyc1otris oxane (ter.t.) 75 199 3 3 —benzer,e 5 337 C H, 6 isoer 46 201 C 12 H,, 1ao er 6 140 a1kv1 ced cyclohexane 47 201 C 1 ,H isomer 7 143 C 2 —beozeoe 43 202 dimethyistyrene 8 149 cyc1coctetrae e (or s tvrenC) 49 202 C 5 —beizerte 9 150 C,—beozene 50 204 C 12 L 6 tsomer 10 151 C H_ :somer 51 204 C..—benzene 11 153 maleio anhy ride ) 52 206 C 12 H, 4 aomer 12 155 53 206 3 11 a 22 5Ooer 13 161 C H, isomer 54 207 C — enzeoe 9 .3 6 14 164 C 3 —beoreoe 55 203 C 12 H 26 isorer 15 165 6 n:s1 ehyde 56 208 aphtha1eoe 16 163 aoi1i e 57 209 C_—be ze e 17 168 2—ami o—2—methy1—1—?ropar.o1 53 211 C, 3 H 23 isomer 18 170 C 3 —bemzene 59 212 C 6 —ber.zene 19 171 C, 1soer 60 213 C—ben:ete 20 177 C,—6etzene 61 216 beozothiazole [ C 7 HNS] 21 178 C H,. isomer 62 217 C H, isor er 1 _3 22 179 C 6 H,, isorner 63 219 C 6 —benzene 23 181 C. isomer 64 221 C_—indoline 24 382 C, 0 H 22 isomer 65 225 C 13 H, 5 isomer 25 132 C — s e 66 225 C_—6eaze e 26 183 C, 0 H 22 isomer 67 226 C 6 —benze e 27 133 cresol 63 227 C 7 —beozeoe 28 183 C, 1 , 2 Isomer 69 228 S—methyi aphtha1ene 29 185 C,—bemzene 0 230 a—roethy1nazhthaie e 30 187 C 4 —ber.zene 71 232 di—r—bury1phenso rhy1e e (tent.) 31 187 C 10 H_ 3 isomer 72 233 C_—benzene 32 183 C 11 H, 2 isomer 73 234 C 13 H, 6 isomer 33 190 C 11 H_, isomer 74 235 C 7 —benzene 34 190 C 11 H isomer 75 236 d phe oxyber.zece 35 190 C 11 H. 0 isomer 76 240 biphenyl 36 191 C 11 H: 9 isoner 77 a octamethyltrisiloxane 37 192 C 5 —benzené 78 a C 11 H 2 , isomer 38 194 C,,H.,, Isomer 79 a dfrerhylnaphthaiene 39 194 isomer 80 a ?—phrhalote 40 193 C—benzene 31 a Imethy1oaphthalC 1e a — Isothermal ------- I i.gure B—s. 40 5 18 ‘lemperature (°C) 60 8() 10 15 Time (mm) ion current p tot do r i tig gas .1 Iquid di roinn tOgra )hy /I11aSS Spe(’ tro— of a I r samp I from the inter i or of a Pinto (8/28/76) atitomobi I in OV—101 SCOT capil 1 ry column was used. See text for condiLioi, ;. lOt ill. met ry A 100 Satup I (‘ vol tifliC 32 Q U’ 15 5 10 I 20 III U 25 30 1 00 (con.) ------- 12fl 1 0 25 70 00 II I I 20 “g il tji e (I Ii Teni cr ittire ( (:) 160 35 160 lime (,!ii) 200 1 .0 65 Figure B—5. (con.) ------- Tempetiture ( C) 260 55 Time (miu ) - 0 0 I I II I II 220 Figure B—5. (con.) ------- Table B—5. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—5. Chromato- Elution aphic Temp. Compound Peak No. ( 0 C) Chromato- Elution graphic Temp. Compound peak No. (°C) £ 43 :3, 47 1-.) :c 1 r ( r 5/or 2 47 C,H, :so er 43 114 C H, 3 13o ,r 3 13 C -L c , er .9 14 . Cr-H iso er 3 2 C’ , 3 i o e 50 146 C 3 H 3 isc er ) i$o er 51 147 scyrene or cvcLo oc: e r ra ene 6 53 C_H. 1 tac e: 52 143 o— 1ene 7 59 CH,, isoaer 53 143 C H isoer 3 61 CH.._ iconer 54 149 C H 3 1sc er 9 63 C_H,. i c .er 53 149 C 9 M , 0 isoner 10 64 vinyl et v1 ether (rent.) 56 150 C 9 0 isoner 11 63 CH., tsoner 57 132 H erhy1pyrt51ne (tent.) 12 71 C.H 1 4soner 53 154 et .yL but3 ldehy5 (tent.) 13 7 C_ ,, isoner 59 155 C 9 H 18 scuer 14 73 C.H:, isoner 60 155 C 3 —alkvl bernzen Isoner 15 75 ace:cne 41 156 C H. isoner 9 13 15 73 CH, isorner 62 157 C H. - Isoner o 9 10 17 73 CH. inner 63 157 C H, isoner 0 .0 9 i 3 15 33 CH isoner 64 133 C H isoer 913 19 82 CH isoner 65 160 0—ninane 23 83 et vl :mnvl e: er 66 161 C 13 H , 0 Isoner 21 84 net vlerne ch1 ride 67 162 C 3 —alkyl herzene isoner 22 53 C_H. jsoer 68 163 benza1deh’ de 23 94 C,H., isoner 69 163 C 3 -alkyl benzene isc er 24 95 bennena 70 163 phenol 25 96 CH., isoer 71 163 C —alkyl bennene isoner 3 26 98 C_it,, isorner 72 167 C 10 H , 3 isoner 27 99 C_H. 6 isoner 73 167 C 3 —alkvl beozene isoner 25 132 C 7 H, i ac er 74 167 oethylstyrene 29 104 C H, isc er 75 167 C H, isorer 716 9 0 30 107 C 7 H ,, t nner 76 167 C 10 H 13 isoner 31 111 cycict exv1a ine (rent.) 77 168 C 10 H , 3 isoner 32 113 C ii. ia oner 73 170 C —alkyl benzene iscoer 33 119 toluene 79 171 C, 0 H 2 , isoner 34 122 C H.. isooer 80 171 C H ., isoner 8 10 2 35 125 C 5 H:, Ssooer 81. 173 C 11 i1 ,, sooer 36 126 C.it, isoner 82 174 C. —alkyl bene 0 10 a 37 126 CsH:, isorner 83 1’S C 1 H 22 isomer 33 123 C 3 H, 3 tsona: 84 175 C 11 H 2 , isomer 39 130 C 3 H 15 Isomer 85 176 C,—alkyl bennoene 1so er 40 132 C 9 H, 3 Isomer 86 176 CUR,, isomer 41 133 C H,. Isomer 87 176 C,—alkyl beozene iscoer S 10 42 135 C 8 H. 5 Isomer 38 177 C 1 ,H, , Isomer 43 133 C 9 H, 3 Isomer 89 177 C 12 H, 6 tsoc.et 44 139 ethylbennoene 90 178 m—cresyl ethyl ether 45 141 C_H,., isoner 91 173 C 11 H , , Isomer 46 141 C 9 H:, Isomer 92 173 dlchlorobenzene 61 ------- (con.) Table B—5. 93 173 C.,:-L isomer -i _6 94 179 C.,d, 6 isomer 95 130 C,—a1 -j1 beozene isomer 4 - 96 130 C,—alkyl benzane isomer 97 130 C H,. isomer 12 _o 98 131 C.—a1 y1 banzene tsomet 99 131 C 11 H,, isomer 100 151 C H,, isomer 11 _.. 101 131 C 1 :’d, Isomer 102 132 cresol 103 183 C,—alkyl benzene isomer 104 183 C, H,, isomer — 105 184 C,,H Isomer 106 185 C,—slkyl benrene isomer 107 185 C 1 ,H,, isomer 108 135 decah ’ drooap ths1eme (tent.) 109 136 C 4 —alkyl benzene isomer 110 137 C 12 H.,, isomer 111 118 C,—alkyl scyrene isomer 112 183 0116,2 isomer 113 188 C ,H, isomer ii. _0 114 188 C H.,, isomer 12 —. 115 139 C 5 —alkvl benzene isomer 116 189 C 1 .,6 26 isomer 117 191 C H,. isomer 11 ..* 116 191 C 11 6 22 isomer 119 191 C 5 —alkyl benzene isomer 120 191 C 12 8., 4 Isomer 121 191 C 12 6 26 isomer 122 191 C H , isomer 12 24 123 193 C 5 —alkvl benzeme isomer 124 193 C 11 6 22 isomer 125 193 C H , isomer 126 193 0126,6 isomer 127 194 C 4 —alkyl benzeae isomer 128 196 C H , isomer 12 2* 129 196 C 12 H 26 isomer 130 196 C 5 —alkyl beazene isomer 131 197 C 5 —slkyl beozene isomer 132 197 C 1 ,,H.,, isomer 133 198 biphenylefle 134 199 C 5 —alkyl beozene isomer 135 199 C 12 H 24 isomer 136 201 C 2 —alkyl styrene Isomer 137 201 C 11 H_ 2 isomer 133 201 C 5 —alkyl benzene isomer 201 C 12 H, 6 isomer 201 C ,H,, isomer —* 202 C,—alkvl stvrene Isomer 202 C 5 —alkyl beozene isomer 202 C H,, Isomer 12 . 204 C 5 —alkyi benzene isomer 204 C 2 —alkyl scyrene isomer 205 C 13 3, 6 isomer 206 C 13 6 23 isomer 206 C I3H.,6 Isomer 206 C H.,, isomer 13 * 206 C 1 .,H,, isomer 203 C 5 —alkyl beazene isomer 208 methvitecrahydronaphcha ler.e 208 C 13 H, 6 isomer 208 C 12 %,, isomer 208 C ,H,, isomer 1., 208 C 12 H, 6 isomer 209 C 12 H., 6 Isomer 210 r aohcha1ene 210 C 5 —alkyl benzer.e isomer 211 mechyltetrahydronaphtha lene 211 C 6 —aikyl beozerie isomer 211 C H , isomer 12 2.. 211 C 12 H, 3 isomer 211 C 13 6, 6 isomer 211 C 11 6 1 , (dimethyldihvdro im4ene or ethyltetrahvdron . .phthaleme 212 C 13 6 2 . isomer 212 C 13 3, 3 isomer 212 C 6 —alkyl beozene isomer 213 C 13 H 28 isomer 214 C 6 —alkyl benzene isomer 214 C 13 H, 6 isomer 14 C 13 6 28 Isomer 214 0133,6 isomer 215 C 13 3., 4 isomer 215 C 11 6 14 isomer 216 C 13 H., 6 isomer 216 trimechylphenOxysilane (SKC) 214 benzothiazOle 217 217 218 218 219 C 13 3., 6 isomer C 6 —alkyl bensene isomer C 13 3, 3 isomer C 7 —alkyl benrene isomer C 11 H 14 isomer Chromato- Elution graphic Temp. Compound Peak No. (°C) Chromato- Elution Temp. Compound Peak No. (°C) 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 62 ------- Table B—5. (con.) C i somer - 5 p.en.i;yri. jne (tent.) isomer C - H. isor er 1 . 3 C..—sLkyl ben ene iso ser C,.H . 3 trichy1Ind 1ine (tent.) C, isomer C , isomer 13 _.. C ,H ,, isomer Is _ C 1 ,H, 9 isomer Isomer C 1 H, 6 Isomer C, H. isomer 5-. C 13 23 Isomer C 1 ,H., isomer uflsaturated C—aikyl benname isomer 201 223 2—met y1napH:ha1ene 202 229 C 14 H, 5 isomer 203 229 C. Ii.. isomer 5 3 204 229 C isomer ls 33 205 229 unsa:srated C 7 —slky l be mene isomer 235 229 C , )L isomer 1s 3 207 229 C 13 .. , isomer 203 230 C 7 —aikyl benzene isomer 209 231 mechy1napHtha1e ie 210 231 C 12 H , isomer 211 232 C H, Isomer is sO 212 232 C 1 , 3 isomer 213 232 C 14 H 26 isomer 214 232 C_—a1 v1 bennene isomer 215 232 unsaturated C 7 —alkvl benrene isomer 216 234 C 16 H 3 , Isomer 217 234 C 5 —a1 y1 benzene Isomer 218 235 C rL isomer 15 0 219 235 C 15 H, 3 isomer 220 235 C H isomer 14 2. 221 235 C 7 —alkyl beozene isomer 222 235 unsaturated C..—alkyl berizene isomer 223 235 C 14 H, 3 Isomer 224 235 C 16 H_, isomer 225 236 isomer isomer 250 240 dimethy1 aphtha1ene 251 240 C 15 H 32 isomer 252 240 dithy1bvdronaphz aiene 253 240 toluene dlisoovsna:e (tent.) 254 240 dimethylnaphthalene 255 240 C 1 H 32 isomer 256 240 C 1 _H 30 isomer 257 240 C H , isomer 16 3s 253 240 unsaturated C 7 -alkyi. beneene Isomer 259 240 phenviladole (tent.) 260 240 C 16 H 25 isomer 261 240 C 15 H 30 Isomer 262 240 C 15 H, 2 isomer 263 240 C 15 H 32 isomer 264 240 C 1 H 3 , isomer 265 243 o tamethylcyclotetrasL1oxane ( I C C) 266 240 cedranoae (C 15 H 2 .0) (tent.) 257 240 C H isomer in 32 263 240 C 15 H, 5 Isomer Chromato- Elution aphic Temp. Compound Peak No. (°C) Chromato- Elution graphic Temp. Compound Peak No. (°C) 135 136 137 153 189 190 191 192 193 194 195 196 197 193 199 200 219 220 220 2:0 5’, 222 5 7 223 223 223 223 223 223 223 224 225 227 225 233 C —aL y1 ben ene Isomer 17 233 C, H , isomer in 223 233 C H - isomer is 229 233 C 17 H 35 Isomer 230 233 C 1 H 32 isomer 231 239 C,H, 3 isomer 232 239 unsaturated C 7 —slkyl benzene isomer 233 239 C H isomer 1. 26 234 240 C H , isomer 16 3. 235 240 biphenyl 236 240 C 14 9. 30 Isomer 237 240 C ,H, isomer 1. z3 238 240 C 14 H 25 Isomer 239 230 C 17 H 2 , Isomer 240 240 C. ,H isomer i. 22 241 240 C 15 H 33 isomer 242 240 C 12 H 16 isomer 243 240 C. , - isomer 244 240 C 15 H 30 Isomer 245 240 C 1 M, 6 isomer 246 240 C _H Isomer is 26 247 240 C 15 H 5 , isomer 245 240 C 1 _H 33 isomer 249 233 unsaturared C 3 — Lky1 beozene 63 ------- TABLE B—5. (con.) Qiromato- Elution graphic Temp. Compound Peak No. (°C) Chromato- E1ution graphic Temp. Compound Peak No. (°C) 269 240 C 16 R 32 isouier 270 240 diphenyl ether (tent.) 271 240 phenyl phenol (tent.) 272 240 long chain propyl ketone 273 240 benryl phenol (tent.) 64 ------- 30000 20000 U i 10000 2 J 0 4 O 6 O - 1Q Q -- .1210 _4 9_____ Iflip ithO .l1l,r(• (1:) 5 . l 9 i 1 g__.. _ ___ _ai _ 4 j° .-. 50 .. iQ Time (mIss) Figure B—6. Total ion current plot during gas liquid chromatography/mass spectroinetry of air sainpl.e from the interior of a Gremlin (8/26/76) automobile. A 100 m OV—1O1 SCOT capillary column was used. See text for condition . Sample volume 35.6 9.. l I 0 - 20JQ ‘ Zi’) . _ 211 Q U 1 b\ 1 ------- Table B—6. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—6. Cbxomato- Elution graphic Temp. Compound Peak No. (°C) Chromato- Elution -- graphic Temp. Compound peak No. (°C) 1 37 pro v1ene 7 122 C M, 3 isoer 2 51 butane 48 125 C_H 1 . iso er 3 51 butane 39 127 dithv1—1, —d1oxoLane (cent.) 3 58 C_H 10 isomer 50 126 C H 1 , tso at 5 58 c 5 a 1 _ isomer 51 128 C 3 H 16 isomer 6 60 C_H, isomer 52 128 C H isonet 7 62 C 5 H, isomer 53 130 C 8 H 16 isomer 8 66 carbon disulfide 54 131 C 3 H 1 , isomer 9 66 ealeic anhydride (temt.) 55 132 hexamethylcyclotrisiloxane (BKC) 10 66 propane nitrile (tent.) 56 134 C 9 H, 0 isonet 11 67 pentyns 57 135 C H 15 isomer 12 69 chiorobutane (tent.) 58 137 C 8 H 16 isomer 13 70 diethylanine (tent.) 59 138 C 3 H 18 isomer 14 72 C H, isomer 60 138 C H isomer 6 . 18 15 74 C 6 H 1 , isomet 61 142 C 2 —benzene 16 78 Methylpentane 62 144 C,—benzene 17 80 C 6 H 12 isomer 63 145 chlorocyclohexanol (tent.) 18 81 methyl sec—butylamine (tent.) 64 165 C 9 H 18 isomer 19 82 C H isomer 65 149 styrerle 6 14 20 82 C 6 H 12 isomer 66 149 C 2 —benzene 21 85 C 6 H 14 isomer 67 149 C 9 H 13 isomer 22 85 C 6 11, 0 isomer 68 150 C 9 i1 20 isomer 23 87 C H • isomer 69 152 pyridine 6 lh 24 90 1,1,1—trichloroethane 70 153 C 3 —benzene 25 94 C 6 H 10 [ hezadiene] 71 153 C 9 H 16 isomer 26 95 benzeme 72 153 C 9 H 18 isomer 27 97 C 7 H 16 6somer 73 154 C 9 H 18 isomer 28 97 C 7 H 14 isomer 74 155 C 3 —benzene 29 99 Cia 16 isomer 75 156 C 10 H, 2 isomer 30 103 C_H isomer 76 156 hexenyl hexenoate 31 104 C 7 H 16 isomer 77 157 C 9 H 16 isomer 32 105 C_H 12 isomer 78 157 C 10 H 2 isomer 33 106 C H , isomer 79 158 n—propylcyclohexane 34 108 CiR isomer 80 159 a—pimene 35 109 c 5 a 16 isomer 81 160 C 10 H 20 isomer 36 111 C H , isomer 82 161 n—propylbenzene 7 14 37 113 C H, isomer 83 162 benzaldehyde 8 i6 38 113 C 8 H 18 isomer 8!. 163 phenol 39 116 C 8 H 16 isomer 85 164 C 10 R., 9 isomer 40 118 CJi 16 isomer 86 164 C 10 H, 2 isomer 41 118 C 7 H , 0 isomer 87 166 methylstyrene 42 118 furfuryl methyl ether (tent.) 88 167 ethyl toluene 43 120 toluene 89 168 C 10 H 13 isomer 44 120 C 8 H 15 isomer 90 169 C 10 a 16 isomer 65 121 C 8 H 16 isomer 91 170 C 3 —bemzene 46 122 C 3 H 16 isomer 92 170 C 30 H, 0 isomer 66 ------- Table B—6. (con.) Chrontato- Elution Chromato- Elution — graphic Temp. Compound graphic Temp. Compound Peak No. (°C) Peak No. (°C) 93 170 C,,i_ 2 1 OOer 197 0. ,{,, t52 met 34 173 C,.d _ Isomer 1 .0 39 Jtmechvl ,:vreme 35 173 01,3:, tsooer 1-SI 199 C, 3,, 1s;m ,r 96 17; C—bemzene 102 203 .1irethyl pheaoi 97 174 C ,,H,, isomer 10) 200 C-benzene 93 176 C-a;nieme 144 :oo C._H, Isomer 99 177 C,,H_ 2 isomer 115 200 C.:H_, Isomer 100 173 cream! ethyl ether I;o 200 C,.,H,, isomer 101 179 C, 1 3,, Isomer 107 200 C;;H,; isomer 102 179 C ,H,. Isomer 143 200 0.23.3 thomer 103 180 aetnyistyrene 149 231 C—benzene 12; 130 C, 0 3, 3 isomer 130 202 hexmchlorce:oame [ rem:.) 105 180 C. ,H,, isomer 151 202 C_—benzerje 106 131 C.-benzene 152 202 C 11 H 4 isomer 107 181 C, 1 3 2 , isomer 133 203 chloroethylbertzeme tsm:.) 103 161 C,—Senzeme 15; 204 ter:ahydroms;hthaleme 109 131 C H,, isomer 155 :o; c. _ , Isomer 11 so 110 182 Isomer 156 204 Ci H :g isomer 111 132 cresol 157 205 dtmethyThhemol 112 132 C.H, isomer 153 206 C.,H isomer — s 13 113 133 C 11 3,, isomer 159 207 C 5 —henmeme 1:4 133 C,—benmene 160 208 methvlte:rahodromophthmene 115 133 0123.6 isomer 161 203 naphthaleme 116 184 C .3 ,, Isomer 162 203 C H isomer ls_ 1_6 117 155 C,—bemzene 163 209 C_—bemmene 118 135 chlomostvreme 16; 210 C.—benzene a 119 135 C .3,, Isomer 165 210 merhy1tetrahvdroma h:hs1eme 1 5 — — 120 136 C 3, isoaer 166 211 C ,H,, Isomer 11 s Q 1 5 121 186 012324 isomer 167 211 012322 Isomer 122 188 die:hlstyrene 163 211 015326 isomer 123 139 C.iH.. isomer 169 211 013323 isomer 124 139 C ,H,, isomer 170 212 C 6 —benmene 125 139 isomer 171 212 C 6 -benzene 126 190 C.—bemzene 172 213 C ,H, - Isomer S i i _o 127 192 C 5 —benzene 173 21; N—r.—burylditeridime (reot.) 123 192 C 1 1 H,, Isomer 17.1 215 C,—bertzene 129 192 0123.. isomer 175 216 methorçibemmsldehvde 130 193 C,,H, 6 Isomer 176 216 013325 isomer 131 193 dimerhylindane 177 217 d1methy1tstrahydromm htha1ene 132 194 C1 H.3 isomer 178 217 C 6 —benzene 133 194 C—benzene 179 213 013324 isomer 134 195 ciiH:o Isomer 130 213 C 13 H, 5 isomer 135 196 C, ,H,, Isomer 181 215 C 13 H, 3 Isomer 136 196 methyl antsole 132 213 methvlterrahvdronaphthalene 137 197 C 5 —benzene 153 220 C 7 —benmeme 133 197 0.1320 Isomer 154 221 C 13 H,, Isomer 67 ------- Table B—6. (con.) 1. :37 159 130 191 192 193 194 195 196 197 193 139 200 201 202 203 204 205 206 207 203 209 210 211 212 213 214 - . 1 a .er C. 5 - isorner _3 —) C— ,enzeae 0 . i .ethy1dLhvdroin3ene C ..—5enze e C , isoaer C .H isoc er 1 3.. C. 3 L . 3 isooer C 1 i., 3 isomr ey1trah dro ap otha1e e ethy1naphtha1e e C. .— oenze te C, JL,. iso oer .., iSOi er ehy1 apha1eoe :i echy1i a opropeny1benzene isoaer C..—benzene diisobutylthiophene (2) C 16 H 32 isoi:ier er y1cyc1ohexeoe C 15 H 30 iso oer r5 ethy1isopropeny1benzene C, 5 H 32 ismer Siphenyl C 1 ,E 30 iso ner C 1 ,H 30 isomer C,,H ., 3 isomer C 1 , H, 6 isomer C.H, —benzene 0 C, H 30 isoer dinethy lpht h.3 le n e isoner di—t—buty lcreso l C 15 H, 3 isomer C. H isomer .o 32 C,—tetrahydrottaphth a le me C 1 32 isomer C . { isomer 1 29 C 16 E 30 isomer C, H 3 , isomer C 15 H,, isomer C 1 H, 9 isomer C 1 i, 0 isomer C I L., isomer 16 . isorer C 16 H 30 isomer C 1 H 3 , isomer Chromato- Elution graphic Temp. Compoufld ?eak No. (°C) Chromato- EluSion graphic Temp. Compound Peak No. (°C) C . isomer 1 0 , imethvi o mthiie me im thv Lrnspn ha1ene dithy1pntr a1 ’me C .3,. isomer 1) . 3 C (,, isomer 1, —* C 15 H, 3 isomer di=ethvinaphtha1e e mechoxyanthracene (tar.t.) 223 223 223 226 226 227 223 228 229 230 231 232 232 233 233 234 235 236 238 239 240 a a a a 115 216 217 213 219 220 221 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 239 239 240 241 a a a a a 3 a a a a a a a a a a a a a 3 a a a a a a a a Isothermal 68 ------- 0 ii uT 01 III II j I j1 lj 10 III l!8 200 14 () 45 Figure 11—7. Total ion current plot during gas liquid chromatography/mass spectrometry of air sampl.e from the interior of a Rabbit (10/9/76) automobile. A 100 m OV—101 SCOT capillary column was used. See text for conditions. Sample volume 11.7 9.. II 20000 10000— 2 4d C) 6() 80 l0 15 100 120 ‘tenipe rat. ure ( C) — 20 4j) 25 Time (mm) JO is ------- Table B—7. ORGANIC COMPOUNDS IDENTIFIED FROM FIGURE B—7. 1 .2 CO, LA 42 - .ethylsilane 2 43 dichlorodifluorometh3ne 3 45 1—butane 4 46 acetaldehyde 5 50 isopentane 5A 50 trichiorofluormethane 53 51 propenal + propanal + furan 6 51 n—perttane 6A 52 acetome 63 52 dinethyl ether + diethyl ether 6C 53 dichioromerhane 7 54 freon 113 (3KG) 7A 54 CS, 75 55 isopropanol + ter—butanol 8 56 isobutyraldehyde 9 58 2—trethylpentane 9A 59 2—methyipropenal ( eut.) 93 59 diethyl sulphide 10 60 3—methylpenrane 1CA 60 n—butanal 103 61 methyl vinyl ketone 11 61 hexafluorobenzene (er) 12 62 n—hexane 13 63 chloroform 13A 64 methyl ethyl ketone 133 65 2,4—dimethylpentane 14 66 iethylcyclopentane + perfluoro— toluene (€1) 14A 66 1,2—dichloroeth .ane 4- isobutyl alcohol n—butyl alcohol C 6 H, 0 isomer benzene cyc lohexane 2— echy1hexane 2 • 3—dimethylhexane 3—nethylbexane dimethylcyclopentane isomer 3—methylbutanal trich loroethy lene dimethylcyclopeotane isomer n—heptane C.,H. isomer C 8 R isomer 24 92 mettvicyclohexane 25 54 C 3 5 19 isomer 25A 87 C,H - isomer 0 10 26 88 tri ethy1pentsne iso r 27 39 toluene 27A 91 C 8 H 13 isomer 28 92 2,4—dimethylbexane 23A 93 C 8 H 16 isomer 29 94 n—hexanal 29A 95 C 8 H 16 isomer 298 97 C 3 16 isomer 30 98 n—octane 31 98 tetrachloroethylene 31A 99 C H isomer o 16 32 102 silane compound 33 104 C 9 !i, 0 isomer 34 105 ethylcyclohexane 35 106 tri ethy1cyc1ohexane + C 9 H, 0 isomers 35A 107 C 9 8 13 isomer 36 108 ethylbenzene 36A 109 trimethylcyclohexane isomer 363 110 2,3—dimethyiheptane 37 110 —xy1ene 38 111 2—methyloctane 38A 112 4—ethylheptane 39 113 3—ethy1hepta e 40 114 styrene or cyclooctatetraene 40A 114 C 9 i 18 isomer 41 115 o—xylene 41A 115 n—heptaldehyde 42 116 C 10 R, 0 isomer 42A 116 C 9 R 13 isomer- 43 118 n—nonane - 44 120 C 9 H 13 + C 10 W, 0 isomers 45 121 isopropylbeozene 45?. 122 C, 0 8, 2 isomer 46 122 C 9 8 16 + C 9 H 18 isomers 47 123 C 10 U 22 isomer 48 124 propycyclohexane 49 125 terpinene isomer 69?. 126 C 10 H 22 isomer 50 126 beozaldehyde 50?. 127 n—propylbenzene + C 10 H, 0 isomer 51 US n—ethyltoluene ChromatO- Elution graphic Temp. Compound Peak No. (°C) Chroniato- Elution graphic Temp. Compound No. (°C) carbon tetrachioride 143 68 l4C 69 15 69 15?. 70 16 71 17 72 17?. 73 18 74 19 75 19?. 75 20 76 20?. 78 21 78 22 79 23 80 70 ------- TABLE B—7. (con.) Chromato- iioE T omato Elution graphic Temp. Compound graphic Temp. Compound Peak No.(°C) ______________________ Peak No. ( 0 C) ______________ 24 ._ .aoner 133 c,, , 52 :: l,: .s:L e.,en e e 72 153 o er 1 2 0 iSomer 73 159 dime Let j e ze ’ e omer 53 131 i sc m r 7 159 C 11 H, 3 some 54 132 l oLu me 75 160 isomer 34A 132 C. . , Iso mer 75 161 dimechvlphenoj isomer 313 133 c,, . isomer 76A 162 C—slk1 benme e i omee —J . 0 S 35 :33 C, , 5 Lsome 77 163 CpH 2 + C 11 H, 0 !so rs 53A 134 isomer 7 ’A 163 pent*jccleiexsne 56 135 1,2,1—tt6liemzeme 161 C 19 H_, isomer 55A 135 C 1 i 23 isomer 77C 155 te raet 5emeeme Isomer 8 dim y1? ieo.o! isomer 33 143 to so ut 10 79 166 C 1 1, 5 boor 53A 113 1,2 ,1— :imechv1bemzeme 30 167 c: 12 _o 39 141 C.—aikyl bore — C. :6:j 1 163 c 15 i 5 . iscoer SIA 153 C 5 —a1yl benze er 39A 11.1 C 1 E... .. coer 82 169 C SL 5 isomer “1:22 iSomer 83 170 r.a : a1eme 61 13 cd ., isomer 172 dodeceme 62 144 b: icyc5o6exaoe 85 175 i—do ecome 62A 145 C—a lkyl benzene + C, H,, 56 j77 C 13 , isomers 87 178 c, 3 73 isomer 63 155 — ropv1 o1uene 180 C 13 H 5 isomer 53A 136 isomer 91 132 he n1yc 5ex 633 146 o 5u::1benzene 9 180 C 13 H,, isomer 64 147 o—poo?v10 0luene 91 184 C, 5 3, 3 isomer 64A 147 C 1 1 H . isomer 9L4 134 C 13 H 18 1 50700 643 133 ,d 2 . Isomer 92 135 C 13 H, 8 smmer 65 148 o—prc?yltolueme 3 136 2—methyldodecame 63A 119 C 10 d 53 isomer 94 is;’ 3—methyidodecon 66 150 diethylbemmene isomer 95 189 C . Is 33 SSA 150 C—sl yi benz r,e isomer 95A 193 C 13 H 26 isoner 67 151 C, H , iscner 953 194 C .H, iS0000 63 152 C,—alkvl benzene isomer 9 196 o—tridecane 4 — 69 154 C, d., isomer 96A 199 C ,i is o -— 14 3 70 155 C — ic-,1 benrone + C 1 d,, 963 205 C ,H, isomer S isc ers 96C 203 C14 123 Isomer 71 156 is—ori000sne 71 ------- 4b 6b I 80 I 100 I 120 Temperature I (0 0 160 I 180 I 200 I I I I I I I 1 I 5 10 15 20 30 35 40 45 Figure B—8. 25 Time (mm) Total ion current plot during gas liquid chromotography/mass spectrometry of a background air sample. A 100 m OV—1O1 SCOT capillary column was used. See text for conditions. Sample volume 35.6 . 6000 — 5000 4000 - 3000 2000 1000 - 0 0 ------- Table B—S. ORGANIC CO OUNDS IDENTIFIED IN ANBIENT AIR BACKGROUND ADJACENT TO THE GRENLIN. Chromato- Elution apbic Temp. Compound Peak No. (°C) Chromato- Elution graphic Temp. Compound Peak No. (°C) 1 39 methylsilana (3KG) 18 90 C E 18 isomer IA 42 CO 2 19 92 ri—octane 2 45 isopeotatoe 19k 93 tetrachioroerhylene 2k 46 CH 10 isomer 20 97 silane compound (3KG) 2B 47 acetaldehyda 20k 100 C 9 H 20 Isomer 2C 48 C 5 H 10 isomer 208 103 ethylbenzerie 3 49 acetone + freon 113 (5KG) 21 105 £—xylene 4 52 C 6 11 12 isomer ZLi . 101 C H 20 isomer 5 53 2—methylpentame 218 108 C 9 }1 20 isomer 5k 54 3—methylpenrane 21C 109 styrerie 6 55 hexafluorobenzene (es) 210 110 o—xylene 7 56 n—hexane 22 111 C 9 H 18 isomer 7k 57 chloroform 23 113 n—nonane lB 58 C 6 H 12 isomer 24 117 silane compound (8KG) 8 59 perfluorotoluene (e’) 24A 121 C 10 H, 2 isomer 8A 60 methylcyclopentane 25 124 benzaldehvde 9 64 banzene 25k 125 m—ethyltoluene 9k 65 carbon tetrachioride 258 126 C 3 —alkylbenzene isomer 98 65 cvc lohexane 26 129 phenol 10 66 2—methylhexane 26k 131 o—ethyltoluene 10k 67 2,3—dimethylpentane 27 132 C 10 H 20 isomer 11 68 3—methylhexane 28 135 n—decame hA 69 dimethylcyclopentane isomer 28k 137 1,2,3—trimethylbeozene 12 70 C 7 11 16 isomer 29 138 C 11 24 isomer 12k 71 isomer 30 143 C 11 H 2 , isomer 13 72 a—heptane 30k 145 acetophenone 13k 73 C 7 H 14 isomer 308 146 C 11 H 24 isomer 13B 76 C..H isomer 30C 148 C,—alkyl benzene isomer i 14 14 77 methycyclohexane 31 151 C 11 Hn 4 Isomer 15 79 C 8 H 18 isomer 32 154 ri—uridecame 16 82 C 8 Hj 8 isomer 32k 165 silane compound (8KG) 17 84 to].uene 32B 170 C 12 }i 24 isomer 17k 85 C 3 H 13 isomer 32C 187 —methy1naphtha1ene 178 87 C H - isomer 320 190 ci.methylnaphthalene 8 in 17C 88 C 8 H 16 isomer 73 ------- 74 ------- APPENDIX C FREQUENCY—PRIORITIZED LIST OF ORGANICS FOL ND IN AUTOMOBILE INTERIORS -7- ------- Table C—i. LIST OF ORGANICS r - z Comoound . E - - . Z t, < > = 0 -. z — - z 0 < ;a > n—propylbenzene x x x x x x C 4 —alkvl beezene isomers x x x x x x C 5 —alkyl benzene isomers x x x x x 1—butene x x x x x x terpinene isomers x x x x X x C 11 H 22 isomer x x x x x x C 13 H, 5 isomer x x x x x x C 9 H 15 isomer x x x x x C 9 H 18 isomer x x x x x C 11 H, 0 isomers x x x x x C 12 H 26 isomers x x x x x C H,isomers x x x x x 12 2-. C 13 H., 3 isomers x x x x x dimethyiphenol isomers x x x x dimethy lstyrene x x x x dimethy lnaphtha lenes x x x x n—butane x x x x n—pentane x x x x C 6 N 10 isomers x x x x C 8 3 16 isomers x x x C H, isomers x x x x 10 LS butylcyclohexane x x x x C 14 H 30 isomers x x x x C 14 H, 3 isomers x x x x 2—methy l—2—propano l x x x cresol x x x carbon disulfide x x x beozothiazole x x x ethy lbenzene x x x C 5 —alkylbenzene isomers x x x dimethyldihydroindene or methy l tetrahydronaphtha lene x x x C 7 —alkylbenzene isomers x x x biphenyl X X X methyistyrene isomers x x x naphthalene x x x 2—butene x x x 76 ------- Table C—i (con.) . r’ — Co moo nd Z = C z .-, - propylcyclohexane x x x isomers branched x x x C 10 H 1 . isomers x x x isomer-s x x x C H 32 isomers x x x C 15 H 30 isomers x x x C 15 N 34 isomers x x x C 16 H 32 isomers x x x l,2,4—trimethylbenzene x x x propenal x x propanal x x 2—methylproperisl (tent.) x x n —butanal x x n—hexanal x long chain propyl. ketone x x di—t--butyl cresol X X furan x x dimethyl ether x x vinyl methyl ether (tent.) x x n —cresyl ethyl ether diphenyl ether (tent.) benzyl phenyl ether (tent.) o—propyitoluene x x —xylene x X dimethylethylbenzene isomers x x djmechylindane x x r.ethyltetrahydronaphthalenes x x maleic anhydride (tent.) x C 3 R 14 isomers x x C 10 H 20 isomers x x pencylcyclohexane x x ri—dodecane x x C 12 H 27 isomers x x C 14 H 26 isomers x x C 15 .1 28 isomers x x C 15 H 24 isomers x x C 17 H isomers x x l—bucanol x x isopropylbenzerze x x 77 ------- Table C—i (con.) : . z - . — Compound z n i-. . t U -‘ z - — - U . 1,2—dibromoethane (tent.) x chiorobutane (tent.) x chiorocyclohexanol x chiorostyrene (rent.) x hexachloroethane (tent.) chloroethylbenzene (tent.) X trjchlorobenzene isomer x 2—merhyipropanal x 3—methylburanal x hexanal isomer x 3—methylbutanal x n—heptarial x 2—butenal x ethylbutanal (tent.) x methoxybeazaldehyde x methyl vinyl ketone x methyl ethyl ketone x 4—methyl—2—peatanone x 2—heptanone X octanone isomer (tent.) x cedranone (C 15 H 24 0) x 2—propanol x 2—methyl—l—propanol x 2—methyl-l-butaaol (tent.) x undecenol (tent.) x ethyiphenol isomer x ethyl acetate x hexenyl hexenate (tent.) Z dierhyl ether x ethyl vinyl ether x furfuryl methyl ether (tent.) x diniethyl—l,4—dioxane (tent.) x methyl anisole x butyl methyl ether x dihydropyran X anisole x diphenoxybenzene x methoxyanthracene (tent.) X phthalate X 78 ------- TABLE C—i. (con.) -. , Compound z n n - , . C j C U C C — — — J C U < c ; N—methyl—2—butylamine (tent.) x diethyj.amine (tent.) x N—n-butylpiperidine (tent.) butylaminodiphenylamine (tent.) X 2—amino—2—methyl—1--propanol x cyclohexylarnine (tent.) x aniline x trimethylindoline (tent.) phenylindole (tent.) x pyridine (cent.) X N—ethylpyridine (tent.) x pheziylpyridine (tent.) x dimethyiquinolifle x propane nitrile (tent.) x propane nitrile (tent.) x 3, 3—dimethylcyclobutane carbonnitrile (tent.) x toluene diisocvanate (tent.) diethyl sulfide diisobutylthiopheCe (tent.) C 8 —alkyl thiOphene (tent.) x tri methylisopropylbenzene x phenylcyclohexane X C 8 —alkyl ben ene x C 2 —alkyl styrene isomers x diethyisryrene isomers x di—t—bucylphenanthrene (tent.) x dimerhyldihydronaphthalenes x tetrahydronaphthaiene x ethvltetrahydronaphthsisne x C,—alkyl tecrahydronaphth3lene dimethyltetrahydrOnaphthalefle diethylbetizene isomer x 1,3,5—trimethyl benzene x —propyltoluan e x tetranethylbeuzene isomer x —ethy1totuene x 79 ------- Table C—i (con.) -. z -. — s-I 0 Compound biphenylene x unsaturated C 6 —allcyl benzene isomers x unsaturated C 7 ’-alkyl benzene isomers x C 9 —alkyl benzene isomer x unsaturated C 8 —alkyl benzene isomers x propene (tent.) x C 4 1 10 isomer x cyclopentene x pentyne x c 5 a 10 isomer x methylpentene x C 7 H 12 isomer x methyl hexyne x methyl cyclohexene isomers x e thylcyclohexane x trimethylpentane isomer x trimethylcyclohexane x 2,3—diinethylheptane x C 10 11 12 isomer decahydronaphthalene (tent.) x triiaobutylene X isomers x C 12 H 18 isomer x hexylcyclohexane x 2—methyldodecane x 3-inethyldodecane x n—tridecane x C 14 B 24 isomers C 14 B 22 isomers x C 15 H 26 isomers x isomers x c 16 a 28 isomers x C 16 H 30 isomers X 80 ------- TECHNJCAL REPORT D,ATA (?ic:se re3d f; r c::o :s o’ r e ‘c ’ r com .1le? 7; 1. REPORT NO. 2. 3. REC P ENTS ACCESSION’ NO. EPA-600/7-77- 149 4. TITLE AND SUBTiTLE 5. REPORT DATE Organic Emissions from Automobile Interiors 7. AUTHOR(S) S.PERFOR 1iNG ORG ZAflON REPORT NO Ruth A. Zweidinger 9. PERFORMING OROANICATION NAME AND ADDRESS Res earch Triangle Institute P.O. Eox 12194 Research Triangle Park, North Carolina 27709 10. PROGRAM ELEMENT NO. EHE 62 4A 11. CONTRACT ORANT NO. 68-02-1325, Task 46 12. SPONSORING AGENCY NAME AND ADDRESS EPA, Office of Research and Development Industrial Environmental Research Laboratory Research Triangle Park, NC 27711 13. TYPE OF REPORT ND PERIOD COVERED Task Final: 7/75-1/76 EPA/6 00/13 1S.SUPPLEMENTARY NOTES IERL—RTP project officer for this report is Joseph A. McSorley, Mail Drop 63, 919/541-2745. 16. AESTRACT The report gives results 0: an eva1uat on of six subcomnact automobiles for the emission of vinyl chloride monomer (VCM) and other organics into the pas- senger compartment. Evaluated were a Ford Pinto, AMC Gremlin, GMC Vega, GMC Chevette, NMC Datsun 710, and VW Rabbit. VCM was quantified using charcoal car- tridges interfaced with gas/liquid chromatography-mass spectrometry in the single- ion detection mode. VCM levels in the Pinto, Gremlin, Vega, and Chevette were less than the 50 ppb detection limit. With improved instrumental parameters, a 2 ppb detection limit was obtained. Under these conditions, VCM was not detected in the Chevette, but was detected in the Rabbit and the Datsun ‘710. Samples were taken for qualitative gas’liquid chromatograohy-maSS spectrometric analysis of each automo- bile, using Tenax G.C. sorbent. This analysis produced a composite list of 147 organic compounds which were identified in the automobiles and not in the ambient air in the vicinity of the test. Another 36 compounds were tentatively identified. 17. KEY WORDS AND DOCU’.lENT ANALYSIS Air Pollution Air Pollution Control l3B Organic Compounds Vinyl Chloride Automobiles Vapors Carcinogens Automobile interiors 07C ‘ 13F 07D lOSE 13. 3iS REUT ON STATEMENT 19, SECURITY CLASS port) Unclassified Unlimited 2O. SECURITY CLASS Th . s ze; Unclassified .—.-.—..-—.....- . . 2i.NO. PACES 09 22. - EPA Form 2220-1 (9-73) ------- |