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tional Technical Information Service, 1982, LMF-93. (18) Miksch, R. R.; Anthon, D. W.; Fanning, L. Z.; Hollowell, C. D. Revzan, K.; Glanville, J. Anal. Chem. 1981, 53, 2118-2123. (19) Singh, J.; Walcott, R.; St. Pierre, C.; Ferrel, T.; Garrison, S.; Gramp, G.; Groah, W. “Evaluation of the Relationship Between Formaldehyde Emissions from Particle Board Mobile Home Decking and Hardwood Plywood Wall Paneling as Determined by Product Test Methods and Formaldehyde Levels in Experimental Mobile Homes”; technical report, U.S.Department Housing and Urban Development, Office of Policy Development and Research, Division of Energy, Building Technology and Standards, March 1982.
(20) Roberts, J. D.; Caeerio, M. C. “Basic Principles of Organic Chemistry”; W. A. Benjamin: New York, NY, 1965; pp 1083-11 15. (21) Johns, W. E.; Jahan-Latiban, A. Wood Fiber 1980, 12, 144-152.
Received for review December 20,1982. Accepted June 29,1983. Research performed for the Consumer Product Safety Commission under Interagency Agreement CPSC-IAG-801463 under U S . Department of Energy Contract DE-AC04-76EV01013. The views expressed in this paper are those of the authors and do not necessarily represent those of The Consumer Product Safety Commision or the U S . Department of Energy.
NOTES Emissions of Ammonia and Amines from Vehicles on the Road William R. Plerson” and Wanda W. Brachaczek
Research Staff, Ford Motor Company, Dearborn, Michigan 48 121 Experiments were conducted in the Allegheny Mountain Tunnel of the Pennsylvania Turnpike in 1981 to evaluate ammonia emissions from gasoline-powered vehicles and heavy-duty diesel vehicles in highway operation. Emission of NH3 and aerosol NH4+from gasoline-powered vehicles was below our detection limit, i.e., K0.28 mmol/km. Emission of NH3 + NH4+ from diesel trucks was 1.45 f 0.35 mmol/km or, stated as NH3, 25 f 6 mg/km (possibly including significant amounts from the livestock hauled by many of these trucks). Dimethyl- and diethylamines were sought at the same time because the two amines are of interest as possible atmospheric precursors of dimethyland diethylnitrosamines which are animal carcinogens that have been reported in air principally in industrial areas. No amines were found; methylamine, ethylamine, dimethylamine, diethylamine, and trimethylamine were all below the detection limits of 0.04-0.3 mg/km (depending on the compound) for gasoline-powered vehicles and 0.08-0.7 mg/km for heavy-duty diesels. Introduction From time to time questions are raised about nitrosamines and nitramines in the environment. These compounds are carcinogenic to animals and hence are suspected human carcinogens (1). Nitrosamines have been reported in ambient air (2-4), especially near industrial sources. Evidently the amount of nitrosamines emitted in vehicle exhaust is inconsequential (5-7). Nitrosamines have been sought in diesel crankcase blowby emissions, with positive (8),negative (6),and equivocal (9) results. The upper limits on the amounts reported are many orders of magnitude too small to account for the nitrosamines reported (2-4) in air samples. The question arises, then, whether dialkylamines are emitted by motor vehicles at rates sufficient to form significant amounts of nitrosamines by reactions in the atmosphere with traces of nitrous acid or even concurrently emitted nitrogen oxides. The answer is definitely no, in the case of gasoline-powered automo0013-936X/83/0917-0757$01.50/0
biles, on the basis of chassis-dynamometerexperiments (5, 10-17). The work reported herein shows that the same holds in an actual on-road setting and for both gasolinepowered and heavy-duty diesel vehicles. The method employed in this study for amine measurements also provided data on ammonia emissions. Such data are of interest from the standpoint of emission inventories and also because ammonia is important in atmospheric chemistry. As a pollutant, ammonia from automotive sources evidently is not significant (18, 19). Ammonia emissions data are available from chassis dynamometer studies (5, 12-1 7,20-26), but heretofore not from roadway studies. Experimental Procedures Amines and ammonia together with their salts were measured in the Allegheny Mountain Tunnel of the Pennsylvania Turnpike, July 22-30,1981. Air was sampled at 3 L/min (known within a few percent) through impingers containing 0.01 N H2S04 (40 mL) to trap the gas-phase amines and ammonia. Upstream of each impinger was a Teflon membrane filter (Ghia “Zefluor”) of 0.2-pm nominal pore diameter to remove particulate matter including ammonium salts, alkylammonium salts, and any amines adsorbed to the aerosol particles. Each filter was immersed, immediately after sampling, in 0.01 N H2S04 (10 mL). The H2S04impinger and filter solutions were analyzed for NH4+and alkylammonium ions by an ion chromatographic procedure patterned after one described elsewhere (27) and also for amines by gas chromatography with a nitrogen-sensitive detector. The gas chromatographic method (28) employs a 1.8 m X 2 mm glass column packed with 4 % Carbowax 20M/0.8% KOH on Carbopak B, the silanized glass wool having been removed from the front of the column in order to prevent adsorptive losses of the amines and to prevent a “memory” effect. Before analysis, the sample solutions were placed in small vials sealed with Teflon-coated septa and then made alkaline by injecting 1N KOH into the vials through
0 1983 American Chemical Society
Envlron. Scl. Technol., Vol. 17, No. 12, 1983 757
Table I. Emission Rates of Ammonia and Amines, 1981 Allegheny Tunnel Experiment: Impingers and Prefilters Combineda mg/kmb gasolineC 1 . 3 i 3.5e
