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Vehicle emissions are a major source of carbonyls, which play an important role in atmospheric chemistry and urban air quality. Yet, little data are available for speciated carbonyls emitted by vehicles and especially by heavy-duty diesel vehicles. On-road vehicle emissions of carbonyls have been measured in May 1999 at the Tuscarora Mountain Tunnel, PA. Ten saturated aliphatic aldehydes, 4 saturated aliphatic ketones, 4 unsaturated aliphatic carbonyls, 4 aliphatic dicarbonyls, and 9 aromatic carbonyls have been identified and their concentrations measured. For light-duty (LD) vehicles, total carbonyl emissions were ca. 6.4 mg/km, and the 10 largest emission factors were, in decreasing order, those of formaldehyde (2.58 +/- 1.05 mg/km, ca. 40% of total carbonyls), acetone, acetaldehyde, heptanal, crotonaldehyde, 2-butanone, propanal, acrolein, methacrolein, and benzaldehyde. For weight class 7-8 heavy-duty diesel vehicles (7-8 HD), total carbonyl emissions were ca. 26.1 mg/km, and the 10 largest emission factors were, in decreasing order, those of formaldehyde (6.73 +/- 2.05 mg/km, ca. 26% of total carbonyls), acetaldehyde, acetone, crotonaldehyde, m-tolualdehyde, 2-pentanone, benzaldehyde, a C5 saturated aliphatic aldehyde isomer, 2,5-dimethylbenzaldehyde, and 2-butanone. Aromatic carbonyls, unsaturated aliphatic aldehydes, and aliphatic dicarbonyls represented larger fractions of the total carbonyl emissions for 7-8 HD vehicles than for LD vehicles. For HD vehicles, formaldehyde and acetaldehyde emission factors measured in this study are ca. 4-5 times lower than those measured in previous work. For LD vehicles, emission factors measured in this study are generally lower than those measured in earlier work and are about the same, within reported uncertainties, as those measured in 1992 in the same highway tunnel.

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The Van Nuys Tunnel experiment conducted in 1987 by Ingalls et al.(see A&WMA Paper 89-137.3), to verify automotive emission inventories as part of the Southern California Air Quality Study (SCAQS), gave higher CO and HC emission-rate values than expected on the basis of automotive-emission models-by factors of approximately 3 and 4, respectively. The CO/NO X and HC/NO X emission-rate ratios moreover were higher than expected-by similar factors (NO X emission rates were about as expected). The purpose of the present paper is to review the literature on dynamometer and on-road (in tunnels and along roadways) testing of inuse vehicles, and on urban-air CO/HC/NO X concentration ratios, to see whether the Van Nuys Tunnel results are reasonable in terms of previous experience. The conclusions are that (1) on-road CO and HC emissions higher than expected have been reported before, (2) on-road CO and HC emissions consistent with the Van Nuys Tunnel results have been reported before, and (3) on-road CO/NO X and HC/NO X emission-rate ratios higher than expected have been reported before. The Van Nuys Tunnel NO X results actually are lower than in other on-road experiments, and the CO/NO X and HC/NO X ratios consequently are higher. The higher-than-predicted CO/NO X and HC/NO X ratios at Van Nuys and other on-road sites suggest richer operation on-road than predicted or than observed in the inuse-vehicle dynamometer tests which serve as the model inputs. Support for these suggestions and conclusions is found in comparison of urban-air and emission-inventory HC/NO X ratios.The Southern California Air Quality Study (SCAQS) is a large cooperative air quality study designed to address the problem of air pollution in the Los Angeles basin by developing a better scientific understanding of the processes in- ImplicationsThis paper suggests the existence of a discrepancy, in California and nationwide, between predicted and measured on-the-road motor vehicle emissions of carbon monoxide and hydrocarbons. It is important to resolve the issue, because it affects the analysis of the 1987 Southern California Air Quality Study (SCAQS) and more generally because it affects air quality modeling and regulatory strategies for motor vehicle emissions in California and nationwide. One component of the SCAQS field measurements was a highway tunnel experiment conducted in Van Nuys, CA, by Ingalls et al. 2>3 with CRC support. The purpose was to determine automotive pollutant emission rates in an on-road setting in the Los Angeles basin, for use in constructing the emissions inventory needed for the SCAQS.The NO X emission rates deduced from the tunnel experiment proved to agree reasonably well with predictions from the CARB EMFAC7C (i.e., version 7C of EMFAC) model, 4 which uses very extensive dynamometer emission rates as inputs, or the similar EPA MOBILE4 model. 5 However, the CO and hydrocarbon (HC) emission rates were substantially higher than predicted, by a factor of 2.7 ± 0.8 on the average for CO and 4.0 ± 1.8 for HC, relative to EMFAC7...

Total and speciated particulate matter (PM2.5 and PM10) emission factors from in-use vehicles were measured for a mixed light- (97.4% LD) and heavy-duty fleet (2.6% HD) in the Sepulveda Tunnel, Los Angeles, CA. Seventeen 1-h test runs were performed between July 23, 1996, and July 27, 1996. Emission factors were calculated from mass concentration measurements taken at the tunnel entrance and exit, the volume of airflow through the tunnel, and the number of vehicles passing through the 582 m long tunnel. For the mixed LD and HD fleet, PM2.5 emission factors in the Sepulveda Tunnel ranged from 0.016 (+/-0.007) to 0.115 (+/-0.019) g/vehicle-km traveled with an average of 0.052 (+/-0.027) g/vehicle.km. PM10 emission factors ranged from 0.030 (+/-0.009) to 0.131 (+/-0.024) g/vehicle. km with an average of 0.069 (+/-0.030) g/vehicle.km. The PM2.5 emission factor was approximately 74% of the PM10 factor. Speciated emission rates and chemical profiles for use in receptor modeling were also developed. PM2.5 was dominated by organic carbon (OC) (31.0 +/- 19.5%) and elemental carbon (EC) (48.5 +/- 20.5%) that together account for 79% (+/-24%) of the total emissions. Crustal elements (Fe, Mg, Al, Si, Ca, and Mn) contribute approximately 7.8%, and the ions Cl-, NO3-, NH3+, SO4(2-), and K+ together constitute another 9.8%. In the PM10 size fraction the particulate emissions were also dominated by OC (31 +/- 12%) and EC (35 +/- 13%). The third most prominent species was Fe (18.5 +/- 9.0%), which is greater than would be expected from purely geological sources. Other geological components (Mg, Al, Si, K, Ca, and Mn) accounted for an additional 12.6%. PM10 emission factors showed some dependence on vehicle speed, whereas PM2.5 did not. For test runs in which the average vehicle speed was 42.6 km/h a 1.7 times increase in PM10 emission factor was observed compared to those runs with an average vehicle speed of 72.6 km/h. Speciated emissions were similar. However, there is significantly greater mass attributable to geological material in the PM10, indicative of an increased contribution from resuspended road dust. The PM2.5 shows relatively good correlation with NOx emissions, which indicates that even at the low percent of HD vehicles, which emit significantly more NOx than LD vehicles, they may also have a significant impact on the PM2.5 levels.

The purpose of the Enhanced Particulate Matter Surveillance Program was to provide scientifically founded information on the chemical and physical properties of dust collected during a period of approximately 1 year in Djibouti, Afghanistan (Bagram, Khowst), Qatar, United Arab Emirates, Iraq (Balad, Baghdad, Tallil, Tikrit, Taji, Al Asad), and Kuwait (northern, central, coastal, and southern regions). To fully understand mineral dusts, their chemical and physical properties, as well as mineralogical inter-relationships, were accurately established. In addition to the ambient samples, bulk soil samples were collected at each of the 15 sites. In each case, approximately 1kg of soil from the top 10 mm at a previously undisturbed area near the aerosol sampling site was collected. The samples were air-dried and sample splits taken for soil analysis. Further sample splits were sieved to separate the <38 µm particle fractions for mineralogical analysis. Examples of major-element and trace-element chemistry, mineralogy, and other physical properties of the 15 grab samples are presented. The purpose of the trace-element analysis was to measure levels of potentially harmful metals while the major-element and ion-chemistry analyses provided an estimate of mineral components. X-ray diffractometry provided a measure of the mineral content of the dust. Scanning electron microscopy with energy dispersive spectroscopy was used to analyze chemical composition of small individual particles. From similarities in the chemistry and mineralogy of re-suspended and ambient sample sets, it is evident that portions of the ambient dust are from local soils.