Long-Term Efficiency of Catalytic Converters Operating in Mexico City

ABSTRACT

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones.

The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NO_x emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure     

On-Road,In-Use Gaseous Emission Measurements by Remote Sensing of School Buses Equipped with Diesel Oxidation Catalysts and Diesel Particulate Filters

Abstract

A remote sensing device was used to obtain on-road and in-use gaseous emission measurements from three fleets of schools buses at two locations in Washington State. This paper reports each fleet’s carbon monoxide (CO), hydrocarbon (HC), nitric oxide (NO), and nitrogen dioxide (NO₂) mean data. The fleets represent current emission retrofit technologies, such as diesel particulate filters and diesel oxidation catalysts, and a control fleet. This study shows that CO and HC emissions decrease with the use of either retrofit technology when compared with control buses of the same initial emission standards. The CO and HC emission reductions are consistent with published U.S. Environmental Protection Agency verified values. The total oxides of nitrogen (NO_x), NO, and the NO₂/NO_x ratio all increase with each retrofit technology when compared with control buses. As was expected, the diesel particulate filters emitted significantly higher levels of NO₂ than the control fleet because of the intentional conversion of NO to NO₂ by these systems. Most prior research suggests that NO_x emissions are unaffected by the retrofits; however, these previous studies have not included measurements from retrofit devices on-road and after nearly 5 yr of use. Two 2006 model-year buses were also measured. These vehicles did not have retrofit devices but were built to more stringent new engine standards. Reductions in HCs and NO_x were observed for these 2006 vehicles in comparison to other non-retrofit earlier model-year vehicles.     

Trends of exhaust emissions from gasoline motor vehicles in the metropolitan area of Mexico city

Light duty gasoline vehicles account for most of CO, hydrocarbons and NO_x emissions to the urban environment in the metropolitan area of Mexico City. In order to ameliorate air pollution, several control measures have been imposed in the last decade, such as: up-grade of gasoline's quality, stringent environmental standards, and catalytic converters. On the other hand and from the beginning of 2001, Tier I emission standards became mandatory for all new model year sold in the country. Car manufacturers in Mexico do not guarantee the performance of their exhaust emissions systems for a given mileage. In this work, we present results on brand new vehicles that indicate that NO_x emission factors, though they are within the Tier I standard, deteriorate rapidly with the travelled distance (mileage).     

A Fuel-Based Motor Vehicle Emission Inventory

Abstract

A fuel-based methodology for calculating motor vehicle emission inventories is presented. In the fuel-based method, emission factors are normalized to fuel consumption and expressed as grams of pollutant emitted per gallon of gasoline burned. Fleet-average emission factors are calculated from the measured on-road emissions of a large, random sample of vehicles. Gasoline use is known at the state level from sales tax data, and may be disaggregated to individual air basins. A fuel-based motor vehicle CO inventory was calculated for the South Coast Air Basin in California for summer 1991. Emission factors were calculated from remote sensing measurements of more than 70,000 in-use vehicles. Stabilized exhaust emissions of CO were estimated to be 4400 tons/day for cars and 1500 tons/day for light-duty and medium- duty trucks, with an estimated uncertainty of ±20% for cars and ±30% for trucks. Total motor vehicle CO emissions, including incremental start emissions and emissions from heavy-duty vehicles were estimated to be 7900 tons/day. Fuelbased inventory estimates were greater than those of California's MVEI 7F model by factors of 2.2 for cars and 2.6 for trucks. A draft version of California's MVEI 7G model, which includes increased contributions from high-emitting vehicles and off-cycle emissions, predicted CO emissions which closely matched the fuel-based inventory. An analysis of CO mass emissions as a function of vehicle age revealed that cars and trucks which were ten or more years old were responsible for 58% of stabilized exhaust CO emissions from all cars and trucks.     

Fast and quantitative measurement of benzene,toluene and C2-benzenes in automotive exhaust during transient engine operation with and without catalytic exhaust gas treatment

Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C₂-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.     

An Analysis of Michigan and California CO Remote Sensing Measurements

Abstract

Remote sensing measurements of CO emissions from on-road vehicles were made in California in 1991 and in Michigan in 1992. It was determined that both fleets had a small linear increase in the high emitter frequency (vehicles emitting more than 4% CO) as a function of vehicle age for 1986 and newer model vehicles. Although high emitting vehicles were only a small minority of the fleet, they had a dominant impact on the mean CO and total CO emitted by the fleet. In Michigan, the highest emitting 5% of passenger cars generated 45% of the CO from cars. In California, the highest emitting 5% of passenger cars generated 38% of the CO from cars. There was a high correlation between the mean CO emitted by each model year of vehicle and the frequency of high emitting vehicles within the model year for both the Michigan and California fleets. The frequency of high emitters within any model year had no obvious relation to that model year’s certification standards. The high emitter frequencies for vehicles less than nine years old were very similar for the California and Michigan fleets. An increase in the high emitter frequency in the ten-year-old and older Michigan passenger car fleet (relative to the California passenger car fleet), suggests, but does not conclusively demonstrate, that the rate of high emitters in Michigan and California is reduced by the inspection and maintenance (I/M) programs.     

A Characterization of Emissions from an Early Model Flexible-Fuel Vehicle

An emission study was conducted on a 1987 Ford Crown Victoria flexible-fuel vehicle, an early prototype which had been driven about 25,000 miles. The vehicle was run on both gasoline and a blend of 85 percent methanol and 15 percent gasoline. Emission rates of regulated pollutants (hydrocarbons, carbon monoxide, nitrogen oxides, formaldehyde, and methanol) and nonregulated pollutants (speciated organic materials) were determined for both exhaust and evaporative emissions. Tests were run varying the driving cycle, ambient temperature and catalytic converter. In general, hydrocarbon composition of exhaust emissions was significantly affected by catalyst replacement and cold starts, slightly affected by driving schedule, and unaffected by ambient temperature and test fuel. Hydrocarbon composition of evaporative emissions was only sensitive to the type of evaporative test being performed: diurnal tests typically had larger fractions of lower molecular weight paraffins than hot soak tests.     

An empirical method for predicting exhaust emissions of regulated pollutants from future vehicle technologies

A methodology is presented for estimating emissions of passenger cars and light commercial vehicles complying with future European Union emission standards, which introduces appropriate reductions over the emission factors of existing vehicle technologies. For three-way catalyst gasoline vehicles, future real-world emissions are assumed to decrease by the same ratio as emission standards. Additionally, distinction is made between emissions during the thermally stabilised emission control system operation and emissions during the cold-start phase, where reductions are mainly due to the decreasing light-off time of future catalyst technologies. In case of diesel vehicles, some of the emission standards, such as 1993 CO, did not represent the actual emission level of vehicles at the time. Therefore, reductions brought over the 1993 emission factor are based both on relevant emission standards reductions and on technological considerations. In a second step, the derived emission factors are corrected to account for vehicle age and fuel quality effects. Vehicle age is introduced in the calculation via emission degradation functions of the total vehicle-accumulated mileage. The impact of improved fuels on the emissions of existing and future vehicle technologies is also modelled by applying correction factors depending on fuel specifications. A number of examples are given by applying the methodology on forecast activity data for different European countries to illustrate the expected effects of future vehicle technologies and fuels.     

Platinum emission rate of automobiles with catalytic converters

Inconsistent data presently available on the platinum emission rate of cars in Germany equipped with catalytic converters are evaluated. Automobile sources of Pt other than autocatalysts are quantified and found to be 1–6 orders of magnitudes lower than the Pt emissions attributed to catalytic converters. A transfer of emission rates derived from test stand experiments to more realistic street conditions reaches 0.8 μg Pt/km. In this manner, data from test stand experiments and from environmental investigations meet in the range of 0.5–0.8 μg Pt/km.     

Airshed Model Evaluation of Reactivity Adjustment Factors Calculated with the Maximum Incremental Reactivity Scale for Transitional-Low Emission Vehicles

Abstract

The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactivity at other conditions, i.e., where NO_x is the limiting precursor.

This study used the Carnegie/California Institute of Technology airshed model to evaluate whether the RAF-adjusted AFV emissions result in ozone impacts equivalent to those of CFV emissions. A matrix of two ozone episodes in the South Coast Air Basin (SoCAB) of California, two base emission inventories, and exhaust emissions from three alternative fuels that meet the first level of the low emission vehicle standards bounds the expected range of conditions. Although very good agreement was found previously for individual NMOG species,² this study noted deviations of up to ±15 percent from the equal ozone impacts for any vehicle/fuel combination required by the California regulations. These deviations appear to be attributable to differences in spatial and temporal patterns of emissions between vehicle fleets, rather than a problem with the MIR approach. The first formally adopted RAF, a value of 0.41 for 85 percent methanol/15 percent gasoline-fueled vehicles, includes a 10 percent increase based on the airshed modeling. The correction to the RAF is different for other fuels and may be different for air basins other than the SoCAB.     

Three decades of on-road mobile source emissions reductions in South Los Angeles

In May 2018, the University of Denver repeated on-road optical remote sensing measurements at two locations in Lynwood, CA. Lynwood area vehicle tailpipe emissions were first surveyed in 1989 and 1991 because the area suffered from a large number of carbon monoxide (CO) air quality violations. These new measurements allow for the estimation of fuel-specific CO and total hydrocarbon (HC) emissions reductions, changes in the longevity of emission-control components, and the prevalence of high emitters in the current fleet. Since 1989 CO emissions decreased approximately factors of 10 (120 ± 8 to 12.3 ± 0.2 gCO/kg of fuel) and 20 (210 ± 8 to 10.4 ± 0.4 gCO/kg of fuel) at our I-710/Imperial Highway and Long Beach Blvd. sites, respectively. These reductions are also reflected in the local ambient air measurements. Tailpipe HC emissions have decreased by a factor of 25 (50 ± 4 to 2.1 ± 0.3 gHC/kg of fuel) since 1991 at the Long Beach Blvd. location. The decreases are so dramatic that the vast majority of vehicles now have HC measurements that are indistinguishable from zero. The decreases have increased the skewedness of the emissions distribution with the 99th percentile now responsible for more than 37% (CO) and 28% (HC) of the totals. Ammonia emissions collected in 2018 at both Lynwood locations peak with 20-year-old vehicles (1998 models), indicating long lifetimes for catalytic converters.

In 1989 and 1991, the on-road Lynwood fleets had significantly higher emissions than fleets observed in other locations within the South Coast Air Basin. The 2018 fleets now have means and emissions by model year that are consistent with those observed at other sites in Los Angeles and the U.S. This indicates that modern vehicle combustion management and after-treatment systems are achieving their goals regardless of community income levels.

Implications: Recent on-road vehicle emission measurements at two locations in the Lynwood, CA area, first visited in 1989, found significant fuel specific CO and HC emission reductions. CO emissions have decreased by a factor of 10 and 20 at each location and HC emissions have declined by a factor of 25. This has increased the skewedness in both species emissions distribution. The 2018 fleets have means and emissions by model year that are now consistent with those observed at other U.S. sites indicating that modern vehicle emissions control advancements are achieving their goals regardless of community income levels.     

Effects of Fuel Type,Driving Cycle,and Emission Status on In-Use Vehicle Exhaust Reactivity

ABSTRACT

The introduction of reformulated gasolines significantly reduced exhaust hydrocarbon (HC) mass emissions, but few data are available concerning how these new fuels affect exhaust reactivity. Similarly, while it is well established that high-emitting vehicles contribute a significant portion of total mobile source HC mass emissions, it is also important to evaluate the exhaust reactivity from these vehicles. The objective of this study was to evaluate the relative influence on in-use vehicle exhaust reactivity of three critical factors: fuel, driving cycle, and vehicle emission status. Nineteen in-use vehicles were tested with seven randomly assigned fuel types and two driving cycles: the Federal Test Procedure (FTP) and the Unified Cycle (UC). Total exhaust reactivity was not statistically different between the FTP and UC cycles but was significantly affected by fuel type. On average, the exhaust reactivity for California Phase 2 fuel was the lowest (16 % below the highest fuel type) among the seven fuels tested for cold start emissions. The average exhaust reactivity for high-emitting vehicles was significantly higher for hot stabilized (11%) and hot start (15%) emissions than for low-emitting vehicles. The exhaust reactivities for the FTP and UC cycles for light-end HCs and carbonyls were significantly different for the hot stabilized mode. There was a significant fuel effect on the mean specific reactivity (SR) for the mid-range HCs, but not for light-end HCs or carbonyls, while vehicle emission status affected the mean SR for all three HC compound classes.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Particle Mass Emission Rates from Current-Technology,Light-Duty Gasoline Vehicles

ABSTRACT

Now that the U.S. Environmental Protection Agency has promulgated new National Ambient Air Quality Standards for PM_2.5, work will begin on generating the data required to determine the sources of ambient PM_2.5 and the magnitude of their contributions to air pollution. This paper summarizes the results of an Environmental Research Consortium program, carried out under the auspices of the U.S. Council for Automotive Research. The program focused on particulate matter (PM) emissions from representative, current-technology, light-duty gasoline vehicles produced by DaimlerChrysler Corp., Ford Motor Co., and General Motors Corp. The vehicles, for the most part taken from the manufacturer's certification and durability fleets, were dynamometer-tested using the three-phase Federal Test Procedure in the companies' laboratories. The test fleet was made up of a mixture of both low-mileage (2K-35K miles) and high-mileage (60K-150K miles) cars, vans, sport utility vehicles, and light trucks. For each vehicle tested, PM emissions were accumulated over 4 cold-start tests, which were run on successive days. PM emission rates from the entire fleet (22 vehicles total) averaged less than 2 mg/mile. All 18 vehicles tested using California Phase 2 reformulated gasoline had PM emission rates less than 2 mg/ mile at both low and high mileages.     

Nitrous oxide emissions from light duty vehicles

Nitrous oxide (N₂O) emissions measurements were made on light duty gasoline and light duty diesel vehicles during chassis dynamometer testing conducted at the Environment Canada and California Air Resources Board vehicle emissions laboratories between 2001 and 2007. Per phase and composite FTP emission rates were measured. A subset of vehicles was also tested using other driving cycles to characterize emissions as a function of different driving conditions. Vehicles were both new (<6500 km) and in-use (6500–160,000 km) and were tested on low sulfur gasoline (<30 ppm) or low sulfur diesel (<300 ppm). Measurements from selected published studies were combined with these new measurements to give a test fleet of 467 vehicles meeting both US EPA and California criteria pollutant emissions standards between Tier 0 and Tier 2 Bin 3 or SULEV. Aggregate distance-based and fuel-based emission factors for N₂O are reported for each emission standard and for each of the different test cycles. Results show that the distinction between light duty automobile and light duty truck is not significant for any of the emission standards represented by the test fleet and the distinction between new and aged catalyst is significant for vehicles meeting all emission standards but Tier 2. This is likely due to the relatively low mileage accumulated by the Tier 2 vehicles in this study as compared to the durability requirement of the standard. The FTP composite N₂O emission factors for gasoline vehicles meeting emission standards more stringent than Tier 1 are substantially lower than those currently used by both Canada and the US for the 2005 inventories. N₂O emission factors from test cycles other than the FTP illustrate the variability of emission factors as a function of driving conditions. N₂O emission factors are shown to strongly correlate with NMHC/NMOG emission standards and less strongly with NO_X and CO emission standards. A review of several published reports on the effect of gasoline sulfur content on N₂O emissions suggests that additional research is needed to adequately quantify the increase in N₂O emissions as a function of fuel sulfur.     

Particle mass emission rates from current-technology, light-duty gasoline vehicles

Now that the U.S. Environmental Protection Agency has promulgated new National Ambient Air Quality Standards for PM2.5, work will begin on generating the data required to determine the sources of ambient PM2.5 and the magnitude of their contributions to air pollution. This paper summarizes the results of an Environmental Research Consortium program, carried out under the auspices of the U.S. Council for Automotive Research. The program focused on particulate matter (PM) emissions from representative, current-technology, light-duty gasoline vehicles produced by DaimlerChrysler Corp., Ford Motor Co., and General Motors Corp. The vehicles, for the most part taken from the manufacturer's certification and durability fleets, were dynamometer-tested using the three-phase Federal Test Procedure in the companies' laboratories. The test fleet was made up of a mixture of both low-mileage (2K-35K miles) and high-mileage (60K-150K miles) cars, vans, sport utility vehicles, and light trucks. For each vehicle tested, PM emissions were accumulated over 4 cold-start tests, which were run on successive days. PM emission rates from the entire fleet (22 vehicles total) averaged less than 2 mg/mile. All 18 vehicles tested using California Phase 2 reformulated gasoline had PM emission rates less than 2 mg/mile at both low and high mileages.     

An Investigation of Idle Emissions Inspection and Maintenance at Altitude

Idle emissions inspection and maintenance was evaluated using a sample of 300 privately owned 1964 through 1973 model-year vehicles operating in the Denver metropolitan area. Ten privately owned stations, licensed by the State of Colorado to perform vehicle safety inspections, were utilized to conduct idle emissions inspection and subsequent maintenance of failed vehicles. Exhaust hydrocarbon (HC) and carbon monoxide (CO) reduction as measured by the 1975 Environmental Protection Agency (EPA) mass emission testing procedures was indicated to be 13% and 8% respectively at a 50 % rejection rate. The average maintenance cost to achieve the reduction was $11.32 per failed vehicle.

The adjustment and repair procedures provided to participating garages were sufficient to achieve significant emissions reduction and training provided to garage personnel was adequate. However, several problems were experienced with station personnel relative to data transmittal and inspection pass/fail limits. Problems were also experienced with respect to correlations between laboratory and garage-type analytical instrumentation.     

Methods of characterizing the distribution of exhaust emissions from light-duty, gasoline-powered motor vehicles in the U.S. fleet

Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM < or = 10 microm in aerodynamic diameter) and PM2.5 (PM < or = 2.5 microm in aerodynamic diameter) indicate that mobile sources can be responsible for over half of the ambient PM measured in an urban area. Recent source apportionment studies attempted to differentiate between contributions from gasoline and diesel motor vehicle combustion. Several source apportionment studies conducted in the United States suggested that gasoline combustion from mobile sources contributed more to ambient PM than diesel combustion. However, existing emission inventories for the United States indicated that diesels contribute more than gasoline vehicles to ambient PM concentrations. A comprehensive testing program was initiated in the Kansas City metropolitan area to measure PM emissions in the light-duty, gasoline-powered, on-road mobile source fleet to provide data for PM inventory and emissions modeling. The vehicle recruitment design produced a sample that could represent the regional fleet, and by extension, the national fleet. All vehicles were recruited from a stratified sample on the basis of vehicle class (car, truck) and model-year group. The pool of available vehicles was drawn primarily from a sample of vehicle owners designed to represent the selected demographic and geographic characteristics of the Kansas City population. Emissions testing utilized a portable, light-duty chassis dynamometer with vehicles tested using the LA-92 driving cycle, on-board emissions measurement systems, and remote sensing devices. Particulate mass emissions were the focus of the study, with continuous and integrated samples collected. In addition, sample analyses included criteria gases (carbon monoxide, carbon dioxide, nitric oxide/nitrogen dioxide, hydrocarbons), air toxics (speciated volatile organic compounds), and PM constituents (elemental/organic carbon, metals, semi-volatile organic compounds). Results indicated that PM emissions from the in-use fleet varied by up to 3 orders of magnitude, with emissions generally increasing for older model-year vehicles. The study also identified a strong influence of ambient temperature on vehicle PM mass emissions, with rates increasing with decreasing temperatures.     

Regulated and speciated hydrocarbon emissions from a catalyst equipped internal combustion engine

In the present work, the effect of engine operating conditions on its exhaust emissions and on catalytic converter operation is studied. A 4-cylinder OPEL 1.6 l internal combustion engine equipped with a hydraulic brake dynamometer was used in all the experiments. For exhaust emissions treatment a typical three-way catalyst was used. The highest hydrocarbon and carbon monoxide engine-out emissions were observed at engine power 2–4 HP. These emissions were decreased as the engine power was increased up to 20 HP. Among the various compounds detected in exhaust emissions, the following ones were monitored at engine and catalyst outlet: methane, hexane, ethylene, acetaldehyde, acetone, benzene, toluene and acetic acid. The concentration of each compound in the catalytic converter effluent was in the range 45–132, 5–12, 10–125, 15–22, 3–7, 3–12, 2–9, 0–6 ppm, respectively. After the required temperature for catalyst operation had been achieved, carbon monoxide tailpipe emissions were dramatically decreased and the observed hydrocarbon conversions were also high. Methane was the most resistant compound to oxidation while ethylene was the most degradable compound over the catalyst. The order from the easiest to the most resistant to oxidation compound was: Alkene>Aromatic>Aldehyde>Ketone>Alkane.     

Development of molecular marker source profiles for emissions from on-road gasoline and diesel vehicle fleets

As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles and diesel vehicles were tested on a chassis dynamometer to develop chemical source profiles for source attribution of atmospheric particulate matter in California's South Coast Air Basin. Gasoline vehicles were tested in cold-start and warm-start conditions, and diesel vehicles were tested through several driving cycles. Tailpipe emissions of particulate matter were analyzed for organic tracer compounds, including hopanes, steranes, and polycyclic aromatic hydrocarbons. Large intervehicle variation was seen in emission rate and composition, and results were averaged to examine the impacts of vehicle ages, weight classes, and driving cycles on the variation. Average profiles, weighted by mass emission rate, had much lower uncertainty than that associated with intervehicle variation. Mass emission rates and elemental carbon/organic carbon (EC/OC) ratios for gasoline vehicle age classes were influenced most by use of cold-start or warm-start driving cycle (factor of 2-7). Individual smoker vehicles had a large range of mass and EC/OC (factors of 40 and 625, respectively). Gasoline vehicle age averages, data on vehicle ages and miles traveled in the area, and several assumptions about smoker contributions were used to create emissions profiles representative of on-road vehicle fleets in the Los Angeles area in 2001. In the representative gasoline fleet profiles, variation was further reduced, with cold-start or warm-start and the representation of smoker vehicles making a difference of approximately a factor of two in mass emission rate and EC/OC. Diesel vehicle profiles were created on the basis of vehicle age, weight class, and driving cycle. Mass emission rate and EC/OC for diesel averages were influenced by vehicle age (factor of 2-5), weight class (factor of 2-7), and driving cycle (factor of 10-20). Absolute and relative emissions of molecular marker compounds showed levels of variation similar to those of mass and EC/OC.