Carbonyl and nitrogen dioxide emissions from gasoline- and diesel-powered motor vehicles

Carbonyls can be toxic and highly reactive in the atmosphere. To quantify trends in carbonyl emissions from light-duty (LD) vehicles, measurements were made in a San Francisco Bay area highwaytunnel bore containing essentially all LD vehicles during the summers of 1999, 2001, and 2006. The LD vehicle emission factor for formaldehyde, the most abundant carbonyl, did not change between 1999 and 2001, then decreased by 61 +/- 7% between 2001 and 2006. This reduction was due to fleet turnover and the removal of MTBE from gasoline. Acetaldehyde emissions decreased by 19 +/- 2% between 1999 and 2001 and by the same amount between 2001 and 2006. Absent the increased use of ethanol in gasoline after 2003, acetaldehyde emissions would have further decreased by 2006. Carbonyl emission factors for medium- (MD) and heavy-duty (HD) diesel trucks were measured in 2006 in a separate mixed-traffic bore of the tunnel. Emission factors for diesel trucks were higher than those for LD vehicles for all reported carbonyls. Diesel engine exhaust dominates over gasoline engines as a direct source of carbonyl emissions in California. Carbonyl concentrations were also measured in liquid-gasoline samples and were found to be low (< 20 ppm). The gasoline brands that contained ethanol showed higher concentrations of acetaldehyde in unburned fuel versus gasoline that was formulated without ethanol. Measurements of NO2 showed a yearly rate of decrease for LD vehicle emissions similar to that of total NOx in this study. The observed NO2/NOx ratio was 1.2 +/- 0.3% and 3.7 +/- 0.3% for LD vehicles and diesel trucks, respectively.     

A predictive model to correlate fuel specifications with on-road vehicles emissions in Mexico

Mexico is currently in the process of implementing its third air management program, which includes control measures targeting emissions reductions from mobile, point, and area sources. Achieving the program goals will require changes in the composition and in physical properties of gasoline and implementing an emissions reduction schedule. For that purpose a study was undertaken to support understanding of the effect of gasoline fuel parameters on exhaust emissions. Specifically, the relative impacts of Reid vapor pressure, distillation parameters, oxygen, sulfur, olefins, and aromatic contents on the exhaust emissions of in-use vehicles of the metropolitan area of Mexico City were investigated. The results were used to develop a model to predict CO, nitrogen oxides, total hydrocarbons, and toxic emissions such as benzene, 1,3-butadiene, formaldehyde, and acetaldehyde. Also a statistical model that predicts evaporative emissions was built. Results of the present model are compared with those obtained using the complex model of the United States Environmental Protection Agency.     

A systems evaluation on the effectiveness of a catalyst retrofit program in China

A low-cost, rare-earth oxide (REO) catalyst has been recommended as part of China's retrofit program for Chinese carbureted vehicles. This study evaluated: (1) the emission reduction efficiency of the REO catalyst during chassis dynamometer testing on the FTP cycle; (2) the effect that fuel properties had on tailpipe emissions and catalyst efficiency; (3) the importance of vehicle premaintenance as part of a retrofit protocol; and (4) the emission reductions obtained following implementation of the program. Results also show that current in-use Chinese noncatalyst, carbureted vehicles operate excessively rich, resulting in extremely high emissions of CO, gaseous toxic compounds, and other non-methane hydrocarbon species (NMHC). Preretrofit maintenance alone has the potential to reduce these emissions by approximately 50%. Dynamometer emission tests showed emissions reductions of >95% for hydrocarbons, CO, and gaseous toxics after retrofit of the REO catalyst. In particular, the relative unit health risk associated with the decrease in emissions of airborne toxic compounds using unleaded Chinese fuel was reduced from 6.33 to 0.30. (Use of low-sulfur California Phase II gasoline rather than current in-use Chinese fuel reduced emissions further.) Following implementation of the program, a follow-up study showed that in-use emissions benefits were considerably less than anticipated, primarily because of poor quality control at the retrofit service centers, a less aggressive preretrofit maintenance procedure, and unauthorized modification to the recommended retrofit control system. Overall results indicate that a carefully controlled retrofit program using REO catalyst technology can reduce emissions significantly. However, well-defined implementation guidelines, and strict adherence to these guidelines are needed to achieve maximum benefits.     

Effects of fuel ethanol content and volatility on regulated and unregulated exhaust emissions for the latest technology gasoline vehicles

Oxygenate content and fuel volatility (distillation) variables are important parameters affecting vehicle exhaust emissions, and data on their effects on the latest technology vehicles are quite limited. For this study, 12 California-certified LEV to SULEV vehicles were tested on a matrix of 12 fuels with varying levels of ethanol concentration (0, 5.7, and 10 vol %), T50 (195, 215, and 235 degrees F), and T90 (295, 330, and 355 degrees F). There were statistically significant interactions between ethanol and T90 for NMHC, ethanol, and T50 for CO and ethanol and T50 for NO(x). NMHC emissions increased with increasing ethanol content at the midpoint and high level of T90 but were unaffected at the low T90 level. CO emissions decreased as the ethanol content increased from the low to the midpoint level for all levels of T50, but between the 5.7 and 10% ethanol levels, CO showed only an increase for the high level of T50. NO(x) emissions increased with ethanol content for some conditions. Non-methane organic gases (NMOG) and toxic emissions were examined for only a subset of fuels with the highest T90 level, with NMOG, acetaldehyde, benzene, and 1-,3-butadiene all found to increase with increasing ethanol content.     

Emissions of aldehydes and ketones from a two-stroke engine using ethanol and ethanol-blended gasoline as fuel

Besides aliphatic gasoline, ethanol-blended gasoline intended for use in small utility engines was recently introduced on the Swedish market. For small utility engines, little data is available showing the effects of these fuels on exhaust emissions, especially concerning aldehydes and ketones (carbonyls). The objective of the present investigation was to study carbonyl emissions and regulated emissions from a two-stroke chain saw engine using ethanol, gasoline, and ethanol-blended gasoline as fuel (0%, 15%, 50%, 85%, and 100% ethanol). The effects of the ethanol-blending level and mechanical changes of the relative air/fuel ratio, lambda, on exhaust emissions was investigated, both for aliphatic and regular gasoline. Formaldehyde, acetaldehyde, and aromatic aldehydes were the most abundant carbonyls in the exhaust. Acetaldehyde dominated for all ethanol-blended fuels (1.2-12 g/kWh, depending on the fuel and lambda), and formaldehyde dominated for gasoline (0.74-2.3 g/kWh, depending on the type of gasoline and lambda). The main effects of ethanol blending were increased acetaldehyde emissions (30-44 times for pure ethanol), reduced emissions of all other carbonyls exceptformaldehyde and acrolein (which showed a more complex relation to the ethanol content), reduced carbon monoxide (CO) and ntirogen oxide (NO) emissions, and increased hydrocarbon (HC) and nitrogen dixodie (NO2) emissions. The main effects of increasing lambda were increased emissions of carbonyls and nitrogen oxides (NOx) and reduced CO and HC emissions. When the two types of gasoline are considered, benzaldehyde and tolualdehyde could be directly related to the gasoline content of aromatics or olefins, but also acrolein, propanal, crotonaldehyde, and methyl ethyl ketone mainly originated from aromatics or olefins, while the main source for formaldehyde, acetaldehyde, acetone, methacrolein, and butanal was saturated aliphatic hydrocarbons.     

Evaluation of the vehicle inspection/maintenance program in the Metropolitan Area of Mexico City

The Inspection/Maintenance Program in the Metropolitan Area of Mexico City (MAMC) mandates a test every 6 months for all gasoline motor vehicles as one of the strategies to decrease emissions of vehicular pollutants. FTP-75 and ASM procedures were performed in our facilities to a fleet of 108 in-use motor vehicles before and after the approval of the I/M mandatory test When our laboratory-simulated ASM data were compared with those of the official certificate, a large difference was observed between them. On the other hand, audits at the test-only centers indicate poor maintenance of the analytical instruments and dynamometers. On the basis of our FTP results, an estimation of the emissions change for the MAMC fleet shows a net 4% decrease in CO emissions, while total hydrocarbons and NOx increased 9 and 8%, respectively. Our results indicate that the I/M system in the MAMC lacks the technical capability and investment to ensure that software and hardware are properly maintained, calibrated, and upgraded. Sometimes limited attention is paid to ensure adequate training of inspectors, auditors, and quality control staff.     

Emissions of regulated pollutants from a spark ignition engine. Influence of fuel and air/fuel equivalence ratio

A spark ignition engine is used to determine the influence of fuel composition and air/fuel equivalence ratio on the exhaust emissions of regulated pollutants. Two specific fuel matrices are used: the first contains eight hydrocarbons and the second contains four oxygenated compounds. A specific experimental design is used for these tests. Fuel aromatics increase the exhaust CO, HC, and NOx at stoichiometry, lean and rich conditions. Lambda is more important than fuel composition in the case of CO and HC. At stoichiometry, the addition of oxygenated compounds can decrease exhaust CO, HC, and NOx up to 30%, 50%, and 60%, respectively. Under these conditions, the addition of 5% of 2-propanol is the most effective for the reduction of CO, the addition of 20% of ethanol forthe reduction of HC, and this of 5% of methyl tributyl ester (MTBE) for the NOx. The addition of oxygenated compounds can decrease CO by 30% at lean conditions, while no decrease is observed at rich ones; HC and NOx can decrease up to 30% and 80%, respectively, under lean conditions and 50% under rich ones. At all lambda tested, exhaust NOx increases with the addition of 20% of 2-propanol.     

Remote sensing study of emissions from motor vehicles in the Metropolitan Area of Mexico City

Remote sensing was employed for the first time to measure nitric oxide (NO) levels of on-road light-duty motor vehicles of the Metropolitan Area of Mexico City (MAMC). The sensor placed at 12 different sites also measured the concentration of CO2, CO, and total hydrocarbons (THC) in the exhaust emissions. A database was compiled containing 122 800 readings, of which 84 650 (69%) records were valid emissions measurements. CO, HC, and NO valid readings were 68.9, 63.4, and 62.9%, respectively, of the total attempted measurements. Furthermore, 42 822 vehicles were number-plate-matched to model year with the information provided by the Inspection/Maintenance Program. The mean emissions of total valid readings for CO, HC, and NO were determined to be 1.31 vol %, 440 ppm (propane), and 914 ppm, respectively. In 1991 and 1994, remote sensing measurements of CO and HC tailpipe emissions were performed in the MAMC in five different locations (30 000 valid readings). Large drops in both pollutants were observed for the intervening years, but sufficient vehicle information was not available at that time to fully explain the observed trends. Compared with those reports, our results point out to a steady decrease in CO and HC exhaust emissions with vehicle model year. The fleet emissions measured exhibit a gamma-distribution, with 10% of the most polluting fleet studied being responsible for 45%, 25%, and 29% of the CO, HC, and NO emissions, respectively. NO emissions in taxis are the highest among the vintage of vehicles, a matter of concern since according to the distance traveled per year, they represent 22% of the total activity in the MAMC.     

Emission of alcohols and carbonyl compounds from a spark ignition engine. Influence of fuel and air/fuel equivalence ratio

A spark ignition engine was used to study the impact of fuel composition and of the air/fuel equivalence (lambda) ratio on exhaust emissions of alcohols and aldehydes/ketones. Fuel blends contained eight hydrocarbons (n-hexane, 1-hexene, cyclohexane, n-octane, isooctane, toluene, o-xylene, and ethylbenzene (ETB)) and four oxygenated compounds (methanol, ethanol, 2-propanol, and methyl tert butyl ether (MTBE)). Exhaust methanol is principally produced from fuel methanol and MTBE but also from ethanol, 2-propanol, isooctane, and hexane. Exhaust ethanol and 2-propanol are produced only from the respective fuel compounds. Exhaust formaldehyde is mainly produced from fuel methanol, acetaldehyde from fuel ethanol, and propionaldehyde from straight-chain hydrocarbons. Exhaust acroleine comes from fuel 1-hexene, acetone from 2-propanol, n-hexane, n-octane, isooctane, and MTBE. Exhaust crotonaldehyde comes from fuel 1-hexene, cyclohexane, n-hexane, and n-octane, methacroleine from fuel isooctane, and benzaldehyde from fuel aromatics. Light pollutants (C1-C2) are most likely formed from intermediate species which are quite independent of the fuel composition. An increase in A increases the exhaust concentration of acroleine, crotonaldehyde, methacroleine, and decreases these of the three alcohols for the alcohol-blended fuels. The concentration of methanol, formaldehyde, propionaldehyde, and benzaldehyde is a maximum atstoichiometry. The exhaust concentration of acetaldehyde and acetone presents a complex behavior: it increases in some cases, decreases in others, or presents a maximum at stoichiometry. The concentration of four aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde) is also linked with the exhaust temperature and fuel H/C ratio.     

A comparison of emissions from vehicles fueled with diesel or compressed natural gas

A comprehensive comparison of emissions from vehicles fueled with diesel or compressed natural gas (CNG) was developed from 25 reports on transit buses, school buses, refuse trucks, and passenger cars. Emissions for most compounds were highest for untreated exhaust emissions and lowest for treated exhaust CNG buses without after-treatment had the highest emissions of carbon monoxide, hydrocarbons, nonmethane hydrocarbons (NMHC), volatile organic compounds (VOCs; e.g., benzene, butadiene, ethylene, etc.), and carbonyl compounds (e.g., formaldehyde, acetaldehyde, acrolein). Diesel buses without after-treatment had the highest emissions of particulate matter and polycyclic aromatic hydrocarbons (PAHs). Exhaust after-treatments reduced most emissions to similar levels in diesel and CNG buses. Nitrogen oxides (NO(x)) and carbon dioxide (CO2) emissions were similar for most vehicle types, fuels, and exhaust after-treatments with some exceptions. Diesel school buses had higher CO2 emissions than the CNG bus. CNG transit buses and passenger cars equipped with three-way catalysts had lower NO(x) emissions. Diesel buses equipped with traps had higher nitrogen dioxide emissions. Fuel economy was best in the diesel buses not equipped with exhaust after-treatment.     

Emissions of toxic pollutants from compressed natural gas and low sulfur diesel-fueled heavy-duty transit buses tested over multiple driving cycles

The number of heavy-duty vehicles using alternative fuels such as compressed natural gas (CNG) and new low-sulfur diesel fuel formulations and equipped with after-treatment devices are projected to increase. However, few peer-reviewed studies have characterized the emissions of particulate matter (PM) and other toxic compounds from these vehicles. In this study, chemical and biological analyses were used to characterize the identifiable toxic air pollutants emitted from both CNG and low-sulfur-diesel-fueled heavy-duty transit buses tested on a chassis dynamometer over three transient driving cycles and a steady-state cruise condition. The CNG bus had no after-treatment, and the diesel bus was tested first equipped with an oxidation catalyst (OC) and then with a catalyzed diesel particulate filter (DPF). Emissions were analyzed for PM, volatile organic compounds (VOCs; determined on-site), polycyclic aromatic hydrocarbons (PAHs), and mutagenic activity. The 2000 model year CNG-fueled vehicle had the highest emissions of 1,3-butadiene, benzene, and carbonyls (e.g., formaldehyde) of the three vehicle configurations tested in this study. The 1998 model year diesel bus equipped with an OC and fueled with low-sulfur diesel had the highest emission rates of PM and PAHs. The highest specific mutagenic activities (revertants/microg PM, or potency) and the highest mutagen emission rates (revertants/mi) were from the CNG bus in strain TA98 tested over the New York Bus (NYB) driving cycle. The 1998 model year diesel bus with DPF had the lowest VOCs, PAH, and mutagenic activity emission. In general, the NYB driving cycle had the highest emission rates (g/mi), and the Urban Dynamometer Driving Schedule (UDDS) had the lowest emission rates for all toxics tested over the three transient test cycles investigated. Also, transient emissions were, in general, higher than steady-state emissions. The emissions of toxic compounds from an in-use CNG transit bus (without an oxidation catalyst) and from a vehicle fueled with low-sulfur diesel fuel (equipped with DPF) were lower than from the low-sulfur diesel fueled vehicle equipped with OC. All vehicle configurations had generally lower emissions of toxics than an uncontrolled diesel engine. Tunnel backgrounds (measurements without the vehicle running) were measured throughout this study and were helpful in determining the incremental increase in pollutant emissions. Also, the on-site determination of VOCs, especially 1,3-butadiene, helped minimize measurement losses due to sample degradation after collection.     

Effect of water/fuel emulsions and a cerium-based combustion improver additive on HD and LD diesel exhaust emissions

One of the major technological challenges for the transport sector is to cut emissions of particulate matter (PM) and nitrogen oxides (NOx) simultaneously from diesel vehicles to meet future emission standards and to reduce their contribution to the pollution of ambient air. Installation of particle filters in all existing diesel vehicles (for new vehicles, the feasibility is proven) is an efficient but expensive and complicated solution; thus other short-term alternatives have been proposed. It is well known that water/diesel (W/ D) emulsions with up to 20% water can reduce PM and NOx emissions in heavy-duty (HD) engines. The amount of water that can be used in emulsions for the technically more susceptible light-duty (LD) vehicles is much lower, due to risks of impairing engine performance and durability. The present study investigates the potential emission reductions of an experimental 6% W/D emulsion with EURO-3 LD diesel vehicles in comparison to a commercial 12% W/D emulsion with a EURO-3 HD engine and to a Cerium-based combustion improver additive. For PM, the emulsions reduced the emissions with -32% for LD vehicles (mass/km) and -59% for the HD engine (mass/ kWh). However, NOx emissions remained unchanged, and emissions of other pollutants were actually increased forthe LD vehicles with +26% for hydrocarbons (HC), +18% for CO, and +25% for PM-associated benzo[a]pyrene toxicity equivalents (TEQ). In contrast, CO (-32%), TEQ (-14%), and NOx (-6%) were reduced by the emulsion for the HD engine, and only hydrocarbons were slightly increased (+16%). Whereas the Cerium-based additive was inefficient in the HD engine for all emissions except for TEQ (-39%), it markedly reduced all emissions for the LD vehicles (PM -13%, CO -18%, HC -26%, TEQ -25%) except for NOx, which remained unchanged. The presented data indicate a strong potential for reductions in PM emissions from current diesel engines by optimizing the fuel composition.     

Remote sensing of in-use heavy-duty diesel trucks

On-road measurements in 2005 of carbon monoxide (CO), hydrocarbons, nitric oxide, nitrogen dioxide, and sulfur dioxide from 1641 individually identified heavy-duty diesel trucks at two locations in Colorado are reported. Carbon monoxide and nitric oxide show increasing emissions with increased altitude. Oxides of nitrogen (NOx) emissions have decreased with more recent model years over the last 10 years but are the same as vehicles that are 20 years old. At the Golden, CO site, there was a statistically significant decrease in fleet emissions of CO and NOx since a similar study in 1999. There was no emission trend for CO or NOx with gross vehicle weight or odometer in units of grams of pollutant per kilogram of fuel consumed. Data from this study suggest that on-road remote sensing can detect illegal, high sulfur fuel use from individual heavy-duty diesel trucks. Ammonia emissions from this study were below the detection limit of the instrument but will be useful as a baseline value for future comparison.     

Exhaust emissions from engines of the Detroit Diesel Corporation in transit buses: a decade of trends

In the U.S.A., exhaust emissions from city buses fueled by diesel are not characterized well because current emission standards require engine tests rather than tests of whole vehicles. Two transportable chassis dynamometer laboratories developed and operated by West Virginia University (WVU) have been used extensively to gather realistic emission data from heavy-duty vehicles, including buses, tested in simulated driving conditions. A subset of these data has been utilized for a comprehensive introspection into the trends of regulated emissions from transit buses over the last 7 years, which has been prompted by continuously tightening restrictions on one hand, along with remarkable technological progress, on the other hand. Two widely used models of diesel engines manufactured by the Detroit Diesel Corporation (DDC) have been selected as a case-study for such an overview, based on full-scale, on-site testing of actual city buses, driven in accordance with the SAE J1376 standard of a Commercial Business District (CBD) cycle. The results provide solid, quantitative evidence that most regulated emissions from engines produced by DDC have declined over the years, especially with the transition from the 6V-92TA to the Series 50 models. This improvement is remarkable mainly for the emissions of particulate matter (PM), that are lower by over 70%, on average, for the Series 50 engines, though the emissions of nitrogen oxides (NOx) exhibit a reversed trend, showing a degradation of about 6%, on average, with the transition from 6V-92TA to the Series 50 engines. The expected trend of decreasing emission levels with the model year of the engine is clear and consistent for particulate matter (PM), hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx), starting with the 1990 models, although it is not conclusive for carbon dioxide (CO2) emissions.     

Hydrocarbon emissions from in-use commercial aircraft during airport operations

The emissions of selected hydrocarbons from in-use commercial aircraft at a major airport in the United States were characterized using proton-transfer reaction mass spectrometry (PTR-MS) and tunable infrared differential absorption spectroscopy (TILDAS) to probe the composition of diluted exhaust plumes downwind. The emission indices for formaldehyde, acetaldehyde, benzene, and toluene, as well as other hydrocarbon species, were determined through analysis of 45 intercepted plumes identified as being associated with specific aircraft. As would have been predicted for high bypass turbine engines, the hydrocarbon emission index was greater in idle and taxiway acceleration plumes relative to approach and takeoff plumes. The opposite was seen in total NOy emission index, which increased from idle to takeoff. Within the idle plumes sampled in this study, the median emission index for formaldehyde was 1.1 g of HCHO per kg of fuel. For the subset of hydrocarbons measured in this work, the idle emissions levels relative to formaldehyde agree well with those of previous studies. The projected total unburned hydrocarbons (UHC) deduced from the range of in-use idle plumes analyzed in this work is greater than a plausible range of engine types using the defined idle condition (7% of rated engine thrust) in the International Civil Aviation Organization (ICAO) databank reference.     

Effects of biodiesel blends and Arco EC-diesel on emissions from light heavy-duty diesel vehicles

Chassis dynamometer tests were performed on seven light heavy-duty diesel trucks comparing the emissions of a California diesel fuel with emissions from four other fuels: ARCO emissions control diesel (EC-D) and three 20% biodiesel blends (one yellow grease and two soy-based). The EC-D and the yellow grease biodiesel blend both showed significant reductions in total hydrocarbons (THC) and carbon monoxide (CO) emissions over the test vehicle fleet. EC-D also showed reductions in particulate matter (PM) emission rates. NOx emissions were comparable for the different fuel types for most of the vehicles tested. The soy-based biodiesel blends showed smaller emissions differences over the test vehicles, including some increases in PM emissions. This is somewhat in contrast to previous studies that have shown larger reductions in THC, CO, and PM for biodiesel blends. The possible influence of different fuels, fuel properties, and engine load on emissions is also discussed.     

Regulated and non-regulated emissions from in-use diesel-electric switching locomotives

Diesel-electric locomotives are vital to the operation of freight railroads in the United States, and emissions from this source category have generated interest in recent years. They are also gaining attention as an important emission source under the larger set of nonroad sources, both from a regulated emissions and health effects standpoint. The present work analyzes regulated (NOx, PM, THC, CO) and non-regulated emissions from three in-use diesel-electric switching locomotives using standardized sampling and analytical techniques. The engines tested in this work were from 1950, 1960, and 1970 and showed a range of NOx and PM emissions. In general, non-regulated gaseous emissions showed a sharp increase as engines shifted from non-idle to idle operating modes. This is interesting from an emissions perspective since activity data shows that these locomotives spend around 60% of their time idling. In terms of polycyclicaromatic hydrocarbon (PAH) contributions, the dominance of naphthalene and its derivatives over the total PAH emissions was apparent, similar to observations for on-road diesel tractors. Among nonnaphthalenic species, itwas observed that lower molecular weight PAHs and n-alkanes dominated their respective compound classes. Regulated emissions from a newer technology engine used in a back-up generator (BUG) application were also compared againstthe present engines; it was determined that use of the newer engine may lower NOx and PM emissions by up to 30%. Another area of interest to regulators is better estimation of the marine engine inventory for port operations. Toward that end, a comparison of emissions from these engines with engine manufacturer data and the newer technology BUG engine was also performed for a marine duty cycle, another application where these engines are used typically with little modifications.     

Quantifying the emission benefits of opacity testing and repair of heavy-duty diesel vehicles

The objective of this study was to begin to quantify the benefits of a smoke opacity-based (SAE J1667 test) inspection and maintenance program. Twenty-six vehicles exhibiting visible smoke emissions were recruited: 14 pre-1991 vehicles and 12 1991 and later model year vehicles. Smoke opacity and regulated pollutant emissions via chassis dynamometer were measured, with testing conducted at 1609 m above sea level. Twenty of the vehicles were then repaired with the goal of lowering visible smoke emission, and the smoke opacity testing and pollutant emissions measurements were repeated. For the pre-1991 vehicles actually repaired, pre-repair smoke opacity averaged 39% and PM averaged 5.6 g/mi. NOx emissions averaged 22.1 g/mi. After repair, the average smoke opacity had declined to 26% and PM declined to 3.3 g/mi, while NOx emissions increased to 30.9 g/mi. For the 1991 and newer vehicles repaired, pre-repair smoke opacity averaged 59% and PM averaged 2.2 g/mi. NOx emissions averaged 12.1 g/mi. After repair, the average opacity had declined to 30% and PM declined to 1.3 g/mi, while NOx increased slightly to 14.4 g/mi. For vehicles failing the California opacity test at >55% for pre-1991 and >40% for 1991 and later model years, the changes in emissions exhibited a high degree of statistical significance. The average cost of repairs was 1088 dollars, and the average is very similar for both the pre-1991 and 1991+ model year groups. Smoke opacity was shown to be a relatively poor predictor of driving cycle PM emissions. Peak CO or peak CO and THC as measured during a snap-acceleration were much better predictors of driving cycle PM emissions.     

Real-time gaseous, PM and ultrafine particle emissions from a modern marine engine operating on biodiesel

Emissions from harbor-craft significantly affect air quality in populated regions near ports and inland waterways. This research measured regulated and unregulated emissions from an in-use EPA Tier 2 marine propulsion engine on a ferry operating in a bay following standard methods. A special effort was made to monitor continuously both the total Particulate Mass (PM) mass emissions and the real-time Particle Size Distribution (PSD). The engine was operated following the loads in ISO 8178-4 E3 cycle for comparison with the certification standards and across biodiesel blends. Real-time measurements were also made during a typical cruise in the bay. Results showed the in-use nitrogen oxide (NOx) and PM(2.5) emission factors were within the not to exceed standard for Tier 2 marine engines. Comparing across fuels we observed the following: a) no statistically significant change in NO(x) emissions with biodiesel blends (B20, B50); b) ～ 16% and ～ 25% reduction of PM(2.5) mass emissions with B20 and B50 respectively; c) a larger organic carbon (OC) to elemental carbon (EC) ratio and organic mass (OM) to OC ratio with B50 compared to B20 and B0; d) a significant number of ultrafine nuclei and a smaller mass mean diameter with increasing blend-levels of biodiesel. The real-time monitoring of gaseous and particulate emissions during a typical cruise in the San Francisco Bay (in-use cycle) revealed important effects of ocean/bay currents on emissions: NO(x) and CO(2) increased 3-fold; PM(2.5) mass increased 6-fold; and ultrafine particles disappeared due to the effect of bay currents. This finding has implications on the use of certification values instead of actual in-use emission values when developing inventories. Emission factors for some volatile organic compounds (VOCs), carbonyls, and poly aromatic hydrocarbons (PAHs) are reported as supplemental data.     

Development and application of a mobile laboratory for measuring emissions from diesel engines. 1. Regulated gaseous emissions

Information about in-use emissions from diesel engines remains a critical issue for inventory development and policy design. Toward that end, we have developed and verified the first mobile laboratory that measures on-road or real-world emissions from engines at the quality level specified in the U.S. Congress Code of Federal Regulations. This unique mobile laboratory provides information on integrated and modal regulated gaseous emission rates and integrated emission rates for speciated volatile and semivolatile organic compounds and particulate matter during real-world operation. Total emissions are captured and collected from the HDD vehicle that is pulling the mobile laboratory. While primarily intended to accumulate data from HDD vehicles, it may also be used to measure emission rates from stationary diesel sources such as back-up generators. This paper describes the development of the mobile laboratory, its measurement capabilities, and the verification process and provides the first data on total capture gaseous on-road emission measurements following the California Air Resources Board (ARB) 4-mode driving cycle, the hot urban dynamometer driving schedule (UDDS), the modified 5-mode cycle, and a 53.2-mi highway chase experiment. NOx mass emission rates (g mi(-1)) for the ARB 4-mode driving cycle, the hot UDDS driving cycle, and the chase experimentwerefoundto exceed current emission factor estimates for the engine type tested by approximately 50%. It was determined that congested traffic flow as well as "off-Federal Test Procedure cycle" emissions can lead to significant increases in per mile NOx emission rates for HDD vehicles.