Revisiting nitrous acid (HONO) emission from on-road vehicles: A tunnel study with a mixed fleet

Nitrous acid (HONO) is an important precursor of OH radicals in the atmosphere. In urban areas, emissions from vehicles are the main source of air pollutants, including reactive nitrogen. Previously reported emission ratios of HONO (HONO/NO_x) from vehicles were measured in the late 1990s and need to be updated due to the significant changes in emission control technologies. We measured the emission ratio of a fleet of vehicles (38% diesel on average) from March 11 to 21, 2015, in a road tunnel in Hong Kong. The emission ratio of 1.24% (±0.35%) obtained is greater than the commonly adopted 0.8% or 0.3%. The elevated emission ratio is found to be related to the presence of vehicles equipped with diesel particle filters (DPFs). Positive correlation between HONO and black carbon (BC) shows that HONO and BC were emitted together, while the lack of correlation or even anticorrelation between HONO/NO_x and BC indicates that the BC-mediated conversion of NO₂ to HONO in the dark was insignificant in the immediate vicinity of the emission sources.

Implications: Vehicular emission is a key source for HONO in the urban atmosphere. However, the most commonly used emission ratio HONO/NO_x in modeling studies was measured more than 15 years ago. Our tunnel study suggests that a mixed fleet nowadays has a higher emission ratio, possibly because of the diesel particle filter (DPF) retrofit program and the growing share of Euro IV or more advanced diesel vehicles. Our study also provides new insight into the role of black carbon in HONO formation from vehicles.     

Radical precursors and related species from traffic as observed and modeled at an urban highway junction

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO_x) ratio of 6.01 ± 0.15 (r ² = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 ± 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO_x and HCHO/CO ratios are largely due to higher NO_x and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO_x emission ratio is around 0.017 ± 0.0009 kg HONO/kg NO_x which is twice as high as in MOVES. The observed NO₂/NO_x emission ratio is around 0.16 ± 0.01 kg NO₂/kg NO_x, which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO₂ emission ratio by a factor of 3 compared with the observations, which is 0.0033 ± 0.0002 kg CO/kg CO₂. This as well as CO/NO_x overestimation is coming from light-duty gasoline vehicles.

Implications: Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals that ultimately contribute to ozone formation. There still exist uncertainties in emission sources of HONO and HCHO and thus regional air quality modeling still tend to underestimate concentrations of free radicals in the atmosphere. This paper demonstrates that the latest U.S. Environmental Protection Agency (EPA) traffic emission model MOVES still shows significant deviations from observed emission ratios, in particular underestimation of HCHO/CO and HONO/NO_x ratios. Improving the performance of MOVES may improve regional air quality modeling.     

Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel

Simultaneous measurements of nitrous acid (HONO) and nitrogen dioxide (NO₂) using a differential optical absorption spectroscopy system, nitrogen oxide (NO) by an in situ chemiluminescence analyser and carbon dioxide (CO₂) by a gas chromatographic technique were carried out in the Wuppertal Kiesbergtunnel. At high traffic density HONO concentrations of up to 45 ppbV were observed. However, at low traffic density unexpectedly high HONO concentrations of up to 10 ppbV were measured caused by heterogeneous HONO formation on the tunnel walls. In addition to the tunnel campaigns, emission measurements of HONO, NO₂, NO and CO₂ from different single vehicles (a truck, a diesel and a gasoline passenger car) were also performed. For the correction of the HONO emission data, the heterogeneous HONO formation on the tunnel walls was quantified by two different approaches (a) in different NO₂ emission experiments in the tunnel without traffic and (b) on tunnel wall residue in the laboratory. The HONO concentration corrected for heterogeneous formation on the tunnel walls, in relation to the CO₂ concentration can be used to estimate the amount of HONO, which is directly emitted from the vehicle fleet. From the measured data, emission ratios (e.g. HONO/NO_x) and emission indices (e.g. mg HONO kg⁻¹ fuel) were calculated. The calculated emission index of 88±18 mg HONO kg⁻¹ fuel allows an estimation of the HONO emission rates from traffic into the atmosphere. Furthermore, the heterogeneous formation of HONO from NO₂ on freshly emitted exhaust particles is discussed.     

Vehicle emissions of radical precursors and related species observed in the 2009 SHARP campaign

The 2009 Study of Houston Atmospheric Radical Precursors (SHARP) field campaign had several components that yielded information on the primary vehicular emissions of formaldehyde (HCHO) and nitrous acid (HONO), in addition to many other species. Analysis of HONO measurements at the Moody Tower site in Houston, TX, yielded emission ratios of HONO to the vehicle exhaust tracer species NO_x and CO of 14 pptv/ppbv and 2.3 pptv/ppbv, somewhat smaller than recently published results from the Galleria site, although evidence is presented that the Moody Tower values should be upper limits to the true ratios of directly emitted HONO, and are consistent with ratios used in current standard emissions models. Several other Moody Tower emission ratios are presented, in particular a value for HCHO/CO of 2.4 pptv/ppbv. Considering only estimates of random errors, this would be significantly lower than a previous value, though the small sample size and possible systematic differences should be taken into account. Emission factors for CO, NO_x, and HCHO, as well as various volatile organic compounds (VOCs), were derived from mobile laboratory measurements both in the Washburn Tunnel and in on-road exhaust plume observations. These two sets of results and others reported in the literature all agree well, and are substantially larger than the CO, NO_x, and HCHO emission factors derived from the emission ratios reported from the Galleria site.

Implications: Emission factors for the species measured in the various components of the 2009 SHARP campaign in Houston, TX, including HCHO, HONO, CO, CO₂, nitrogen oxides, and VOCs, are needed to support regional air quality monitoring. Components of the SHARP campaign measured these species in several different ways, each with their own potential for systematic errors and differences in vehicle fleets sampled. Comparisons between data sets suggest that differences in sampling place and time may result in quite different emission factors, while also showing that different vehicle mixes can yield surprisingly similar emission factors.     

NOx emission calculations for bulk carriers by using engine power probabilities as weighting factors

An important marine pollution issue identified by the International Maritime Organization (IMO) is NO_x emissions; however, the stipulated method for determining the NO_x certification value does not reflect the actual high emission factors of slow-speed two-stroke diesel engines over long-term slow steaming. In this study, an accurate method is presented for calculating the NO_x emission factors and total amount of NO_x emissions by using the actual power probabilities of the diesel engines in four types of bulk carriers. The proposed method is suitable for all types and purposes of diesel engines, is not restricted to any operating modes, and is highly accurate. Moreover, it is recommended that the IMO-stipulated certification value calculation method be modified accordingly to genuinely reduce the amount of NO_x emissions. The successful achievement of this level of reduction will help improve the air quality, especially in coastal and port areas, and the health of local residents.

Implications: As per the IMO, the NO_x emission certification value of marine diesel engines having a rated power over 130 kW must be obtained using specified weighting factor (WF)-based calculation. However, this calculation fails to represent the current actual situation. Effective emission reductions of 6.91% (at sea) and 31.9% (in ports) were achieved using a mathematical model of power probability functions. Thus, we strongly recommend amending the certification value of NO_x Technical Code 2008 (NTC 2008) by removing the WF constraints, such that the NO_x emissions of diesel engines is lower than the Tier-limits at any load level to obtain genuine NO_x emission reductions.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Comparison of the MOVES2010a,MOBILE6.2, and EMFAC2007 mobile source emission models with on-road traffic tunnel and remote sensing measurements

The Desert Research Institute conducted an on-road mobile source emission study at a traffic tunnel in Van Nuys, California, in August 2010 to measure fleet-averaged, fuel-based emission factors. The study also included remote sensing device (RSD) measurements by the University of Denver of 13,000 vehicles near the tunnel. The tunnel and RSD fleet-averaged emission factors were compared in blind fashion with the corresponding modeled factors calculated by ENVIRON International Corporation using U.S. Environmental Protection Agency's (EPA's) MOVES2010a (Motor Vehicle Emissions Simulator) and MOBILE6.2 mobile source emission models, and California Air Resources Board's (CARB's) EMFAC2007 (EMission FACtors) emission model. With some exceptions, the fleet-averaged tunnel, RSD, and modeled carbon monoxide (CO) and oxide of nitrogen (NO_x) emission factors were in reasonable agreement (±25%). The nonmethane hydrocarbon (NMHC) emission factors (specifically the running evaporative emissions) predicted by MOVES were insensitive to ambient temperature as compared with the tunnel measurements and the MOBILE- and EMFAC-predicted emission factors, resulting in underestimation of the measured NMHC/NO_x ratios at higher ambient temperatures. Although predicted NMHC/NO_x ratios are in good agreement with the measured ratios during cooler sampling periods, the measured NMHC/NO_x ratios are 3.1, 1.7, and 1.4 times higher than those predicted by the MOVES, MOBILE, and EMFAC models, respectively, during high-temperature periods. Although the MOVES NO_x emission factors were generally higher than the measured factors, most differences were not significant considering the variations in the modeled factors using alternative vehicle operating cycles to represent the driving conditions in the tunnel. The three models predicted large differences in NO_x and particle emissions and in the relative contributions of diesel and gasoline vehicles to total NO_x and particulate carbon (TC) emissions in the tunnel.

Implications: Although advances have been made to mobile source emission models over the past two decades, the evidence that mobile source emissions of carbon monoxide and hydrocarbons in urban areas were underestimated by as much as a factor of 2–3 in past inventories underscores the need for on-going verification of emission inventories. Results suggest that there is an overall increase in motor vehicle NMHC emissions on hot days that is not fully accounted for by the emission models. Hot temperatures and concomitant higher ratios of NMHC emissions relative to NO_x both contribute to more rapid and efficient formation of ozone. Also, the ability of EPA's MOVES model to simulate varying vehicle operating modes places increased importance on the choice of operating modes to evaluate project-level emissions.     

Study of Miller timing on exhaust emissions of a hydrotreated vegetable oil (HVO)-fueled diesel engine

The effect of intake valve closure (IVC) timing by utilizing Miller cycle and start of injection (SOI) on particulate matter (PM), particle number, and nitrogen oxide (NO_x) emissions was studied with a hydrotreated vegetable oil (HVO)-fueled nonroad diesel engine. HVO-fueled engine emissions, including aldehyde and polyaromatic hydrocarbon (PAH) emissions, were also compared with those emitted with fossil EN590 diesel fuel. At the engine standard settings, particle number and NO_x emissions decreased at all the studied load points (50%, 75%, and 100%) when the fuel was changed from EN590 to HVO. Adjusting IVC timing enabled a substantial decrease in NO_x emission and combined with SOI timing adjustment somewhat smaller decrease in both NO_x and particle emissions at IVC??50 and??70 °CA points. The HVO fuel decreased PAH emissions mainly due to the absence of aromatics. Aldehyde emissions were lower with the HVO fuel with medium (50%) load. At higher loads (75% and 100%), aldehyde emissions were slightly higher with the HVO fuel. However, the aldehyde emission levels were quite low, so no clear conclusions on the effect of fuel can be made. Overall, the study indicates that paraffinic HVO fuels are suitable for emission reduction with valve and injection timing adjustment and thus provide possibilities for engine manufacturers to meet the strictening emission limits.

Implications: NO_x and particle emissions are dominant emissions of diesel engines and vehicles. New, biobased paraffinic fuels and modern engine technologies have been reported to lower both of these emissions. In this study, even further reductions were achieved with engine valve adjustment combined with novel hydrotreated vegetable oil (HVO) diesel fuel. This study shows that new paraffinic fuels offer further possibilities to reduce engine exhaust emissions to meet the future emission limits.

Supplementary Materials: Supplementary materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a complete list of analysed PAH compounds.     

Idle Emissions from Heavy-Duty Diesel and Natural Gas Vehicles at High Altitude

ABSTRACT

Idle emissions of total hydrocarbon (THC), CO, NO_x, and particulate matter (PM) were measured from 24 heavy-duty diesel-fueled (12 trucks and 12 buses) and 4 heavy-duty compressed natural gas (CNG)-fueled vehicles. The volatile organic fraction (VOF) of PM and aldehyde emissions were also measured for many of the diesel vehicles. Experiments were conducted at 1609 m above sea level using a full exhaust flow dilution tunnel method identical to that used for heavy-duty engine Federal Test Procedure (FTP) testing. Diesel trucks averaged 0.170 g/min THC, 1.183 g/min CO, 1.416 g/min NO_x, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NO_x, and 0.048 g/min PM.

Results are compared to idle emission factors from the MOBILE5 and PART5 inventory models. The models significantly (45-75%) overestimate emissions of THC and CO in comparison with results measured from the fleet of vehicles examined in this study. Measured NO_x emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NO_x emissions increased with Health and Environment; June 30, 1999 (available from the authors).     

Deriving fuel-based emission factor thresholds to interpret heavy-duty vehicle roadside plume measurements

Remote sensing devices have been used for decades to measure gaseous emissions from individual vehicles at the roadside. Systems have also been developed that entrain diluted exhaust and can also measure particulate matter (PM) emissions. In 2015, the California Air Resources Board (CARB) reported that 8% of in-field diesel particulate filters (DPF) on heavy-duty (HD) vehicles were malfunctioning and emitted about 70% of total diesel PM emissions from the DPF-equipped fleet. A new high-emitter problem in the heavy-duty vehicle fleet had emerged. Roadside exhaust plume measurements reflect a snapshot of real-world operation, typically lasting several seconds. In order to relate roadside plume measurements to laboratory emission tests, we analyzed carbon dioxide (CO₂), oxides of nitrogen (NO_X), and PM emissions collected from four HD vehicles during several driving cycles on a chassis dynamometer. We examined the fuel-based emission factors corresponding to possible exceedances of emission standards as a function of vehicle power. Our analysis suggests that a typical HD vehicle will exceed the model year (MY) 2010 emission standards (of 0.2 g NO_X/bhp-hr and 0.01 g PM/bhp-hr) by three times when fuel-based emission factors are 9.3 g NO_X/kg fuel and 0.11 g PM/kg using the roadside plume measurement approach. Reported limits correspond to 99% confidence levels, which were calculated using the detection uncertainty of emissions analyzers, accuracy of vehicle power calculations, and actual emissions variability of fixed operational parameters. The PM threshold was determined for acceleration events between 0.47 and 1.4 mph/sec only, and the NO_X threshold was derived from measurements where after-treatment temperature was above 200°C. Anticipating a growing interest in real-world driving emissions, widespread implementation of roadside exhaust plume measurements as a compliment to in-use vehicle programs may benefit from expanding this analysis to a larger sample of in-use HD vehicles.

Implications: Regulatory agencies, civil society, and the public at large have a growing interest in vehicle emission compliance in the real world. Leveraging roadside plume measurements to identify vehicles with malfunctioning emission control systems is emerging as a viable new and useful method to assess in-use performance. This work proposes fuel-based emission factor thresholds for PM and NOx that signify exceedances of emission standards on a work-specific basis by analyzing real-time emissions in the laboratory. These thresholds could be used to prescreen vehicles before roadside enforcement inspection or other inquiry, enhance and further develop emission inventories, and potentially develop new requirements for heavy-duty inspection and maintenance (I/M) programs, including but not limited to identifying vehicles for further testing.     

Idle Emissions from Medium Heavy-Duty Diesel and Gasoline Trucks

Abstract

Idle emissions data from 19 medium heavy-duty diesel and gasoline trucks are presented in this paper. Emissions from these trucks were characterized using full-flow exhaust dilution as part of the Coordinating Research Council (CRC) Project E-55/59. Idle emissions data were not available from dedicated measurements, but were extracted from the continuous emissions data on the low-speed transient mode of the medium heavy-duty truck (MHDTLO) cycle. The four gasoline trucks produced very low oxides of nitrogen (NO_x) and negligible particulate matter (PM) during idle. However, carbon monoxide (CO) and hydrocarbons (HCs) from these four trucks were approximately 285 and 153 g/hr on average, respectively. The gasoline trucks consumed substantially more fuel at an hourly rate (0.84 gal/hr) than their diesel counterparts (0.44 gal/hr) during idling. The diesel trucks, on the other hand, emitted higher NO_x (79 g/hr) and comparatively higher PM (4.1 g/hr), on average, than the gasoline trucks (3.8 g/hr of NO_x and 0.9 g/hr of PM, on average). Idle NO_x emissions from diesel trucks were high for post-1992 model year engines, but no trends were observed for fuel consumption. Idle emissions and fuel consumption from the medium heavy-duty diesel trucks (MHDDTs) were marginally lower than those from the heavy heavy-duty diesel trucks (HHDDTs), previously reported in the literature.     

Variability in the primary emissions and secondary gas and particle formation from vehicles using bioethanol mixtures

Bioethanol for use in vehicles is becoming a substantial part of global energy infrastructure because it is renewable and some emissions are reduced. Carbon monoxide (CO) emissions and total hydrocarbons (THC) are reduced, but there is still controversy regarding emissions of nitrogen oxides (NO_x), aldehydes, and ethanol; this may be a concern because all these compounds are precursors of ozone and secondary organic aerosol (SOA). The amount of emissions depends on the ethanol content, but it also may depend on the engine quality and ethanol origin. Thus, a photochemical chamber was used to study secondary gas and aerosol formation from two flex-fueled vehicles using different ethanol blends in gasoline. One vehicle and the fuel used were made in the United States, and the others were made in Brazil. Primary emissions of THC, CO, carbon dioxide (CO₂), and nonmethane hydrocarbons (NMHC) from both vehicles decreased as the amount of ethanol in gasoline increased. NO_x emissions in the U.S. and Brazilian cars decreased with ethanol content. However, emissions of THC, CO, and NO_x from the Brazilian car were markedly higher than those from the U.S. car, showing high variability between vehicle technologies. In the Brazilian car, formation of secondary nitrogen dioxide (NO₂) and ozone (O₃) was lower for higher ethanol content in the fuel. In the U.S. car, NO₂ and O₃ had a small increase. Secondary particle (particulate matter [PM]) formation in the chamber decreased for both vehicles as the fraction of ethanol in fuel increased, consistent with previous studies. Secondary to primary PM ratios for pure gasoline is 11, also consistent with previous studies. In addition, the time required to form secondary PM is longer for higher ethanol blends. These results indicate that using higher ethanol blends may have a positive impact on air quality.

Implications: The use of bioethanol can significantly reduce petroleum use and greenhouse gas emissions worldwide. Given the extent of its use, it is important to understand its effect on urban pollution. There is a controversy on whether there is a reduction or increase in PM emission when using ethanol blends. Primary emissions of THC, CO, CO₂, NO_x, and NMHC for both cars decreased as the fraction of ethanol in gasoline increased. Using a photochemical chamber, the authors have found a decrease in the formation of secondary particles and the time required to form secondary PM is longer when using higher ethanol blends.     

Nitrogen oxide emission calculation for post-Panamax container ships by using engine operation power probability as weighting factor: A slow-steaming case

In this study, the nitrogen oxide (NO_x) emission factors and total NO_x emissions of two groups of post-Panamax container ships operating on a long-term slow-steaming basis along Euro–Asian routes were calculated using both the probability density function of engine power levels and the NO_x emission function. The main engines of the five sister ships in Group I satisfied the Tier I emission limit stipulated in MARPOL (International Convention for the Prevention of Pollution from Ships) Annex VI, and those in Group II satisfied the Tier II limit. The calculated NO_x emission factors of the Group I and Group II ships were 14.73 and 17.85 g/kWhr, respectively. The total NO_x emissions of the Group II ships were determined to be 4.4% greater than those of the Group I ships. When the Tier II certification value was used to calculate the average total NO_x emissions of Group II engines, the result was lower than the actual value by 21.9%. Although fuel consumption and carbon dioxide (CO₂) emissions were increased by 1.76% because of slow steaming, the NO_x emissions were markedly reduced by 17.2%. The proposed method is more effective and accurate than the NO_x Technical Code 2008. Furthermore, it can be more appropriately applied to determine the NO_x emissions of international shipping inventory.

Implications: The usage of operating power probability density function of diesel engines as the weighting factor and the NO_x emission function obtained from test bed for calculating NO_x emissions is more accurate and practical. The proposed method is suitable for all types and purposes of diesel engines, irrespective of their operating power level. The method can be used to effectively determine the NO_x emissions of international shipping and inventory applications and should be considered in determining the carbon tax to be imposed in the future.     

Real-world fuel use and gaseous emission rates for flex fuel vehicles operated on E85 versus gasoline

Flex fuel vehicles (FFVs) typically operate on gasoline or E85, an 85%/15% volume blend of ethanol and gasoline. Differences in FFV fuel use and tailpipe emission rates are quantified for E85 versus gasoline based on real-world measurements of five FFVs with a portable emissions measurement system (PEMS), supplemented chassis dynamometer data, and estimates from the Motor Vehicle Emission Simulator (MOVES) model. Because of inter-vehicle variability, an individual FFV may have higher nitrogen oxide (NO_x) or carbon monoxide (CO) emission rates on E85 versus gasoline, even though average rates are lower. Based on PEMS data, the comparison of tailpipe emission rates for E85 versus gasoline is sensitive to vehicle-specific power (VSP). For example, although CO emission rates are lower for all VSP modes, they are proportionally lowest at higher VSP. Driving cycles with high power demand are more advantageous with respect to CO emissions, but less advantageous for NO_x. Chassis dynamometer data are available for 121 FFVs at 50,000 useful life miles. Based on the dynamometer data, the average difference in tailpipe emissions for E85 versus gasoline is ?23% for NO_x, ?30% for CO, and no significant difference for hydrocarbons (HC). To account for both the fuel cycle and tailpipe emissions from the vehicle, a life cycle inventory was conducted. Although tailpipe NO_x emissions are lower for E85 versus gasoline for FFVs and thus benefit areas where the vehicles operate, the life cycle NO_x emissions are higher because the NO_x emissions generated during fuel production are higher. The fuel production emissions take place typically in rural areas. Although there are not significant differences in the total HC emissions, there are differences in HC speciation. The net effect of lower tailpipe NO_x emissions and differences in HC speciation on ozone formation should be further evaluated.

Implications: Reported comparisons of flex fuel vehicle (FFV) tailpipe emission rates for E85 versus gasoline have been inconsistent. To date, this is the most comprehensive evaluation of available and new data. The large range of inter-vehicle variability illustrates why prior studies based on small sample sizes led to apparently contradictory findings. E85 leads to significant reductions in tailpipe nitrogen oxide (NO_x) and carbon monoxide (CO) emission rates compared with gasoline, indicating a potential benefit for ozone air quality management in NO_x-limited areas. The comparison of FFV tailpipe emissions between E85 and gasoline is sensitive to power demand and driving cycles.     

Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston,TX

Nitrous acid is an important component of nighttime N-oxide chemistry, and provides a significant source of both OH and NO in polluted urban air masses shortly after sunrise. Several recent studies have called for new sources of HONO to account for daytime levels much higher than are consistent with current understanding. However, measurement of HONO is problematic, with most in-situ techniques reporting higher values than simultaneous optical measurements by long-path DOAS, especially during daytime. The discrepancy has been attributed to positive interference in the in-situ techniques, negative interference in DOAS retrievals, the difficulty of comparing the different air masses sampled by the methods, or combinations of these.During August and September 2006, HONO mixing ratios from collocated long-path DOAS and automated mist-chamber/ion chromatograph (MC/IC) systems ranged from several ppbv during morning rush hour to daytime minima near 100 pptv. Agreement between the two techniques was excellent across this entire range during many days, showing that both instruments accurately measured HONO during this campaign. A small bias towards higher LP-DOAS observations at night can be attributed to slow vertical mixing leading to pronounced HONO profiles. A positive daytime bias of the MC/IC instrument during several days in late August/early September was correlated with photochemically produced compounds such as ozone, HNO₃ and HCHO, but not with NO₂, NO_x, HO₂NO₂, or the NO₂ photolysis rate. While an interferant could not be identified organic nitrites appear a possible explanation for our observations.     

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.     

Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies

Both similarities and differences in summertime atmospheric photochemical oxidation appear in the comparison of four field studies: TEXAQS2000 (Houston, 2000), NYC2001 (New York City, 2001), MCMA2003 (Mexico City, 2003), and TRAMP2006 (Houston, 2006). The compared photochemical indicators are OH and HO₂ abundances, OH reactivity (the inverse of the OH lifetime), HO_x budget, OH chain length (ratio of OH cycling to OH loss), calculated ozone production, and ozone sensitivity. In terms of photochemical activity, Houston is much more like Mexico City than New York City. These relationships result from the ratio of volatile organic compounds (VOCs) to nitrogen oxides (NO_x), which are comparable in Houston and Mexico City, but much lower in New York City. Compared to New York City, Houston and Mexico City also have higher levels of OH and HO₂, longer OH chain lengths, a smaller contribution of reactions with NO_x to the OH reactivity, and NO_x-sensitivity for ozone production during the day. In all four studies, the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) are significant, if not dominant, HO_x sources. A problematic result in all four studies is the greater OH production than OH loss during morning rush hour, even though OH production and loss are expected to always be in balance because of the short OH lifetime. The cause of this discrepancy is not understood, but may be related to the under-predicted HO₂ in high NO_x conditions, which could have implications for ozone production. Three photochemical indicators show particularly high photochemical activity in Houston during the TRAMP2006 study: the long portion of the day for which ozone production was NO_x-sensitive, the calculated ozone production rate that was second only to Mexico City's, and the OH chain length that was twice that of any other location. These results on photochemical activity provide additional support for regulatory actions to reduce reactive VOCs in Houston in order to reduce ozone and other pollutants.     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys,California

As part of the 2010 Van Nuys tunnel study, researchers from the University of Denver measured on-road fuel-specific light-duty vehicle emissions from nearly 13,000 vehicles on Sherman Way (0.4 miles west of the tunnel) in Van Nuys, California, with its multispecies Fuel Efficiency Automobile Test (FEAT) remote sensor a week ahead of the tunnel measurements. The remote sensing mean gram per kilogram carbon monoxide (CO), hydrocarbon (HC), and oxide of nitrogen (NO_x) measurements are 8.9% lower, 41% higher, and 24% higher than the tunnel measurements, respectively. The remote sensing CO/NO_x and HC/NO_x mass ratios are 28% lower and 20% higher than the comparable tunnel ratios. Comparisons with the historical tunnel measurements show large reductions in CO, HC, and NO_x over the past 23 yr, but little change in the HC/NO_x mass ratio since 1995. The fleet CO and HC emissions are increasingly dominated by a few gross emitters, with more than a third of the total emissions being contributed by less than 1% of the fleet. An example of this is a 1995 vehicle measured three times with an average HC emission of 419 g/kg fuel (two-stroke snowmobiles average 475 g/kg fuel), responsible for 4% of the total HC emissions. The 2008 economic downturn dramatically reduced the number of new vehicles entering the fleet, leading to an age increase (>1 model year) of the Sherman Way fleet that has increased the fleet's ammonia (NH₃) emissions. The mean NH₃ levels appear little changed from previous measurements collected in the Van Nuys tunnel in 1993. Comparisons between weekday and weekend data show few fleet differences, although the fraction of light-duty diesel vehicles decreased from the weekday (1.7%) to Saturday (1.2%) and Sunday (0.6%).

Implications: On-road remote sensing emission measurements of light-duty vehicles on Sherman Way in Van Nuys, California, show large historical emission reductions for CO and HC emissions despite an older fleet arising from the 2008 economic downturn. Fleet CO and HC emissions are increasingly dominated by a few gross emitters, with a single 1995 vehicle measured being responsible for 4% of the entire fleet's HC emissions. Finding and repairing and/or scrapping as little as 2% of the fleet would reduce on-road tailpipe emissions by as much as 50%. Ammonia emissions have locally increased with the increasing fleet age.     

Emission Factors for High-Emitting Vehicles Based on On-Road Measurements of Individual Vehicle Exhaust with a Mobile Measurement Platform

ABSTRACT

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO_x), and particle mass with aerodynamic diameter below 2.5 μm (PM_2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO_x, black carbon (BC), PM_2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO_x and CO fleet-average emission factors and more than 60% of PM_2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM_2.5, and NO_x tended to cluster among the same vehicles.

IMPLICATIONS This study presents the characterization of on-road vehicle emissions in Wilmington, CA, by sampling individual vehicle plumes. Approximately 5% of the vehicles were high emitters, whose emissions were more than 5 times the fleet-average values. These high emitters were responsible for 30% and more than 50% of the average emission factors of LDGVs and HDDVs, respectively. It is likely that as the overall fleet becomes cleaner due to more stringent regulations, a small fraction of the fleet may contribute a growing and disproportionate share of the overall emissions. Therefore, long-term changes in on-road emissions need to be monitored.