Summer and winter nonmethane hydrocarbon emissions from on-road motor vehicles in the Midwestern United States

On-road vehicle emission rates of nonmethane hydrocarbons (NMHCs) were measured in two tunnels in Milwaukee, WI, in summer 2000 and winter 2001. Seasonal ambient temperatures in the Midwestern United States vary more widely than in locations where most studies of NMHC emissions from vehicle fleets have been conducted. Ethanol is the added fuel oxygenate in the area, and, thus, emissions measured here are of interest as other regions phase out methyl tertiary butyl ether and increase the use of ethanol. Total emissions of NMHCs in three types of tunnel tests averaged 4560 +/- 800 mg L(-1) fuel burned (average +/- standard error). To investigate the impact of cold start on vehicle emissions, samples were collected as vehicles exited a parking structure in subzero temperatures. NMHC emissions in the subzero cold-start test were 8830 +/- 190 mg L(-1) fuel-nearly double the tunnel emissions. Comparison of ambient data for the Milwaukee area with tunnel emissions showed the impact of seasonal differences in fuels and emissions on the urban atmosphere. Composition of fuel samples collected from area gas stations in both seasons was correlated with vehicle emissions; the predominant difference was increased winter emissions of lighter hydrocarbons present in winter gasoline. A chemical mass balance model was used to determine the contributions of whole gasoline and gasoline headspace vapors to vehicle emissions in the tunnel and cold-start tests, which were found to vary with season. Results of the mass balance model also indicate that partially combusted components of gasoline are a major contributor to emissions of aromatic compounds and air toxic compounds, including benzene, toluene, xylenes, napthalene, and 1,3-butadiene, whereas air toxics hexane and 2,2,4-trimethylpentane are largely attributed to gasoline and headspace vapors.     

Source Fingerprints for Volatile Non-Methane Hydrocarbons

Non-methane hydrocarbon (NMHC) source profiles consisting of 35 hydrocarbon species were measured for vehicle and petroleum refinery emissions. Refueling emissions were found to be sensitive to the grade and volatility class of fuel and to be composed mainly of saturated hydrocarbons such as n-butane and 2-methy I butane. Unsaturated and aromatic hydrocarbons, which are released from the tailpipe of vehicles as products of combustion and unburned fuel, were more prevalent in roadway emissions comprising approximately 34 percent of the total NMHCs. Cold-start emissions were nearly indistinguishable from the roadway emission profile. The only significant differences were in toluene, ethylene and acetylene, which may be related to the efficiency of combustion when the vehicle is initially started. Saturated hydrocarbon distributions of the hot-soak profiles were found to be similar to refueling emissions. The only significant difference in the profiles was in the aromatic content, which may be related to the grade of the gasoline and the effectiveness of evaporative emission control devices. The temporal variation in refinery emissions was significant and may be related to variations in refinery activities such as the production and blending of feed stocks to produce different fuels.     

Characterising sources and sinks of rural VOC in eastern France

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.     

Methane and carbon dioxide emissions from Shan-Chu-Ku landfill site in northern Taiwan

To investigate the methane and carbon dioxide emissions from landfill, samples were taken of material up to 5 years old from Shan-Chu-Ku landfill located in the northern part of Taiwan. Atmospheric concentrations of carbon dioxide, methane and nitrous oxide ranged from 310 to 530, 2.64 to 20.16 and 0.358 to 1.516 ppmv with the measurement of gas-type open-path Fourier transform infra-red (FTIR) spectroscopy during February 1998 to March 2000, respectively. Average methane emission rate was 13.17, 65.27 and 0.99 mgm(-2)h(-1) measured by the gas chromatography chamber method in 1-2, 2-3 and 5 year-old landfill, respectively. Similarly, average carbon dioxide emission rate was 93.70, 314.60 and 48.46 mgm(-2)h(-1), respectively. About 2-3 year-old landfill had the highest methane and carbon dioxide emission rates among the tested areas, while 5 year-old landfill was the least. Methane emission rate at night in most tested locations was higher than that in the daytime. Total amount of methane and carbon dioxide emission from this landfill was around 171 and 828 ton in 1999, respectively.     

Criteria and Air-Toxic Emissions from In-Use Automobiles in the National Low-Emission Vehicle Program

Abstract

The U.S. Environmental Protection Agency (EPA) implemented a program to identify tailpipe emissions of criteria and air-toxic contaminants from in-use, light-duty low-emission vehicles (LEVs). EPA recruited 25 LEVs in 2002 and measured emissions on a chassis dynamometer using the cold-start urban dynamometer driving schedule of the Federal Test Procedure. The emissions measured included regulated pollutants, particulate matter, speciated hydrocarbon compounds, and carbonyl compounds. The results provided a comparison of emissions from real-world LEVs with emission standards for criteria and air-toxic compounds. Emission measurements indicated that a portion of the in-use fleet tested exceeded standards for the criteria gases. Real-time regulated and speciated hydrocarbon measurements demonstrated that the majority of emissions occurred during the initial phases of the cold-start portion of the urban dynamometer driving schedule. Overall, the study provided updated emission factor data for real-world, in-use operation of LEVs for improved emissions modeling and mobile source inventory development.     

Criteria and air-toxic emissions from in-use automobiles in the National Low-Emission Vehicle program

The U.S. Environmental Protection Agency (EPA) implemented a program to identify tailpipe emissions of criteria and air-toxic contaminants from in-use, light-duty low-emission vehicles (LEVs). EPA recruited 25 LEVs in 2002 and measured emissions on a chassis dynamometer using the cold-start urban dynamometer driving schedule of the Federal Test Procedure. The emissions measured included regulated pollutants, particulate matter, speciated hydrocarbon compounds, and carbonyl compounds. The results provided a comparison of emissions from real-world LEVs with emission standards for criteria and air-toxic compounds. Emission measurements indicated that a portion of the in-use fleet tested exceeded standards for the criteria gases. Real-time regulated and speciated hydrocarbon measurements demonstrated that the majority of emissions occurred during the initial phases of the cold-start portion of the urban dynamometer driving schedule. Overall, the study provided updated emission factor data for real-world, in-use operation of LEVs for improved emissions modeling and mobile source inventory development.     

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.     

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.     

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.     

Penetration of Evaporative Emissions into a Home from an M85-Fueled Vehicle Parked in an Attached Garage

ABSTRACT

The use of both oxygenated fuels in carbon monoxide (CO) nonattainment areas and reformulated gasoline in ozone nonattainment areas has been mandated by the 1990 Clean Air Act Amendments. Methanol has been proposed as an alternative fuel for CO nonattainment areas. Its use will potentially increase indoor methanol inhalation exposure resulting from the evaporation of metha-nol vapor from methanol-fueled vehicles parked in residential garages. Indoor air concentrations of metha-nol, benzene, and toluene were measured in a residential home with an attached garage. The effects of vehicle emission control devices (charcoal canister hose connection); home heating, ventilation, and air conditioning (HVAC) fans; ambient air, garage, and fuel tank temperatures; and wind speed were examined.

The disconnection of the charcoal canister hose, which simulates a spent evaporative emission control device, resulted in elevated benzene, toluene, and metha-nol concentrations in the garage and attached home. Higher fuel tank temperatures resulted in higher benzene and toluene concentrations in the garage, but not methanol. The concentrations for all compounds in the garage and concentrations of benzene and toluene in the adjacent room were lower when the HVAC fan was on than when it was off, while the concentrations of all three compounds in the rest of the house were higher, although these differences were not statistically significant. Thus, the portion of the population that parks cars in garages attached to homes will experience increased methanol exposures if methanol is used as an automotive fuel.     

Measured carbon monoxide concentrations from stock and reduced-emission prototype portable generators operated in an attached garage

There is concern about the hazard of acute residential CO exposures from portable gasoline-powered generators, which can result in death or serious adverse health effects in exposed individuals. To address this hazard, the U.S. Consumer Product Safety Commission has developed low CO emission prototype generators by adapting off-the-shelf emission control technologies onto commercially available generators. A series of tests was conducted to characterize the indoor CO concentrations resulting from portable generators operating in the attached garage of a research house under seven different test house/garage configurations. The tested generators include both unmodified and modified low CO emission prototypes. It was found that CO concentrations varied widely, with peak house CO concentrations ranging from under 10 ppm to over 10,000 ppm. The highest concentrations in the house resulted from operation of the unmodified generator in the garage with the garage bay door closed and the house access door open. The lowest concentrations resulted from operation of a modified low CO emission prototype in the garage with the garage bay door open and the house access door closed. These tests documented reductions of up to 98% in CO concentrations due to emissions from two low CO emission portable generators compared to a stock generator.

Implications: Improper portable generator use has caused 800 U.S. deaths in the past 14 years. Generators operated in attached garages can cause CO to quickly reach deadly levels. Two low-emission prototypes generators were tested and had CO emissions reduced by up to 98%. Low-emission generators can reduce the risk of consumer poisonings and deaths.     

Real-World In-Use Activity,Fuel Use,and Emissions for Nonroad Construction Vehicles: A Case Study for Excavators

Abstract

A study design was developed and demonstrated for deployment of a portable emission measurement system (PEMS) for excavators. Excavators are among the most commonly used vehicles in construction activities. The PEMS measured nitric oxide, carbon monoxide, hydrocarbons, carbon dioxide, and opacity-based particulate matter. Data collection, screening, processing, and analysis protocols were developed to assure data quality and to quantify variability in vehicle fuel consumption and emissions rates. The development of data collection procedures was based on securing the PEMS while avoiding disruption to normal vehicle operations. As a result of quality assurance, approximately 90% of the attempted measurements resulted in valid data. On the basis of field data collected for three excavators, an average of 50% of the total nitric oxide emissions was associated with 29% of the time of operation, during which the average engine speed and manifold absolute pressure were significantly higher than corresponding averages for all data. Mass per time emission rates during non-idle modes (i.e., moving and using bucket) were on average 7 times greater than for the idle mode. Differences in normalized average rates were influenced more by intercycle differences than intervehicle differences. This study demonstrates the importance of accounting for intercycle variability in real-world in-use emissions to develop more accurate emission inventories. The data collection and analysis methodology demonstrated here is recommended for application to more vehicles to better characterize real-world vehicle activity, fuel use, and emissions for nonroad construction equipment.     

Penetration of evaporative emissions into a home from an M85-fueled vehicle parked in an attached garage

The use of both oxygenated fuels in carbon monoxide (CO) nonattainment areas and reformulated gasoline in ozone nonattainment areas has been mandated by the 1990 Clean Air Act Amendments. Methanol has been proposed as an alternative fuel for CO nonattainment areas. Its use will potentially increase indoor methanol inhalation exposure resulting from the evaporation of methanol vapor from methanol-fueled vehicles parked in residential garages. Indoor air concentrations of methanol, benzene, and toluene were measured in a residential home with an attached garage. The effects of vehicle emission control devices (charcoal canister hose connection); home heating, ventilation, and air conditioning (HVAC) fans; ambient air, garage, and fuel tank temperatures; and wind speed were examined. The disconnection of the charcoal canister hose, which simulates a spent evaporative emission control device, resulted in elevated benzene, toluene, and methanol concentrations in the garage and attached home. Higher fuel tank temperatures resulted in higher benzene and toluene concentrations in the garage, but not methanol. The concentrations for all compounds in the garage and concentrations of benzene and toluene in the adjacent room were lower when the HVAC fan was on than when it was off, while the concentrations of all three compounds in the rest of the house were higher, although these differences were not statistically significant. Thus, the portion of the population that parks cars in garages attached to homes will experience increased methanol exposures if methanol is used as an automotive fuel.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Spatiotemporal analysis of traffic emissions in over 5000 municipal districts in Brazil

Exposure to traffic emission is harmful to human health. Emission inventories are essential to public health policies aiming at protecting human health, especially in areas with incomplete or nonexistent air pollution monitoring networks. In Brazil, for example, only 1.7% of municipal districts have a monitoring network, and only a few studies have reported data on vehicle emission inventories. No studies have presented emission inventories by municipality. In this study, we predicted vehicular emissions for 5570 municipal districts in Brazil during the period 2001–2012. We used a top-down method to estimate emissions. Carbon dioxide (CO₂) is the pollutant with the highest emissions, with approximately 190 million tons per year during the period 2001–2012). For the other traffic-related pollutants, we predicted annual emissions of 1.5 million tons for carbon monoxide (CO), 1.2 million tons of nitrogen oxides (NO_x), 209,000 tons of nonmethane hydrocarbons (NMHC), 58,000 tons of particulate matter (PM), and 42,000 tons for methane (CH₄). From 2001 to 2012, CO, NMHC, and PM emissions decreased by 41, 33, and 47%, respectively, whereas those CH₄, NO_x, and CO₂ increased by 2, 4, and 84%, respectively. We estimated uncertainties in our study and found that NO_x was the pollutant with the lowest percentage difference, 8%, and NMHC with the highest one, 30%. For CO, CH₄, CO₂, and PM, the values were 22, 14, 21, and 20%, respectively. Finally, we found that during 2001 and 2012 emissions increased in the Northwest and Northeast. In contrast, pollutant emissions, except for CO₂, decreased in the Southeast, South, and part of Midwest. Our predictions can be critical to efforts developing cost-effective public policies tailored to individual municipal districts in Brazil.

Implications: Emission inventories may be an alternative approach to provide data for air quality forecasting in areas where air quality data are not available. This approach can be an effective tool in developing spatially resolved emission inventories.     

Evaluation of non-methane hydrocarbon (NMHC) emissions based on an ambient air measurement in Tokyo area,Japan

Non-methane hydrocarbons (NMHCs) are known to have an important role on air quality due to their high reactivity. NMHC analysis has been performed on 148 ambient air samples collected at five different sites in the Kanto area (Tokyo metropolitan area and surrounding six prefectures) of Japan in summer and winter of 2008, and fifty NMHCs have been determined and quantified. A field measurement campaign has been conducted at one of the busiest intersections in Tokyo metropolitan area in winter of 2008. NMHC emissions are evaluated through comparison of distributions of individual NMHCs emitted from motor vehicles, which are estimated from the measurements, with those determined from the current emissions inventory. The comparison revealed that the measured distributions of acetylene, ethylene and toluene showed a good agreement with those estimated from the emissions inventory (the values estimated from the measurements are a factor of 1.5, 0.56 and 2.3 larger than the emissions inventory in median, respectively), however, propane and isobutane are found to be significantly underestimated in the emissions inventory (the measured values were a factor of 18 and 5.1 larger than the emissions inventory, respectively). The significant underestimate of propane can be explained by that the current emissions inventory does not consider emissions from liquefied propane gas (LPG) fueled vehicles. However, for isobutane, reasons for the underestimate are still unclear. Another field measurement has been conducted in summer of 2008, where the air samples have been collected at three different sites on the ground and by a helicopter as well. Remarkable high concentrations of 1-butene and cis- and trans-2-butenes have been sporadically observed in the samples collected at Urayasu in the coastal area of Tokyo bay. Calculated propylene equivalent (PE) concentrations of butenes revealed that those have a significantly important role in ozone formation when the air plume is affected by emissions from their emission sources. The PE concentrations of butenes varied from 0.1 to 39 ppbC, and accounted for 1.5–75% of total PE concentrations at Urayasu. Most of the continuous air quality monitoring stations does not record concentrations of individual hydrocarbons, therefore, the importance of reactive and low concentration hydrocarbon such as butenes might be overlooked in the current emissions inventory and/or air quality model. In this paper, the reliability of NMHC emissions is evaluated based on the field measurements. Their possible impacts on air quality in the Kanto area are discussed as well, based on the calculated propylene equivalent concentrations.     

Continuous Monitoring of Methane and Other Hydrocarbons In Urban Atmospheres

Continuous measurements of total hydrocarbons (and other organic substances) and of methane were made in Cincinnati and Los Angeles for three-month periods. Some of the measurements were made during episodes of photochemical air pollution. Two instruments, one for measurement of total hydrocarbons and the other for methane, were operated in parallel. Both incorporated flame ionization detectors having greater sensitivity than commercial flame ionization instruments. The flame ionization analysis for methane was made specific by use of an adsorbent carbon column preceding the analyzer to retain all organic substances except methane. Subtracting the methane concentration values from those for total hydrocarbons gave nonmethane hydrocarbon concentrations. The data showed diurnal patterns of concentrations of methane and nonmethane hydrocarbons in the atmosphere. Average hourly values for methane were strikingly similar in Los Angeles and in Cincinnati (2.6 and 2.4 ppm, respectively); those for nonmethane hydrocarbons were four times as high in Los Angeles (3.0 and 0.8 ppm, respectively). A bimodal frequency distribution pattern of the concentrations suggested that atmospheric ventilation was either good or poor, with less than a random amount of time in intermediate stages. The width of the methane frequency distribution peak was about half the width of that for nonmethane hydrocarbons, indicating a different and more constant source for the former.     

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.     

Speciation of non-methane hydrocarbons (NMHCs) from anthropogenic sources in Beirut,Lebanon

The chemical composition of emissions from the different anthropogenic sources of non-methane hydrocarbons (NMHC) is essential for modeling and source apportionment studies. The speciated profiles of major NMHC sources in Lebanon, including road transport, gasoline vapor, power generation, and solvent use were established. Field sampling have been carried out by canisters in 2012. Around 67 NMHC (C2 to C9) were identified and quantified by using a gas chromatograph equipped with a flame ionization detector. Typical features of the roadway emissions included high percentages of isopentane, butane, toluene, xylenes, ethylene, and ethyne. Gasoline evaporation profiles included high percentage of the C4–C5 saturated hydrocarbons reaching 59 %. The main compounds of the power generator emissions are related to combustion. Toluene and C8–C9 aromatics were the most abundant species in emissions from paint applications. Finally, the impact of the use of region-specific source profile is tackled regarding the implication on air quality.     

On-road measurement of vehicle tailpipe emissions using a portable instrument

A study design procedure was developed and demonstrated for the deployment of portable onboard tailpipe emissions measurement systems for selected highway vehicles fueled by gasoline and E85 (a blend of 85% ethanol and 15% gasoline). Data collection, screening, processing, and analysis protocols were developed to assure data quality and to provide insights regarding quantification of real-world intravehicle variability in hot-stabilized emissions. Onboard systems provide representative real-world emissions measurements; however, onboard field studies are challenged by the observable but uncontrollable nature of traffic flow and ambient conditions. By characterizing intravehicle variability based on repeated data collection runs with the same driver/vehicle/route combinations, this study establishes the ability to develop stable modal emissions rates for idle, acceleration, cruise, and deceleration even in the face of uncontrollable external factors. For example, a consistent finding is that average emissions during acceleration are typically 5 times greater than during idle for hydrocarbons and carbon dioxide and 10 times greater for nitric oxide and carbon monoxide. A statistical method for comparing on-road emissions of different drivers is presented. Onboard data demonstrate the importance of accounting for the episodic nature of real-world emissions to help develop appropriate traffic and air quality management strategies.