On-Road Measurement of Vehicle Tailpipe Emissions Using a Portable Instrument

Abstract

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.     

A Comparison of Tailpipe,Dilution Tunnel,and Wind Tunnel Data in Measuring Motor Vehicle PM

ABSTRACT

Comparison between particle size distributions recorded directly at the tailpipes of both diesel and gasoline vehicles and measurements made using a conventional dilution tunnel reveals two problems incurred when using the latter method for studying particle number emissions. One is the potential for particulate matter (PM) artifacts originating from hydrocarbon material stored in the transfer hose connecting the tailpipe to the dilution tunnel, and the other is the particle coagulation (as well as condensation and chemical changes) that occurs during the transport. Both are potentially generic to current PM emissions measurement practices. The artifacts typically occur as a nanoparticle mode (10–30 nm) that is 2–4 orders of magnitude larger than what is present in the vehicle exhaust and can easily be mistaken for a similar mode that can arise from the nucleation of hydrocarbon or SO₄ ^2-components in the exhaust under appropriate dilution rates. Wind tunnel measurements are in good agreement with those made directly from the tailpipe and substantiate the potential for artifacts. They reveal PM levels for the recent model port fuel injection (PFI) gasoline vehicles tested that are small compared with the ambient background particle level during steady-state driving. The PM emissions recorded for drive cycles such as the Federal Test Procedure (FTP) and US06 occur primarily during acceleration, as has been previously noted. Light-duty diesel vehicle emissions normally exhibit a single lognormal mode centered between 55 and 80 nm, although a nonartifact nanoparticle mode in some cases appears at a 70-mph cruise up a grade.     

An Aerosol Sampler for Determination of Particle Concentration as a Function of Size and Time

A high flow rate four-stage impacfor was developed for the determination of aerosol concentration as a function of both particle size and time. The unit is very useful for long-term sampling intervals (24 hr) and for sampling very dusty atmospheres. Gas-borne particulate matter is collected out on four rotating drums, each with a collection surface area of about 10 sq in.; this allows a large quantity of materials to be collected without danger of particle build-up and blow-off. A particle size-collection efficiency calibration for the unit is presented together with experimental data on wall losses, surface coatings, and other important operational considerations.     

A High-Volume Sampler for the Determination of Particle Size Distributions in Ambient Air

A size selective particle sampler has been developed for continuous sampling of the urban aerosol over periods ranging from hours to weeks, providing relatively large sample weights. The system, which is now operating in New York City, uses a parallel array of two-stage samplers. The cyclones used as the first stage collectors have 50% particle retention at 3.5,2.5,1.5 and 0.5 µm aerodynamic diameter, respectively. Undersize particles which pass through the cyclones are captured on glass fiber filters. Equal intake velocities are assured by using flow equalizers on the inlets to the cyclones. Accurate control of the flow through the cyclones is obtained by the use of an integrated circuit pressure transducer in conjunction with a specially designed feedback control circuit. The collection efficiencies of the cyclone were calibrated using monodisperse ferric oxide test aerosols tagged with Tc-99m. Mass balances of the par-ticulates collected on the cyclones and filters are obtained for the five sampling stages. Preliminary results show the distributions of the total suspended particulates in New York City to be bimodal. The distributions of lead, copper, and manganese with particle size are also discussed.     

Design and Testing of a New Size Classifying Isokinetic Sequential Aerosol Sampler

Two versions of a size-classifying isokinetic sequential aerosol sampler (SCISAS) have been designed, built, tested, and deployed in a field program in the southwestern United States. The SCISAS units can operate at unattended sites, exposing four or more filter types simultaneously, in two size ranges, for six sampling time Intervals. Design considerations included theoretical estimates of aerosol particle losses in the 0-15 μm size range.

SCISAS prototypes have been tested to evaluate their sampling efficiency as a function of flow rate, the sensitivity of the sampling efficiency to isokinetic matching within the SCISAS sampling stack, the equivalency of their sampling ports, and their passive deposition characteristics. The prototypes were also compared to several other types of aerosol filtration samplers already in common use. These tests show that particle loss mechanisms within the SCISAS usually cause no more than 5 percent losses, and that the SCISAS units agree, within one to two measurement uncertainty intervals, with other types of aerosol samplers.     

Comparison of Particle Size Distributions and Elemental Partitioning from the Combustion of Pulverized Coal and Residual Fuel Oil

ABSTRACT

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impac-tion as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments.

Experimental results on the mass and compositions of particles between 0.03 and >20 μm in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-μm aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large.

Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM <2.5 μm without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (~0.1 μm). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM <2.5 μm and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.     

Development and Evaluation of an Impactor for a PM2.5 Speciation Sampler

ABSTRACT

A conventional impactor for a particle speciation sampler was developed and validated through laboratory and field tests. The speciation sampler consists of the following components: a PM_2.5 conventional impactor that removes particles larger than 2.5 μm, an all-glass, coated honeycomb diffusion denuder, and a 47-mm filter pack. The speciation sampler can operate at two different sampling rates: 10 and 16.7 L/min. An experimental characterization of the impactor’s performance was conducted. The impactor’s collection efficiency was examined as a function of critical design parameters such as Reynolds number, the distance from the nozzle exit to the impac-tion plate, and the impaction substrate coating method. The bounce of particles larger than the cut point was successfully minimized by using a greased surface as the im-paction substrate. Additionally, a series of field intercomparison experiments were conducted at both 10 and 16.7 L/min airflow. PM_2.5 mass and SO₄ ^2- concentrations were measured and compared with the Federal Reference Method (FRM) and found to be in good agreement. Results of the laboratory chamber tests also indicated that the impactor’s performance was in good agreement with the FRM.     

Woodstove Smoke and CO Emissions: Comparison of Reference Methods with the VPI Sampler

A new field sampler has been developed for measuring the particulate matter (PM) and carbon monoxide emissions of woodburning stoves. Particulate matter is determined by carbon balance and the workup of a sample train which is similar to a room-temperature EPA Method 5G train. A steel tank, initially evacuated, serves as the motive force for sampling and also accumulates a gas sample for post-test analysis of time-averaged stack CO and CO₂ concentrations. Workup procedures can be completed, within 72 hours of sampler retrieval. The system has been compared to reference methods in two laboratory test series involving six different woodburning appliances and two independent laboratories. The correlation of field sampler emission rates and reference method rates is strong.     

Atmospheric Aerosol Composition and Concentration as a Function of Particle Size and of Time

As a step toward better understanding the reactive Los Angeles air basin atmosphere, a study was undertaken at the University of California—Riverside Campus, to determine the composition and concentration of atmospheric particulate matter as a function of particle size and time. The study involved developing a method for obtaining size-classified, time-fractionated aerosol samples amenable to chemical and physical (including microscopic) analysis. During a 15-day period, samples were obtained over 4-hr periods and subsequently analyzed for nitrate, sulfate, iron, and lead. Concentration of six gaseous pollutantsj total aerosol light-scattering, and several meteorological measurements were simultaneously recorded and averaged over the 4-hr intervals. This data was presented graphically to show the diurnal variation in and relationship between gaseous, particulate, and meteorological measurements. A strong relationship between gaseous peroxyacetyl nitrate, particulate nitrate, and aerosol light-scattering was found. High concentrations of ammonium nitrate particles, mainly in the 0.5-2μ, diameter size range, were found in the atmospheric particulate samples collected on days of very high smog (very limited visibility).     

Size Distribution and Sources of Aerosol in Launceston,Australia, during Winter 1997

ABSTRACT

As part of a pilot study into the chemical and physical properties of Australian fine particles, a suite of aerosol samples was collected at Ti Tree Bend in Launceston, Tasmania, during June and July 1997. This period represents midwinter in the Southern Hemisphere, a period when aerosol sources in Launceston are dominated by smoke from domestic wood burning. This paper describes the results from this measurement campaign, with the aim of assessing the effect of wood smoke on the chemical and physical characteristics of ambient aerosol. A micro orifice uniform deposit impactor (MOUDI) was used to measure the size distributions of the aerosol from 0.05 to 20 n m aerodynamic diameter. Continuous measurements of fine particle mass were made using a PM_2.5 tapered element oscillating microbalance (TEOM) and light scattering coefficients at 530 nm were measured with nephelometers.

Mass size distributions tended to be bimodal, with the diameter of the dominant mode tending to smaller sizes with increases in total mass. Non-sea salt potassium and polycyclic aromatic hydrocarbons (PAHs) were used as chemical tracers for wood smoke. Wood smoke was found to increase absolute particle mass (enough to regularly exceed air quality standards), and to concentrate mass in a single mode below 1 μm aerodynamic diameter. The acid-base equilibrium of the aerosol was altered by the wood smoke source, with free acidity hydrogen ion, non-sea salt sulfate, and ammonium concentrations being higher and the concentration of all species, including nitrate (to differing extents), focused in the fine particle size ranges. The wood smoke source also heavily influenced the aerosol scattering efficiency, adding to a strong diurnal cycle in both mass concentration and light scattering.     

A Comparison of the Size Distribution of Particulates Emitted from Air,Mechanical, and Steam Atomized Oil Fired Burners

Particulate size distributions were obtained in the effluent gases from three steam generating boilers of a power station employing mechanical, steam, and air systems for heavy fuel atomization. Samples were obtained with an eight-stage cascade impactor. The air atomized burner produced the lowest particulate loading, the greatest percentage of particulates by weight in the submicron range, and particulates with the lowest combustible content.     

Comparison of Fine Particles and the Relationship between Particle Variations and Meteorology at an Urban Site and a Remote Site in the Eastern United States

Abstract

This study compared the variations in the mass of certain particles at an urban site, Washington, DC, and at a remote site, Shenandoah National Park, VA, in the eastern United States. Seven years (1991-1997) of Interagency Monitoring of Protected Visual Environments (IMPROVE) fine particulate matter (PM_2.5), PM₁₀, coarse fraction, SO₄ ^2?, and total sulfur data were used for this study together with available meteorology/climatology data. Various statistical modeling and analysis procedures, including time series analysis, factor analysis, and regression modeling, were employed. Time series of the constituents were divided into four terms: the long-term mean, the intra-annual perturbation, the interannual perturbation, and the synoptic perturbation. PM_2.5 at the two sites made up ~72% of the total mass for PM₁₀, and the coarse fraction made up the remaining 28%, on average. Thirty-one percent of the PM_2.5 at the DC site and 42% at the Shenandoah site was SO₄ ^2?, based on average data for the entire period. At the DC site, the two main contributors to the constituent mass were the long-term mean and the synoptic perturbation terms, and at the Shenandoah site, they were the long-term mean and the intra-annual perturbation terms. This suggested that the constituent mass at the two sites was affected by very different processes. The terms that provided the principal contribution to the constituent mass at the two sites were studied in detail.

At the DC site, dew point trends, a climate variable, were the primary driver of the 7-year trends for PM_2.5, PM₁₀, the coarse fraction, and total sulfur, and SO₂ emission trends were the primary driver of the trends for SO₄ ^2?. SO₂ emission trends influenced the trends for PM_2.5 and total sulfur, appearing as the second term in the model, but only parameters dealing with climate trends had significant effects on the trends for PM₁₀ and the coarse fraction. At the Shenandoah site, only parameters dealing with climate trends affected long-term particle trends.     

Aerosol Particle Number Concentration Measurements in Five European Cities Using TSI-3022 Condensation Particle Counter over a Three-Year Period during Health Effects of Air Pollution on Susceptible Subpopulations

Abstract

In this study, long-term aerosol particle total number concentration measurements in five metropolitan areas across Europe are presented. The measurements have been carried out in Augsburg, Barcelona, Helsinki, Rome, and Stockholm using the same instrument, a condensation particle counter (TSI model 3022). The results show that in all of the studied cities, the winter concentrations are higher than the summer concentrations. In Helsinki and in Stockholm, winter concentrations are higher by a factor of two and in Augsburg almost by a factor of three compared with summer months. The winter maximum of the monthly average concentrations in these cities is between 10,000 cm^-3 and 20,000 cm^-3, whereas the summer min is ?;5000–6000 cm^-3. In Rome and in Barcelona, the winters are more polluted compared with summers by as much as a factor of 4–10. The winter maximum in both Rome and Barcelona is close to 100,000 cm^-3, whereas the summer minimum is >10,000 cm^-3. During the weekdays the maximum of the hourly average concentrations in all of the cities is detected during the morning hours between 7 and 10 a.m. The evening maxima were present in Barcelona, Rome, and Augsburg, but these were not as pronounced as the morning ones. The daily maxima in Helsinki and Stockholm are close or even lower than the daily minima in the more polluted cities. The concentrations between these two groups of cities are different with a factor of about five during the whole day. The study pointed out the influence of the selection of the measurement site and the configuration of the sampling line on the observed concentrations.     

A Comparison of the Spectral Distribution of Solar Radiation in a Polluted and a Clear Air Mass

Two spectroradiometer measurements are presented to illustrate differences in the spectrum of sunlight in the 0.45–0.7 μ band. Only two spectral observations are presented, one in an apparently clean cloud-free air mass, the other under a heavily polluted air mass. Both observations were taken near Houston, Texas, on 12 November 1968 at about 1800 GMT. A 23% loss in the intensity of light is attributed to attenuation by pollution in the atmosphere.     

Comparison of the particle size distribution of heavy-duty diesel exhaust using a dilution tailpipe sampler and an in-plume sampler during on-road operation

Originally constructed to develop gaseous emission factors for heavy-duty diesel trucks, the U.S. Environmental Protection Agency's (EPA) On-Road Diesel Emissions Characterization Facility has been modified to incorporate particle measurement instrumentation. An electrical low-pressure impactor designed to continuously measure and record size distribution data was used to monitor the particle size distribution of heavy-duty diesel truck exhaust. For this study, which involved a high-mileage (900,000 mi) truck running at full load, samples were collected by two different methods. One sample was obtained directly from the exhaust stack using an adaptation of the University of Minnesota's air-ejector-based mini-dilution sampler. The second sample was pulled from the plume just above the enclosed trailer, at a point approximately 11 m from the exhaust discharge. Typical dilution ratios of about 300:1 were obtained for both the dilution and plume sampling systems. Hundreds of particle size distributions were obtained at each sampling location. These were compared both selectively and cumulatively to evaluate the performance of the dilution system in simulating real-world exhaust plumes. The data show that, in its current residence-time configuration, the dilution system imposes a statistically significant bias toward smaller particles, with substantially more nanoparticles being collected than from the plume sample.     

Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer

Size-resolved, 24-h aerosol samples were collected from June–July 2001 by means of an Andersen high-volume cascade impactor. Sampling was conducted in a central avenue (Patission) characterised by heavy traffic, 21 m above street level, in the Athens city centre. Samples were analysed by atomic absorption spectrometry and gas chromatography to determine the size distribution of nine metallic elements (Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) and n-alkanes (with carbon numbers in the range 18–35). The aerosol mass median diameter (MMD) was calculated by means of probit analysis on the cumulative mass concentration size distribution for each metals and n-alkane. The total n-alkane mass concentration (TNA) in total suspended particles (TSP) ranged from 72 to 1506 ng m⁻³ while the total metal concentration ranged from 5.6 to 28.6 μg m⁻³. The results showed that metals such as Cd, V and Ni are characterised by a MMD <1 μm, while the MMD for Pb and Mn are ∼1 μm. Such metals are generally considered to have anthropogenic emission sources. Other metals such as Al, Fe, Cu and Cr were found to have MMD=2–6 μm, which generally originate from soil dust or mechanical abrasion processes. The Carbon number profile of n-alkane compounds showed a strong anthropogenic source with only a minor biogenic influence. The concentration of most n-alkanes was characterised by high variability during the sampling period, in contrast to the concentration of most trace metals. Most n-alkanes had a unimodal size distribution with MMD=1–2 μm similar to those of some trace metals (Pb, Mn), which originate mostly from vehicle emissions. This is a strong indication that these species have a common source. Finally, gas–particle partitioning of n-alkanes was also examined for different particle sizes by means of the relationship between the partition constant K_p and saturation vapour pressure (p_L⁰) as proposed by current sorption models.     

Particle Concentrations Inside a Tavern Before and After Prohibition of Smoking: Evaluating the Performance of an Indoor Air Quality Model

Abstract

Measurements were made of respirable suspended particles (RSP) in a large sports tavern on 26 dates over approximately two years in which smoking was allowed, followed by measurements on 50 dates during the year after smoking was prohibited. The smoking prohibition occurred without warning when the city government passed a regulation restricting smoking in local restaurants and taverns. Two follow-up field surveys, consisting of 24 and 26 visits, respectively, were conducted to measure changes in RSP levels after smoking was prohibited. No decrease in tavern attendance was evident after smoking was prohibited. During the smoking period, the average RSP concentration was 56.8 |ig/m3 above the outdoor concentrations, but the average abruptly dropped to 5.9 ug/m3 above outdoor levels—a 90% decrease— on 24 visits in the first two months immediately after smoking was prohibited (first follow-up study). A second set of 26 follow-up visits (matched by time of day, day of the week, and season to the earlier smoking visits) yielded an average concentration of 12.9 jig/m3 above the outdoor levels, or an overall decrease in the average RSP concentration of 77% compared with the smoking period. During the smoking period, RSP concentrations more than 100 ug/m3 above outdoor levels occurred on 30.7% of the visits. During the 50 nonsmoking visits, 92% of the RSP concentrations were less than 20 u,g/m3 above outdoor levels, and no concentration exceeded 100 ug/m3 on any nonsmoking visit. The data show there was a striking decline in indoor RSP concentrations in the tavern after smoking was prohibited. The indoor concentration observed in the nonsmoking periods (9.1 u.g/m3 average for all nonsmoking visits) was attributed to cooking and resuspended dust. A mathematical model based on the mass balance equation was developed that included smoking, cooking, and resuspended dust. Using cigarette emission rates from the literature, the tavern volume of 521 m3, and the air exchange rate measured in the tavern under conditions regarded by the management as "typical," the model predicted 42.5 ug/m3 for an average smoking count of 1.17 cigarettes, which compared favorably with the average concentration of 43.9 ng/m3 observed in the tavern. A regression analysis indicated that the active smoking count explained over 50% of the variation of the RSP concentrations measured on different dates. The mathematical model can be used to estimate RSP concentrations from smoking in other similar taverns under similar conditions.     

Comparison of a mass balance and an ecosystem model approach when evaluating the carbon cycling in a lake ecosystem

Carbon budgets are frequently used in order to understand the pathways of organic matter-in ecosystems, and they also have an important function in the risk assessment of harmful substances. We compared two approaches, mass balance calculations and an ecosystem budget, to describe carbon processing in a shallow, oligotrophic hardwater lake. Both approaches come to the same main conclusion, namely that the lake is a net autotrophic ecosystem, in spite of its high dissolved organic carbon and low total phosphorus concentrations. However, there were several differences between the carbon budgets, e.g. in the rate of sedimentation and the air-water flux of CO2. The largest uncertainty in the mass balance is the contribution of emergent macrophytes to the carbon cycling of the lake, while the ecosystem budget is very sensitive towards the choice of conversion factors and literature values. While the mass balance calculations produced more robust results, the ecosystem budget gave valuable insights into the pathways of organic matter transfer in the ecosystem. We recommend that when using an ecosystem budget for the risk assessment of harmful substances, mass balance calculations should be performed in parallel in order to increase the robustness of the conclusions.     

Comparison of the heavy metal bioaccumulation capacity of an epiphytic moss and an epiphytic lichen

This study compared the heavy metal bioaccumulation capacity in the epiphytic moss Scorpiurum circinatum and the epiphytic lichen Pseudevernia furfuracea, exposed in bags for 3 months in the urban area of Acerra (S Italy). The content of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn was measured by ICP-MS. The results showed that both species accumulated all the heavy metals assayed. The moss had the highest bioaccumulation capacity for all metals and showed a more constant and linear accumulation trend than the lichen. Intra-tissue heavy metal bioaccumulation was assessed by X-ray microanalysis applied to ESEM operated in high and low vacuum and ESEM modes.