Presence of alkyllead in rural and urban air: Evaluation of some sources of alkyllead pollution of the atmosphere in Norway

Concentrations of alkyllead in ambient air were measured, as well as in car exhaust and in gasoline vapours. In Oslo the concentration in air ranged from 0.010 to 0.100 μg Pb m⁻³, and these values were compared to the concentrations (< 0.001 μg Pb m⁻³) measured in a low traffic rural area of Norway. The amount of alkyllead in car exhaust varied between 0.1 and 15 μg Pb m⁻³, which was between 0.01 and 0.5% of the amount of inorganic lead in exhaust. Evaporation of alkyllead from parked cars was estimated at 0.5 mg Pb per day per car. The concentrations of alkyllead in saturated gasoline vapour were found to be 10–20 mg Pb m⁻³ at ambient air temperatures.     

Simulation of the evolution of particle size distributions in a vehicle exhaust plume with unconfined dilution by ambient air

Over the past several years, numerous studies have linked ambient concentrations of particulate matter (PM) to adverse health effects, and more recent studies have identified PM size and surface area as important factors in determining the health effects of PM. This study contributes to a better understanding of the evolution of particle size distributions in exhaust plumes with unconfined dilution by ambient air. It combines computational fluid dynamics (CFD) with an aerosol dynamics model to examine the effects of different streamlines in an exhaust plume, ambient particle size distributions, and vehicle and wind speed on the particle size distribution in an exhaust plume. CFD was used to calculate the flow field and gas mixing for unconfined dilution of a vehicle exhaust plume, and the calculated dilution ratios were then used as input to the aerosol dynamics simulation. The results of the study show that vehicle speed affected the particle size distribution of an exhaust plume because increasing vehicle speed caused more rapid dilution and inhibited coagulation. Ambient particle size distributions had an effect on the smaller sized particles (approximately 10 nm range under some conditions) and larger sized particles (>2 microm) of the particle size distribution. The ambient air particle size distribution affects the larger sizes of the exhaust plume because vehicle exhaust typically contains few particles larger than 2 microm. Finally, the location of a streamline in the exhaust plume had little effect on the particle size distribution; the particle size distribution along any streamline at a distance x differed by less than 5% from the particle size distributions along any other streamline at distance x.     

Using a source–receptor approach to characterize the volatile organic compounds from control device exhaust in a science park

The science parks have helped shape Taiwan as a high-tech island with a good reputation worldwide. But some complaints on air pollution from the science parks have recently risen. To better understand the environmental effects of volatile organic compounds (VOCs) emitted from various high-tech factories in a science park, this study uses a source–receptor approach to characterize the environmental effects of VOCs from control device exhaust in Taichung Science Park. The chemical mass balance model (CMB8.2) of field measurements of 30 stacks and ambient air at nine sites was used to identify the source and relative contribution of ambient VOCs. The exhaust gas of various pollution control devices was also sampled by drawing a stream of the gases from the exhaust duct at its sampling port. The VOC source profile of each control device exhaust was determined using a database of noncharacteristic compounds. Monthly ambient concentrations of 167 VOCs were divided into monsoon datasets to investigate the effect of monsoon conditions on the emission of VOCs in the science park. This study also suggests a method for determining the optimum source profile in source–receptor modeling, and identifies and analyzes the sources of ambient VOCs at nine sites during southwest and northeast monsoons. Results show a direct relationship between the relative contribution of each source and its control device efficiency. The proposed source–receptor approach can characterize the environmental effect of air pollutants from various factories and successfully assess the efficiency of various control devices.     

Assessment of the Contribution of Chemical Species to The Eye Irritation Potential of Photochemical Smog

Eye irritation measurements are available from smog chamber solar Irradiations of selected hydrocarbon-nitrogen oxide mixtures. These results have been used to compute eye irritation intensity parameters for formaldehyde, acrolein, peroxyacetyl nitrate, and peroxypropionyl nitrate. Peroxypropionyl nitrate is the most irritating of these four substances. The relative contribution of various pairs of eye Irritants in ambient air mixtures to eye irritation has been calculated from the ambient air concentrations and the eye irritation intensity parameters. The relative contribution of the four eye irritants to a "typical" ambient air mixture has been computed. Formaldehyde appears to be the single most significant eye irritant. Other potential ambient air eye irritants are discussed. The relationships between the hydrocarbon control strategies and eye irritation are considered.     

Fluorocarbons in the Los Angeles Basin

Ambient air concentrations of fluorocarbon 11 (fluorotrichloromethane) and fluoro-carbon 12 (dichlorodifluoromethane) have been measured using a gas chro-matograph equipped with a pulsed, electron capture detector. Air samples taken on a moderately smoggy day in July 1970, at several locations near Los Angeles gave average readings of fluorocarbon 12, 0.7 ppb and fluorocarbon 11, 0.56 ppb. These readings were contrasted with those taken in early February 1973 when the air was clear and marked with turbulence due to several seasonal rain storms. The readings of both fluorocarbon 1 1 and 12 averaged about 25% less during clear weather than those taken during moderate smog. The effects of weather conditions on the concentration were also dramatically pointed out by the February samples, in that as much as a tenfold change in concentrations of both fluorocarbons from location to location and from day to day at the same location was observed. A concentration versus altitude study clearly revealed that fluorocarbons are trapped by an inversion layer. Examination of air samples taken in the vicinity of factories known to be users of fairly large quantities of fluorocarbons revealed in part how large users contribute to the atmospheric concentrations of fluorocarbons. A comparison of fluorocarbon levels in homes and public buildings with ambient outside air levels revealed that the concentrations in some homes and buildings may be as much as several thousand times as high as levels in outside air. Inside the homes and public buildings, levels were as high as one-half of a part per million. Long term photolysis studies in simulated sunlight of both fluorocarbons 11 and 12 in ambient air samples and in air samples with 1 ppm of hydrocarbon and 1 ppm of nitrogen oxides revealed that the two fluorocarbons are photochemically stable even when photolyzed for several weeks.     

Distribution of Light Hydrocarbons in Ambient Air

The diversity of hydrocarbons which are present in ambient polluted air provide a potentially rich source of information concerning the nature of this type of pollution. Measurements of the relative amounts of various hydrocarbons can be correlated with the various possible sources. Since hydrocarbon reactivities vary widely it is also possible to estimate the extent to which various individual hydrocarbons have reacted. Except for samples taken deliberately near sources of hydrocarbon pollution these air samples invariably resemble auto exhaust with an addition of natural gas and of C₃–C₅ paraffins which resemble gasoline vapor. Samples taken in industrial areas and near the smoke plume from a brush fire showed distinctive differences in composition. During the smog season in the fall of 1968 good data were obtained of “typical” or “representative” samples of light, medium and heavy smog. These show the expected depletion of more reactive hydrocarbons in a much more convincing way than before. By comparing these distributions with composition in unreacted samples and by making use of data from bottle irradiations, it was possible to estimate the contribution of the various hydrocarbons in terms of “amount reacted.” The amounts of higher hydrocarbons present and reacted were also estimated from gasoline composition.     

Ambient air analysis round robin

A laboratory intercomparison study was carried out to determine the current capability of Canadian laboratories for the analysis of dioxins and furans in ambient air. Seven laboratories (government and private) participated in the analysis of exposed foam/filter samples, ambient air extracts and standard mixtures. The results indicated that a number of laboratories were capable of the aforementioned analyses; however, further analytical methodology development is also required.     

The impact of NOx,CO and VOC emissions on the air quality of Zurich airport

To study the impact of emissions at an airport on local air quality, a measurement campaign at the Zurich airport was performed from 30 June 2004 to 15 July 2004. Measurements of NO, NO₂, CO and CO₂ were conducted with open path devices to determine real in-use emission indices of aircraft during idling. Additionally, air samples were taken to analyse the mixing ratios of volatile organic compounds (VOC). Temporal variations of VOC mixing ratios on the airport were investigated, while other air samples were taken in the plume of an aircraft during engine ignition. CO concentrations in the vicinity of the terminals were found to be highly dependent on aircraft movement, whereas NO concentrations were dominated by emissions from ground support vehicles. The measured emission indices for aircraft showed a strong dependence upon engine type. Our work also revealed differences from emission indices published in the emission data base of the International Civil Aviation Organisation. Among the VOC, reactive C₂–C₃ alkenes were found in significant amounts in the exhaust of an engine compared to ambient levels. Also, isoprene, a VOC commonly associated with biogenic emissions, was found in the exhaust, however it was not detected in refuelling emissions. The benzene to toluene ratio was used to discriminate exhaust from refuelling emission. In refuelling emissions, a ratio well below 1 was found, while for exhaust this ratio was usually about 1.7.     

Particulate organic compounds emitted from motor vehicle exhaust and in the urban atmosphere

The emission rate of particle-phase petroleum biomarkers in vehicular exhaust compared to the concentrations of these biomarkers in ambient air is used to determine the particulate organic compound concentration due to primary particle emissions from motor vehicles in the southern California atmosphere. A material balance on the organic particulate matter emitted from motor vehicle traffic in a Los Angeles highway tunnel first is constructed to show the proportion which is solvent-extractable and which will elute from a GC column, the ratio of resolved to unresolved compound mass, the portion of the resolved material that can be identified as single organic compounds, and the contribution of different classes of organic compounds to the overall identified fraction. It is shown that the outdoor ambient concentrations of the petroleum biomarkers track primary emissions measured in the highway tunnel, confirming that direct emissions of these compounds from vehicles govern the observed ambient petroleum biomarker concentrations. Using organic chemical tracer techniques, the portion of fine organic particulate matter in the Los Angeles atmosphere which is attributable to direct particle emissions from vehicle exhaust is calculated to vary from 7.5 to 18.3% at different sites throughout the air basin during a summertime severe photochemical smog episode. A similar level of variation in the contribution of primary motor vehicle exhaust to fine particulate organic matter concentrations during different times of day is seen. While peak atmospheric concentrations of fine particulate organic carbon are observed during the 1200–1600 PDT afternoon sampling period, only 6.3% of that material is apportioned to the directly emitted particles from vehicle exhaust. During the morning traffic peak between 0600–1000 PDT, 19.1% of the fine particulate organic material is traced to primary emissions from motor vehicles.     

The Effect of Fuel Composition on Atmospheric Aerosol Due to Auto Exhaust

Aerosols attributable to automobile exhaust can be classified as two types—primary aerosol (initially present in the exhaust) and secondary aerosol (generated photochemically from hydrocarbons and nitrogen oxides in the exhaust). In this study, investigation was made of possible effects of motor-fuel composition on the formation of these aerosols. Secondary aerosol, of principal interest in this work, was produced by irradiating auto exhaust in Battelle-Columbus’ 610 ft³ environmental chamber. A limited number of determinations of primary aerosol in diluted auto exhaust was made at the exit of a 36 ft dilution runnel. Determination of both primary and secondary aerosol was based on light-scattering measurements.

Exhaust was generated with seven full-boiling motor gasolines, both leaded and nonleaded, in a 1967 Chevrolet which was not equipped with exhaust-emission control devices. Changes in fuel composition produced a maximum factor of three difference in light scattering due to primary aerosol. Aerosol yields, for consecutive driving cycles on the same fuel, vary considerably; as a result, ranking the fuels on the basis of average primary aerosol yield was not very meaningful. In addition to fuel composition, the more important independent variables are initial SO₂ concentration, relative humidity and initial hydrocarbon concentration. Statistical analysis of the data indicates that the seven test fuels can be divided into two arbitrary groups with regard to secondary aerosol-forming potential. The fuels in the lower light-scattering group had aromatic contents of 15 and 21%, while those in the higher light-scattering group had aromatic contents of 25, 48, and 55%. Although the fuels can be grouped on the basis of a compositional factor, the grouping of fuels with aromatic content ranging from 25 to 55% indicates that this compositional factor cannot be equated simply with aromatic content. In an associated study of the aerosol-forming potential of individual hydrocarbons prominent in auto exhaust, it was observed that aromatics produce substantially more photochemical aerosol than olefins and paraffins. However, experiments with binar/hydrocarbon mixtures containing aromatjcs, as well as in these exhaust experiments, a strong dependence of aerosol yield on the aromatic components is is not observed. Thus, the data indicate that the dependence of secondary aerosol formation on fuel factors is a complex one and cannot be predicted solely on the basis of a sirigle hydrocarbon component reactivity scale.

The two types of automobile aerosol did not have the same dependence on fuel, composition. The variation in total light scattering attributable to primary plus secondary aerosol was less than that due to either component alone. It therefore was concluded that the light scattering due to automobile exhaust emissions in these experiments was not significantly affected by changing fuel composition.     

Enhancement of PAN abundance in the Pacific marine air upon contact with selected surfaces

Peroxyacetyl nitrate (PAN) concentrations in the marine air of the eastern Pacific Ocean were found to increase by a factor of 1–6 (average 3.2 ± 1.4) over their normal values when the ambient air was stored in an all-glass environment for a period of 1–2 min prior to analysis. This 20–170 ppt enhancement in PAN levels appeared to vary diurnally. No strong evidence for latitudinal dependence was found. The phenomenon of surface PAN enhancement in the marine air could not be duplicated with samples of highly polluted city air or with laboratory-generated PAN/air mixtures. The mechanisms by which this additional PAN is generated in marine air are not known, but some speculations are presented. Additional systematic studies are required to identify the cause(s) of this “apparent PAN” formation.     

A New Approach to Setting Vehicle Emission Standards

Urban ambient air quality trend analysis was evaluated as an alternative to rollback analysis to estimate vehicle emission standards needed to achieve national ambient air quality standards. Examination of the trends of monthly maximum 8 hour average carbon monoxide concentrations, central business district traffic activity, and emission rates from vehicles on the road suggests that the automotive exhaust emission standard for carbon monoxide derived in response to the requirements of the Clean Air Act Amendments of 1970 may be ten times too severe. The excessive stringency of the vehicle emission standard for carbon monoxide was confirmed by two different analyses of the correlation between annual mean carbon monoxide concentration and frequency of occurrence of carbon monoxide concentrations above the level of the 8-hour standard. One correlation analysis using all available CAMP data involved an empirical approach and the other assumed that carbon monoxide concentrations are described by the lognormal distribution. Based on the analysis of CAMP air quality data, a vehicle carbon monoxide emission standard of approximately 29 grams per mile appears adequate to meet the ambient air quality standard. The large difference between the results of this analysis and the 1976 Federal vehicle carbon monoxide emission standard indicates the advisability of applying this methodology to verification of the standards for hydrocarbons and oxides of nitrogen.     

Identification of a potential source of chloroform in urban air: Preliminary Communication

A new potential source of elevated chloroform (CHCl₃) concentrations in urban air is reported. The exhaust gases from gasoline internal combustion engines operated on conventional “leaded” fuel and not equipped with catalytic converters contain parts-per-billion concentrations of chloroform which can, in congested urban areas, contribute significantly to the ambient concentration of chloroform. Exhaust gases from engines burning conventional “leaded” gasoline contain much higher levels of chloroform than do exhaust gases from engines equipped with catalytic converters and operating on “nonleaded” gasoline.     

Ambient concentrations and correlations of hydrocarbons and halocarbons in the vicinity of an airport

Concentrations of sixteen volatile hydrocarbons present in internal combustion engine exhaust gases and two halogenated hydrocarbons have been measured in ambient air samples at six sites around Gatwick Airport. Correlations between their concentrations have been drawn in an attempt to establish the exact nature of the sources of these emissions, together with consideration of the overall hydrocarbon profiles.     

Ambient levels of carbonyl compounds and their sources in Guangzhou,China

Ambient levels of carbonyl compounds and their possible sources, vehicular exhaust and cooking exhaust, were studied at seven places in Guangzhou, including five districts (a residential area, an industrial area, a botanical garden, a downtown area and a semi-rural area), a bus station and a restaurant during the period of June–September 2003. Nineteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Only little changes were found in carbonyl concentration levels in the five different districts because of their dispersion and mixture in the atmosphere in summer. The lower correlations between the carbonyls’ concentrations might result from the mixture of carbonyls derived from different sources, including strong photochemical reactions at noon in summer. Formaldehyde and acetaldehyde were the main carbonyls in bus station, while straight-chain carbonyls were comparatively abundant in cooking exhaust. Besides vehicular exhaust, cooking might be another major source of carbonyl compounds in Guangzhou City, especially for high molecular weight carbonyls.     

Estimation of Smog Effects in the Hydrocarbon-Nitric Oxide System

Hydrocarbon components (propylene, simulated auto exhaust, or authentic auto exhaust) were irradiated in the presence of nitric oxide in large chambers instrumented for measurements of numerous variables. Eye irritation was measured using a selected panel of human subjects. The various dependent variables are presented as functions of the reactant concentrations by means of contour diagrams derived by computer treatment. The effect of “hydrocarbon” and nitric oxide levels on smog effects are discussed; the observed relationships between end effects and reaction rates are considered. The study simulated the effects of varying degrees of vehicular emissions control over one or both reactants and has a bearing on the establishment of vehicle emission standards in California.     

Ethylene: An Urban Air Pollutant

Ethylene is an unusual air pollutant in that it is a plant hormone. Motor vehicle exhaust is a primary source. In the Washington, D. C, area, ethylene concentrations ranged from 700 ppb in the city center to 39 ppb in areas outside the circumferential beltway. Plants grown in these concentrations of ethylene, using controlled environment chambers, exhibited typical symptoms of ethylene toxicity: reduced growth, premature senescence, and reduced flowering and fruit production. When plants were grown in carbon-filtered ambient air, which was also filtered through KMnO₄ to remove ethylene by oxidation, growth, flowering, and fruit production increased. These observations demonstrate that ethylene air pollution is a continual source of stress for plant growth and development in an urban environment.     

Development of a High-Temperature Subtractive Analyzer for Hydrocarbons

This paper discusses the development of a high-temperature subtractive analyzer for separating the hydrocarbons present in gaseous mixtures into two categories— reactive hydrocarbons and unreactive hydrocarbons. The analyzer utilizes the ability of selected substances to absorb certain groups of hydrocarbons and their derivatives from a gas mixture and is designed for operation with a flame ion-ization detector. The body of information presented in this paper is directed to individuals concerned with the analysis of the exhaust gases of gas turbine engines or other combustion sources as stationary power plants. The analyzer grew out of an investigation of a previously reported subtractive analyzer system which operates at ambient temperature. Current state-of-the-art requirements for the accurate determination of total hydrocarbons at the concentrations present in turbine exhaust gases necessitate that sampling and measurements be conducted at elevated temperatures (325-375°F), rather than ambient temperature, to reduce or eliminate condensation and wall adsorption sampling errors. To fulfill this requirement, the sampling lines and flame ionization detector must be heated. After tests determined that the previously reported scrubber system would not remove the same hydrocarbons at elevated temperature levels as it did at ambient temperatures, an investigation of the effectiveness of various absorbents at elevated temperatures was conducted. This led to the development and test of the high-temperature subtractive analyzer concept discussed in this report. In its final form, one path of this unit contains no absorbent, the second contains a column of concentrated H₂SO₄ on Ultraport and a column containing PdSO₄ and H₂SO₄ on Ultraport. The two columns are connected in series. The absorbents remove olefins, aromatics, acetylene, and oxygenated hydrocarbons but pass paraffins. As the final step in this program, a comparison of the two subtractive analyzers was made using the exhaust from a gas turbine combustion system.     

我国汽车排气污染净化研究

本文在调研１９８３年来我国有关汽车排气净化研究的文献基础上，综述了机内净化，机外净化和燃料处理三方面的研究水平与成果，着重探讨了汽车尾气催化净化技术和催化剂的研究。结合我国目前汽车工业和城市机动车污染现状，借鉴国外机动车污染控制的发展道路，提出了我国机动车污染控制技术的发展方向，并对进一步开展汽车排气净化研究提出了建议。     

Evaluations of the chemical mass balance method for determining contributions of gasoline and diesel exhaust to ambient carbonaceous aerosols

The US. Department of Energy Gasoline/Diesel PM Split Study was conducted to assess the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the relative contributions of emissions from gasoline (or spark ignition [SI]) and diesel (or compression ignition [CI]) engines to ambient concentrations of fine particulate matter (PM2.5) in California's South Coast Air Basin (SOCAB). In this study, several groups worked cooperatively on source and ambient sample collection and quality assurance aspects of the study but worked independently to perform chemical analysis and source apportionment. Ambient sampling included daily 24-hr PM2.5 samples at two air quality-monitoring stations, several regional urban locations, and along freeway routes and surface streets with varying proportions of automobile and truck traffic. Diesel exhaust was the dominant source of total carbon (TC) and elemental carbon (EC) at the Azusa and downtown Los Angeles, CA, monitoring sites, but samples from the central part of the air basin showed nearly equal apportionments of CI and SI. CI apportionments to TC were mainly dependent on EC, which was sensitive to the analytical method used. Weekday contributions of CI exhaust were higher for Interagency Monitoring of Protected Visual Environments (IMPROVE; 41+/-3.7%) than Speciation Trends Network (32+/-2.4%). EC had little effect on SI apportionment. SI apportionments were most sensitive to higher molecular weight polycyclic aromatic hydrocarbons (indeno[123-cd]pyrene, benzo(ghi)perylene, and coronene) and several steranes and hopanes, which were associated mainly with high emitters. Apportionments were also sensitive to choice of source profiles. CI contributions varied from 30% to 60% of TC when using individual source profiles rather than the composites used in the final apportionments. The apportionment of SI vehicles varied from 1% to 12% of TC depending on the specific profile that was used. Up to 70% of organic carbon (OC) in the ambient samples collected at the two fixed monitoring sites could not be apportioned to directly emitted PM emissions.