Regulated and speciated hydrocarbon emissions from a catalyst equipped internal combustion engine

In the present work, the effect of engine operating conditions on its exhaust emissions and on catalytic converter operation is studied. A 4-cylinder OPEL 1.6 l internal combustion engine equipped with a hydraulic brake dynamometer was used in all the experiments. For exhaust emissions treatment a typical three-way catalyst was used. The highest hydrocarbon and carbon monoxide engine-out emissions were observed at engine power 2–4 HP. These emissions were decreased as the engine power was increased up to 20 HP. Among the various compounds detected in exhaust emissions, the following ones were monitored at engine and catalyst outlet: methane, hexane, ethylene, acetaldehyde, acetone, benzene, toluene and acetic acid. The concentration of each compound in the catalytic converter effluent was in the range 45–132, 5–12, 10–125, 15–22, 3–7, 3–12, 2–9, 0–6 ppm, respectively. After the required temperature for catalyst operation had been achieved, carbon monoxide tailpipe emissions were dramatically decreased and the observed hydrocarbon conversions were also high. Methane was the most resistant compound to oxidation while ethylene was the most degradable compound over the catalyst. The order from the easiest to the most resistant to oxidation compound was: Alkene>Aromatic>Aldehyde>Ketone>Alkane.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Pre- and post-catalyst-, fuel-, velocity- and acceleration-dependent benzene emission data of gasoline-driven EURO-2 passenger cars and light duty vehicles

The benzene emission characteristics of six gasoline-driven EURO-2 vehicles, three passenger cars and three light duty vehicles, have been determined by time-resolved chemical ionization mass spectrometry. Aliquots of the exhaust gas were monitored pre- and post-catalyst with two independently operating mass spectrometers. Each vehicle was driven with two different fuels having benzene contents of 1 and 2 vol%. Seven driving cycles—including the European (EDC) and the US (FTP-75) driving cycle—with a total driving time of about 8800 s were studied. Herein, we discuss the average emission characteristics of the entire fleet at transient driving in the velocity range of 0–150 km h⁻¹. The conversion efficiencies of the involved catalytic systems were deduced from the pre- and post-catalyst data. On average, the vehicles showed optimal benzene conversion efficiencies (>95%) in the velocity range of 30–90 km h⁻¹. When driving below 20 or above 100 km h⁻¹ reduced benzene conversion was found (80–82%). No benzene conversion was observed when driving above 130 km h⁻¹. In contrast, the post-catalyst benzene emissions exceeded those of the untreated exhaust gas by 19–49%. Thus on an average, benzene was formed across the catalysts under these conditions. In addition, the influence of the benzene content of the gasoline on the tail-pipe emissions was also studied. The use of the gasoline with 1 vol% benzene instead of 2 vol% induced a 20–30% reduction of the post-catalyst emissions when driving below 50 km h⁻¹. The fuel effect became smaller above 100 km h⁻¹ and was even negative at high engine load (>130 km h⁻¹). Thus under these conditions, when benzene is formed across the catalyst, the amount of the emitted benzene was independent of the benzene level of the fuel.     

Concentrations of benzene and toluene in the atmosphere of the southwestern area at the Mexico City Metropolitan Zone

The Mexico City Metropolitan Zone (MCMZ) presents important emissions of hazardous air pollutants. It is well documented that the MCMZ suffers a critical air pollution problem due to high ozone and particulate matter concentrations. However, toxic air pollutants such as benzene and toluene have not been considered. Benzene has accumulated sufficient evidence as a human carcinogen, and the ratio benzene/toluene is an excellent indicator to evaluate control strategies efficiency.In order to evaluate the levels of these two air toxic pollutants in the MCMZ, ambient air samples were collected in canisters and analyzed with a gas chromatograph with a flame ionization detector, according to procedures described in the United States Environmental Protection Agency (USEPA) method TO-15. Quality assurance was performed collecting duplicate samples which were analyzed in replicate to quantify the precision of air-quality measurements.Three different sites located in the Southwestern area in the MCMZ were selected for the sampling: the University campus, a gas station, and a vertical condominium area, in the same neighborhood, which presents different activities. At these sites, grab air samples were collected during the morning hours (7–8 a.m.), while for the University area, 24 h integrated air samples were collected simultaneously, with grab samples.Benzene concentrations (24 h sampling) in the atmosphere around the University campus have similar present levels as in other cities of North America. Mean values in this site were about 1.7 ppb.A significant variation exists between the benzene and toluene concentrations in the studied sites, being the more critical values than those registered at the gas station (an average of 25.8 ppb and a maximum of 141 ppb of benzene). There is a fuel regulation for gasoline in Mexico, which allows a maximum of 1 percent of benzene. However, since more than 60 percent of vehicles do not have catalytic converters (models before 1991) it is expected that most of this benzene be emitted through exhaust pipe. Another strategy being implemented is the use of vapor recovery systems at the gas stations. Vehicles emission control technology must be matched with adequate fuel characteristics in the problem area where it will be implemented, to achieve maximum emission reductions.     

Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

Dilution and aerosol dynamics within a diesel car exhaust plume—CFD simulations of on-road measurement conditions

Vehicle particle emissions are studied extensively because of their health effects, contribution to ambient PM levels and possible impact on climate. The aim of this work was to obtain a better understanding of secondary particle formation and growth in a diluting vehicle exhaust plume using 3-d information of simulations together with measurements. Detailed coupled computational fluid dynamics (CFD) and aerosol dynamics simulations have been conducted for H₂SO₄–H₂O and soot particles based on measurements within a vehicle exhaust plume under real conditions on public roads.Turbulent diffusion of soot and nucleation particles is responsible for the measured decrease of number concentrations within the diesel car exhaust plume and decreases coagulation rates. Particle size distribution measurements at 0.45 and 0.9 m distance to the tailpipe indicate a consistent soot mode (particle diameter D_p∼50 nm) at variable operating conditions. Soot mode number concentrations reached up to 10¹³ m⁻³ depending on operating conditions and mixing.For nucleation particles the simulations showed a strong sensitivity to the spatial dilution pattern, related cooling and exhaust H₂SO_4(g). The highest simulated nucleation rates were about 0.05–0.1 m from the axis of the plume. The simulated particle number concentration pattern is in approximate accordance with measured concentrations, along the jet centreline and 0.45 and 0.9 m from the tailpipe. Although the test car was run with ultralow sulphur fuel, high nucleation particle (D_p⩽15 nm) concentrations (>10¹³ m⁻³) were measured under driving conditions of strong acceleration or the combination of high vehicle speed (>140 km h⁻¹) and high engine rotational speed (>3800 revolutions per minute (rpm)).Strong mixing and cooling caused rapid nucleation immediately behind the tailpipe, so that the highest particle number concentrations were recorded at a distance, x=0.45 m behind the tailpipe. The simulated growth of H₂SO₄–H₂O nucleation particles was unrealistically low compared with measurements. The possible role of low and semi-volatile organic components on the growth processes is discussed. Simulations for simplified H₂SO₄–H₂O–octane–gasoil aerosol resulted in sufficient growth of nucleation particles.     

VOC composition and ozone-forming potential of the exhaust gas of in-use motorcycles

The emission profile of volatile organic compounds (VOC) and the ozone-forming potential (OP) of the exhaust gas of six in-use motorcycles (four 4-stroke- and two 2-stroke-engines) were determined. The motorcycles were tested on a chassis dynamometer in a real-world driving cycle. The analysis involved the C2–C12-hydrocarbons as well as the aldehydes and ketones. Additionally, the regulated THC and NO_x emissions were measured according to the test procedure for type approval (ECE 40). Two vehicles did not fulfil the THC emission standard, whereas all vehicles met the requirements for NO_x emission. The aromatic fuel components toluene and xylene, and the combustion products ethene and propene contributed most to the OP of the VOC emission. The highest OP was found with the 2-stroke engines. The VOC profile of the emissions varied with vehicle and driving conditions. The reactivity of the exhaust gas, defined as gram ozone per gram of non-methane organic gases (NMOG), increased with vehicle speed.     

Aerosol number size distributions within the exhaust plume of a diesel and a gasoline passenger car under on-road conditions and determination of emission factors

A new setup has been developed and built to measure number size distributions of exhaust particles and thermodynamic parameters under real traffic conditions. Measurements have been performed using a diesel and a gasoline passenger car driving with different speeds and engine conditions. Significant number of nucleation mode particles was found only during high load conditions, i.e. high car and engine speeds behind the diesel car. The number concentration of soot mode particles varied within a factor of two for different engine conditions while the concentration of nucleation mode particles varied up to two orders of magnitude. The results show that roadside measurements are still quite different from those behind the tailpipe. Beside dilution transformation processes within the first meter behind the tailpipe also play an important role, such as nucleation and growth. Emission factors were calculated and compared with those obtained by other studies. Emission factors for particles larger than 25 nm (primary emissions) varied within 1.1 × 10¹⁴ km^?1 and 2.7 × 10¹⁴ km^?1 for the diesel car and between 0.6 × 10¹² km^?1 and 3.5 × 10¹² km^?1 for the gasoline car. The advantage of these measurements is the exhaust dilution under atmospheric conditions and the size-resolved measurement technique to divide into primary emitted and secondary formed particles.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Urban roadside aromatic hydrocarbons in three cities of the Pearl River Delta,People's Republic of China

Urban roadside levels of benzene, toluene, ethylbenzene and xylenes (BTEX) were investigated in three typical cities (Guangzhou, Macau and Nanhai) in the Pearl River Delta Region of south China. Air samples were collected at typical ground level microenvironments by multi-bed adsorbent tubes. The BTEX concentrations were determined by thermal desorption–gas chromatography–mass selective detector (TD–GC–MSD) technique. The mean concentrations of benzene, toluene, ethylbenzene and xylenes were, respectively, 51.5, 77.3, 17.8 and 81.6 μg/m³ in Guangzhou, 34.9, 85.9, 24.1, 95.6 μg/m³ in Macau, and 20.0, 39.1, 3.0 and 14.2 μg/m³ in Nanhai. The relative concentration distribution pattern and mutual correlation analysis indicated that in Macau BTEX were predominantly traffic-related while in Guangzhou benzene had sources other than vehicle emission. In Nanhai, both benzene and toluene had different sources other than vehicle emission. The samples collected from Guangzhou showed that BTEX had significant higher concentrations in November than those in July.     

Mercury emissions from automobiles using gasoline,diesel, and LPG

Mercury (Hg) emissions from gasoline, diesel, and liquefied petroleum gas (LPG) vehicles were measured and speciated (particulate, oxidized, and elemental mercury). First, three different fuel types were analyzed for their original Hg contents; 571.1±4.5 ng L⁻¹ for gasoline, 185.7±2.6 ng L⁻¹ for diesel, and 1230.3±23.5 ng L⁻¹ for LPG. All three vehicles were then tested at idling and driving modes. Hg in the exhaust gas was mostly in elemental form (Hg⁰), and no detectable levels of particulate (Hg^p) or oxidized (Hg²⁺) mercury were measured. At idling modes, Hg concentrations in the exhaust gas of gasoline, diesel, and LPG vehicles were 1.5–9.1, 1.6–3.5, and 10.2–18.6 ng m⁻³, respectively. At driving modes, Hg concentrations were 3.8–16.8 ng m⁻³ (gasoline), 2.8–8.5 ng m⁻³ (diesel), and 20.0–26.9 ng m⁻³ (LPG). For all three vehicles, Hg concentrations at driving modes were higher than at idling modes. Furthermore, Hg emissions from LPG vehicle was highest of all three vehicle types tested, both at idling and driving modes, as expected from the fact that it had the highest original fuel Hg content.     

Composition and emissions of VOCs in main- and side-stream smoke of research cigarettes

It is well known that mainstream (MS) and sidestream (SS) cigarette smoke contains a vast number of chemical substances. Previous studies have emphasized SS smoke rather than MS smoke to which smokers are exposed, and most have used chamber tests that have several disadvantages such as wall losses. Emissions from standard research cigarettes have been measured, but relatively few constituents have been reported, and only the 1R4F (low nicotine) cigarette type has been tested. This study provides a comprehensive characterization of total, MS and SS smoke emissions for the 1R5F (ultra low nicotine), 2R4F (low nicotine), and 1R3F (standard nicotine) research cigarettes research cigarettes, including emission factors for a number of toxic compounds (e.g., benzene) and tobacco smoke tracers (e.g., 2,5-dimethyl furan). Emissions of volatile organic compounds (VOCs) and particulate matter (PM) are quantified using a dynamic dilution emission measurement system that is shown to produce accurate, rapid and reproducible results for over 30 VOCs and PM. SS and MS emissions were accurately apportioned based on a mass balance of total emissions. As expected, SS emissions greatly exceeded MS emissions. The ultra low nicotine cigarette had lower emissions of most VOCs compared to low and standard nicotine cigarettes, which had similar emissions. Across the three types of cigarettes, emissions of benzene (296–535 μg cig⁻¹), toluene (541–1003 μg cig⁻¹), styrene (90–162 μg cig⁻¹), 2-dimethyl furan (71–244 μg cig⁻¹), naphthalene (15–18 μg cig⁻¹) and other VOCs were generally comparable to or somewhat higher than literature estimates using chamber tests.     

Cold start extra emissions as a function of engine stop time: Evolution over the last 10 years

Cars with catalysts show a significant increase in exhaust emissions at engine start. These extra emissions are expressed as the difference, over a particular driving cycle, between emissions generated when the vehicle is started and when the engine or the catalyst are stably warm. Experimental data, suitable for the assessment of cold start emissions, are usually available for completely cooled engines. Most results originate from tests at ambient temperature of 20–30 °C and with an engine stop time of at least 12 h. On the other hand, data including shorter stop times are very rare.The present work investigates the influence of exhaust emissions with shorter stop times, i.e. 0.5, 1, 2 and 4 h. The main goal consists in the comparison of emissions exhausted by recent car models (Euro-4) against emissions assessed in the framework of a similar campaign 10 years ago (FAV1/Euro-1 vehicles).A short survey of the current extra emission estimation methods is presented in this paper. It is shown that some methods are not suited for providing correct estimations in all cases. We discuss the fact that different estimation methods can show either similar or completely different results depending on the evolution behaviour of the hot emissions.Due to new technologies, e.g. the catalyst and improved engine control algorithms, emissions have been considerably reduced over the last 10 years. In this study it is determined how the relative extra emissions, i.e. extra emissions relative to the extra emissions for the standard stop time of 12 h, expressed as a function of stop time have changed. We may claim with caution that for medium stop times of 0.5–4 h the average relative extra emissions of Euro-4 vehicles are well below the average of the relative extra emissions of Euro-1 vehicles.     

Chemical and physical characterization of emissions from birch wood combustion in a wood stove

The purpose of this study was to characterize the emissions of a large number of chemical compounds emitted from birch wood combustion in a wood stove. Birch wood is widely used as fuel in Swedish household appliances. The fuel load was held constant during six experiments.Particles <2.5 μm in diameter were collected and the size distribution of the particles was measured. The results were compared to the size distribution in road traffic emissions. It could be seen that the number distribution differed between the sources. In traffic exhaust, the number of particles maximized at 20 nm, while the number distribution from wood burning ranged from 20 to 300 nm. The ratio K/Ca on particles was found to be significantly different in wood burning compared to road dust, range 30–330 for the former and 0.8±0.15 for the latter. The source profile of common elements emitted from wood burning differed from that found on particles at a street-level site or in long-distance transported particles.The ratio toluene/benzene in this study was found to be in the range 0.2–0.7, which is much lower than the ratio 3.6±0.5 in traffic exhaust emissions.Formaldehyde and acetone were the most abundant compounds among the volatile ketones and aldehydes. The emission factor varied between 180–710 mg/kg wood for formaldehyde and 5–1300 mg/kg wood for acetone. Of the organic acids analyzed (3,4,5)-trimethoxy benzoic acid was the most abundant compound. Of the PAHs reported, fluorene, phenanthrene, anthracene, fluoranthene and pyrene contribute to more than 70% of the mass of PAH. Of the elements analyzed, K and Si were the most abundant elements, having emission factors of 27 and 9 mg/kg wood, respectively.Although fluoranthene has a toxic equivalence factor of 5% of benzo(a)pyrene (B(a)P), it can be seen that the toxic potency of fluoranthene in wood burning emissions is of the same size as B(a)P. This indicates that the relative carcinogenic potency contribution of fluoranthene in wood smoke would be about 40% of B(a)P.     

Aromatic hydrocarbons in the atmospheric environment. Part III: personal monitoring

As part of a larger study, personal sampling of the aromatic hydrocarbons benzene, toluene, ethylbenzene and the isomeric xylenes (BTEX) was carried out by 55 nonsmoking volunteers for a period of 14 days. Thirty-nine persons lived in a rural area near Hannover (Germany) with hardly any traffic at all, while 16 persons lived in a high-traffic city street in Hannover. The personal exposure level of the persons in the rural area (some commuting to Hannover) was: 2.9, 24.8, 2.4 and 7.7 μg m⁻³ for benzene, toluene, ethylbenzene and the sum of xylenes, respectively, while the corresponding data for the high traffic city streets were 4.0, 22.2, 2.8 and 9.7 μg m⁻³ (geometric means). Four microenvironments have been monitored which contribute to the total exposure to BTEX, i.e. the home, the outdoor air, the workplace and the car cabin. The most important microenvironment for non-working persons is the private home. The concentration of most BTEX in the private home is almost equal to the personal exposure level, demonstrating that the indoor pollution in the home makes by far the highest contribution to the total exposure. For working people (mostly office workers), the workplace is the second most important microenvironment contributing to the total BTEX exposure. Taking all working persons into consideration (independent of the location of their private home) the personal exposure level is higher by a factor of 1.2–1.4 than that of the workplace (for toluene this factor is 2.2). As already found by others, very high BTEX concentrations may be found in car cabins, in particular, if the engine is gasoline-driven. In the cabin of 44 cars in the rural/urban area average benzene concentrations (geometric mean) of 12/14 μg m⁻³ and a maximum value of ∼550 μg m⁻³ were found. On average, the participating volunteers drove their car for 45 min day⁻¹ (i.e. 3% of the day). Nevertheless, the car cabin constitutes about 10% of the total benzene exposure. Refueling of the car during the 14-day sampling period has only a small effect on the personal exposure level.     

Influence of fuel composition on polycyclic aromatic hydrocarbon emissions from a fleet of in-service passenger cars

The composition of exhaust emissions from eight in-service passenger cars powered by liquefied petroleum gas (LPG) and unleaded petrol (ULP) were measured on a chassis dynamometer at two driving speeds (60 and 80 km h⁻¹) with the aims of evaluating their polycyclic aromatic hydrocarbon (PAH) contents and investigating the effects of the type of fuel on vehicle performance, ambient air quality and associated health risks. Naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene were the most prominent PAHs emitted by both ULP and LPG powered cars. The total emission factors of PAHs from LPG cars were generally lower than (but statistically comparable with) those of ULP cars. Similarly, the total BAP_eq of the PAHs emitted by LPG cars were lower than those from ULP cars. Multi-criteria decision making (MCDM) methods showed that cars powered by LPG fuel performed better than those powered by ULP fuel in term of PAH levels. The implications of these observations on the advantages and disadvantages of using ULP and LPG fuels are discussed.     

Methanol measurements in the lower troposphere near Innsbruck (047°16′N; 011°24′E), Austria

Diurnal variations on a time scale of minutes of the mixing ratios of methanol were measured using proton transfer reaction mass spectrometry (PTR-MS) technique during 67 days throughout the time span from November 1996 to July 1998 together with benzene and other volatile organic compounds at the western outskirts of Innsbruck, Austria. Comparison with the course of the mixing ratio of benzene, which served as marker for traffic emissions, as well as the observation of a seasonal variation allowed to distinguish between different sources for methanol release into the troposphere. Strong evidence for methanol removal via deposition on dew-wetted surfaces is obtained from the comparison of meteorological data with methanol mixing ratios. The mean volume mixing ratio of total methanol was 7.5 nmol mol⁻¹. Mixing ratios ranged from 0.03 up to 45 nmol mol⁻¹.     

Measurement of nucleation and soot mode particle emission from a diesel passenger car in real world and laboratory in situ dilution

Uncertainties still remain in the size and number emission of nucleation and soot mode particles from diesel vehicles and understanding of the nucleation process under different ambient conditions. Particle emission measurements were carried out with a EURO-3 certified European diesel passenger car running on low (<10 ppm S) and high (310 ppm S) sulfur fuel. A newly developed in situ diluter which sampled exhaust continuously from the tailpipe and diluted in two steps by a factor of 500–6000 was employed to study nucleation particle formation under well-controlled temperature and humidity conditions. Particle emission measurements were also carried out with a mobile laboratory chasing the exhaust plume of the same vehicle in summer (19–25 °C) and winter (9 °C), with no significant difference of the nucleation or soot mode particle emission found. The particle size distributions compared well with those measured in the laboratory with the same vehicle under identical driving conditions. Simple nucleation and coagulation calculations were compared with the atmospheric and laboratory measurements. It was shown that the primary dilution step had the largest impact on the nucleation mode formation, while the model overpredicted the influence of temperature and humidity. No nucleation mode particles were observed running the diesel vehicle on low (<10 ppm S) fuel.     

Ambient levels of volatile organic compounds in the atmosphere of Greater Cairo

Ambient volatile organic compounds (VOCs) samples were collected at three locations, two in urban areas in Greater Cairo (Ramsis and Haram) and background one in rural area in Menofiya province (Kafr El-Akram), during the period of June, 2004–August, 2004. The highest concentrations of VOCs were found in Ramsis, whereas the lowest concentrations were detected in Kafr El-Akram, and the difference in mean concentrations were statistically significant (p<0.001). Among all of the measured VOCs species, the contribution of individual VOC to the total VOCs concentration were very similar in Ramsis and Haram locations, toluene was the most abundant compound followed by (m, p)-xylene. This similarity implies a similar emission sources of VOCs in both urban locations, vehicle exhausts are the dominant one. Greater Cairo has high levels of volatile aromatic hydrocarbons compared with many polluted cities in the world. The BTEX (benzene: toluene: ethylbenzene: xylenes) concentration ratios were (2.01:4.94:1:4.95), (2.03:4.91:1:4.87) and (2.31:2.98:1:2.59) in Ramsis, Haram and Kafr El-Akram, respectively. The average toluene/benzene (T/B), (m, p)-xylene/benzene ((m, p)-X/B) and o-xylene/benzene (o-X/B) concentration ratios were 2.45, 1.61and 0.85, respectively in Ramsis and 2.42, 1.61 and 0.78, respectively in Haram. The ratios in both urban locations were of the same magnitude and close to those obtained from automotive exhausts, indicating that the ambient BTEX originate mainly from motor vehicle emissions. However, the (T/B), ((m, p)-X/B) and (o-X/B) concentration ratios were 1.29, 0.71 and 0.41 in Kafr El-Akram, respectively. These ratios were lower than those found in Ramsis and Haram locations and in automotive exhaust, suggesting that the BTEX in Kafr El-Akram do not come from a local source and are exclusively results from the diffusion and dispersion of VOCs produced from the traffic density in the surrounding cities. Significant positive correlation coefficients (p<0.001) were found between the concentrations of BTEX compounds at the three sampling locations. The diurnal variation of VOCs concentrations in Ramsis location showed two daily peaks linked to traffic density.     

On-road remote sensing of liquefied petroleum gas (LPG) vehicle emissions measurement and emission factors estimation

In the present study, the real-world on-road liquefied petroleum gas (LPG) vehicle/taxi emissions of carbon monoxide (CO), hydrocarbon (HC) and nitric oxide (NO) were investigated. A regression analysis approach based on the measured LPG vehicle emission data was also used to estimate the on-road LPG vehicle emission factors of CO, HC and NO with respect to the effects of instantaneous vehicle speed and acceleration/deceleration profiles for local urban driving patterns. The results show that the LPG vehicle model years and driving patterns have a strong correlation to their emission factors. A unique correlation of LPG vehicle emission factors (i.e., g km⁻¹ and g l⁻¹) on different model years for urban driving patterns has been established. Finally, a comparison was made between the average LPG, and petrol [Chan, T.L., Ning, Z., Leung, C.W., Cheung, C.S., Hung, W.T., Dong, G., 2004. On-road remote sensing of petrol vehicle emissions measurement and emission factors estimation in Hong Kong. Atmospheric Environment 38, 2055–2066 and 3541] and diesel [Chan, T.L., Ning, Z., 2005. On-road remote sensing of diesel vehicle emissions measurement and emission factors estimation in Hong Kong. Atmospheric Environment 39, 6843–6856] vehicle emission factors. It has shown that the introduction of the replacement of diesel taxis to LPG taxis has alleviated effectively the urban street air pollution. However, it has demonstrated that proper maintenance on the aged LPG taxis should also be taken into consideration.