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.     

Comparison of particle light scattering and fine particulate matter mass in central California

Particle light scattering (Bsp) from nephelometers and fine particulate matter (PM2.5) mass determined by filter samplers are compared for summer and winter at 35 locations in and around California's San Joaquin Valley from December 2, 1999 to February 3, 2001. The relationship is described using particle mass scattering efficiency (sigmasp) derived from linear regression of Bsp on PM2.5 that can be applied to estimated PM2.5 from nephelometer data within the 24-hr filter sampling periods and between the every-6th-day sampling frequency. An average of sigmaSp = 4.9 m2/g was found for all of the sites and seasons; however, sigmasp averaged by site type and season provided better PM2.5 estimates. On average, the sigmasp was lower in summer than winter, consistent with lower relative humidities, lower fractions of hygroscopic ammonium nitrate, and higher contributions from fugitive dust. Winter average sigmasp were similar at non-source-dominated sites, ranging from 4.8 m2/g to 5.9 m2/g. The sigmasp was 2.3 m2/g at the roadside, 3.7 m2/g at a dairy farm, and 4.1 m2/g in the Kern County oilfields. Comparison of Bsp from nephelometers with and without a PM2.5 inlet at the Fresno Supersite showed that coarse particles contributed minor amounts to light scattering. This was confirmed by poorer correlations between Bsp and coarse particulate matter measured during a fall sampling period.     

High Volume Sampling: Errors Incurred during Passive Sample Exposure Periods

The current Federal EPA reference method for the determination of total suspended particulate matter (TSP) in the atmosphere is the high volume method (hi-vol).¹ The hi-vol sampler is normally operated for a 24 hr period by drawing air through an 8 X 10 in. glass fiber filter at an air sampling flow rate of between 40-60 cfm. TSP samples are presently collected in this manner every 6th day (61 samples/year). Results are used to determine compliance with existing National Primary Ambient Air Quality Standards for TSP (i.e., 260 µg/m³, maximum 24 hr average, not to be exceeded more than once a year; 75 µg/m³, annual geometric mean). However, when the sampling frequency is diminished to only 61 out of a possible 365 measurements each year, the degree of certainty associated with meeting these air quality standards is also decreased.^2,3 This partial sampling schedule also introduces other sampling errors. One such error caused by the exposure of the collection filter both prior and subsequent to the desired sampling day is the subject of the following discussion.     

Condensed Sulfur Trioxide—Particulate or Vapor?

Sulfuric acid from condensed sulfur trioxide (SO₃) has been found in the filtering medium used in the EPA/APCO, WP-50, and high-volume sampling methods. The amount of sulfuric acid ranged from 1 8 to 78% of the total particulate matter found when sampling emissions from oil-fired boilers. These levels were high enough to determine whether a unit is in compliance with regulations. A question is raised as to whether condensed sulfur trioxide should be included in particulate measurements or eliminated after analyzing the filter medium.     

Evaluation of Regenerative-air Vacuum Street Sweeping on Geological Contributions to PM10

Street sweeping is often proposed as a means of reducing the emissions from paved roads. The objective of this study was to evaluate the effectiveness of street sweeping on ambient particulate matter concentrations and to determine the difference In source contributions to PM10 concentrations between street sweeping and non-street sweeping periods.

Chemically-speciated measurements of PM10 and PM2.5 were taken in the commercial section of Reno, Nevada, for a one-month sampling period. The Chemical Mass Balance (CMB) model was applied to these data and an average of approximately 50 percent of the PM10 was apportioned to resuspended geological material. During half of the sampling period, streets In the vicinity of the sampling site were completely swept with a regenerative-air vacuum sweeper, while no sweeping was performed during the remainder of the experiment. Ratios of primary geological contributions divided by primary motor vehicle contributions to PM10 were compared between sweeping and non-sweeping periods using analysis of variance. This ratio of source contributions minimizes the effects of variations in traffic volume and meteorological dispersion. No significant differences in geological contributions to PM10 were detected as a result of regenerative-air vacuum street sweeping.     

The Precision Associated with the Sampling Frequencies of Total Particulate at Indianapolis,Indiana

The frequency distribution of total suspended particulate matter for Indianapolis, Ind., was examined in order to determine the precision associated with any given sampling scheme. By assuming a basic log_e-normal distribution, a theoretical set of confidence intervals about the geometric mean was derived for random sampling. Verification of the log_e-normal distribution was made for particulate matter in Indianapolis. Application of the derived confidence intervals revealed that for a 30-day period 20 samples must be taken to ensure that the 90% confidence interval will be within 10% of the geometric mean. Analysis of the records for 19 sampling locations within Indianapolis revealed that only 2 sites possessed sufficient data to allow monthly climatological evaluation over the period 1968-1970.     

Determination of fine particulate semi-volatile organic material at three eastern U.S. sampling sites

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 microm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of approximately 0.5 microm.     

Metallic Element Composition of Particulate Matter During Day and Night Sampling at a Traffic Site

Day and night period sampling programs were carried out using a versatile air pollutant system to collect fine particulate matter (PM_2.5) and coarse particulate matter (PM_2.5–10) simultaneously at a traffic junction that is only 60 m from HungKuang University located in Central Taiwan. Therefore, HungKuang University is regarded as the traffic sampling site in this study. Similar measurements were carried out in a previous 2013 study by Fang and colleagues during October 2012 to November 2012. Determination of metallic element composition of fine and coarse particulates collected during the day and the night was accomplished with inductively coupled plasma atomic emission spectrometry (ICP-AES). The results indicated that there were no significant differences in composition of metallic elements Zn, Cu, Cr, Mn, Fe, Pb, and Cd in either coarse or fine particles for both day and night sampling periods. The statistical results indicated no significant differences for metallic elements in the PM_2.5–10 particulates for day and night sampling periods. Also, no significant differences were noted for metallic elements in the PM_2.5 particulates for day and night sampling periods at this traffic sampling site. The proposed reason is the limited sampling period employed in this study. Another potential reason is the presence of traffic that runs heavily both day and night being a major contributor to the ambient air metallic pollutants in this region.     

柴油机排气微粒过滤催化处理技术及进展

介绍了柴油机微粒后处理催化捕集器特点 ,评述了过滤器催化再生方法 ,综述了蜂窝陶瓷载体涂层及催化剂活性组分研究现状。重点阐述了微粒再生催化剂研究进展及其发展趋势     

Determination of Fine Particulate Semi-Volatile Organic Material at Three Eastern U.S. Sampling Sites

ABSTRACT

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 μm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of ~0.5 μm.     

杭州市空气颗粒物污染特征及变化规律研究

根据2006—2010年杭州市空气颗粒物的监测数据及2002、2006、2008年空气颗粒物来源解析结果,对杭州市空气颗粒物浓度、化学组分与污染来源等特征的变化规律进行分析,以期为空气颗粒物污染控制提供决策依据。结果表明,近年来杭州市PM10浓度有所下降,但一类功能区PM10仍超出《环境空气质量标准》(GB 3095—1996)的要求(≤0.04mg/m3),杭州市空气颗粒物污染以细颗粒物为主,空气颗粒物的二次转化、机动车尾气尘等产生的二次粒子污染相对严重;煤烟尘对杭州市PM10的贡献率下降明显,城市扬尘、二次粒子和机动车尾气尘对PM10的贡献率有所增加,是杭州市PM10的主要来源。     

某高密度街区大气颗粒物质量浓度分布特征实测研究

为研究城市高密度街区大气颗粒物浓度分布特征,2019年秋季对上海市某高密度街区道路大气颗粒物浓度、空气温度、相对湿度、地理位置、车辆与道路图像视频信息进行了同步移动在线监测,并结合街区内固定站数据和后向轨迹模拟结果,总结了影响街区大气颗粒物浓度变化的主要因素。结果表明:城市大气颗粒物背景拟合值处于较低水平时,街区内的大气颗粒物浓度变化和影响因素易被识别;机动车污染源对大气颗粒物浓度贡献大,其中大型机动车的影响明显;户外施工和道路清扫会引起大气颗粒物浓度上升,其中PM₁₀上升更明显;交通密度大的十字路口大气颗粒物浓度通常较高;城市高架的盖状结构会阻碍大气颗粒物在垂直方向上的扩散,引起局部大气颗粒物浓度上升;街区内高大浓密的乔木对近地面的大气颗粒物屏蔽效果不理想,甚至有助于颗粒物累积;早晚高峰时段大气颗粒物浓度较非高峰时段高。     

某高密度街区大气颗粒物质量浓度分布特征实测研究

为研究城市高密度街区大气颗粒物浓度分布特征,2019年秋季对上海市某高密度街区道路大气颗粒物浓度、空气温度、相对湿度、地理位置、车辆与道路图像视频信息进行了同步移动在线监测,并结合街区内固定站数据和后向轨迹模拟结果,总结了影响街区大气颗粒物浓度变化的主要因素。结果表明:城市大气颗粒物背景拟合值处于较低水平时,街区内的大气颗粒物浓度变化和影响因素易被识别;机动车污染源对大气颗粒物浓度贡献大,其中大型机动车的影响明显;户外施工和道路清扫会引起大气颗粒物浓度上升,其中PM₁₀上升更明显;交通密度大的十字路口大气颗粒物浓度通常较高;城市高架的盖状结构会阻碍大气颗粒物在垂直方向上的扩散,引起局部大气颗粒物浓度上升;街区内高大浓密的乔木对近地面的大气颗粒物屏蔽效果不理想,甚至有助于颗粒物累积;早晚高峰时段大气颗粒物浓度较非高峰时段高。     

Atmospheric Polycyclic Aromatic Hydrocarbons at a Point Source of Emissions. Part A: Identification and Determination of Polycyclic Aromatic Compounds in Airborne Particulate Matter Near a Horizontal Stud Soderberg Plant

Abstract

This paper summarizes the sampling and analytical methods developed to identify and measure polycyclic aromatic hydrocarbons (PAH) and related aromatic compounds near a Horizontal Stud Soderberg plant at Jonquiere, Quebec, Canada. The primary source of PAH is the coal tar pitch used as a binder in Soderberg anodes. Twice a week at a number of sampling sites, airborne particulate matter was collected on glass-fiber filters using a Hi-Vol sampler for a twenty-four hour period. Organics on the filter were Soxhlet extracted with benzene.

Identification was done by gas chromatography-mass spectrometry (GC-MS). The vast majority of compounds present were PAH, but small amounts of alkyl PAH and polycyclic aromatic compounds with heteroatoms such as nitrogen, oxygen and sulfur were also identified. Based on the GC-MS identification, a group of 14 PAH was selected for monitoring. Frequent PAH determinations revealed that the ratio of Benzo(a- )Pyrene to total PAH on the Hi-Vol filters is relatively constant in ambient air from one sampling station to another.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

A High Volume Stack Sampler

This paper deals with the development design, and trial application of a sampling train to gather a relatively large amount of particulate sample in a short period of time. With air pollution sources installing control equipment to reduce emissions to the required low levels, it becomes necessary to use a sampling device which can collect a representative sample in a reasonable period of time. Some of the sampling trains currently being specified are expensive, awkward, and nearly impossible to use under field conditions. The high-volume train overcomes ail of these shortcomings and has some additional advantages. It uses the same glass fiber filter that is specified for ambient air particulate sampling so the emission test results are directly comparable to ambient air sampling data. The laboratories currently weighing and analyzing the glass filters need no additional equipment for the emission sampling analysis. The sample collected by the high-volume probe may be analyzed microscopically for size and characteristics of the particles. This is very important if control equipment is to be specified for the process or source. The high-volume sampler was evaluated on field tests of wood fired boilers, incinerators, wigwam burners, asphalt batching plants, seed cleaning plants, and wood fiber filtration systems. The results of several typical tests using the sampler on these sources are included in the paper.     

Evaluation of catalyzed and electrically heated filters for removal of particulate emissions from diesel-A- and JP-8-fueled engines

In-service diesel engines are a significant source of particulate matter (PM) emissions, and they have been subjected to increasingly strict emissions standards. Consequently, the wide-scale use of some type of particulate filter is expected. This study evaluated the effect of an Engelhard catalyzed soot filter (CSF) and a Rypos electrically heated soot filter on the emissions from in-service diesel engines in terms of PM mass, black carbon concentration, particle-bound polycyclic aromatic hydrocarbon concentration, and size distribution. Both filters capture PM. The CSF relies on the engine's exhaust to reach the catalyst regeneration temperature and oxidize soot, whereas the electrically heated filter contains a heating element to oxidize soot. The filters were installed on several military diesel engines. Particle concentrations and compositions were measured before and after installation of the filter and again after several months of operation. Generally, the CSF removed at least 90% of total PM, and the removal efficiency improved or remained constant after several months of operation. In contrast, the electrical filters removed 44-69% of PM mass. In addition to evaluating the soot filters, the sampling team also compared the results of several real-time particle measurement instruments to traditional filter measurements of total mass.     

Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in the urban environment of Delhi

This paper reports on polycyclic aromatic hydrocarbons (PAHs) in the atmospheric particulate matter of Jawaharlal Nehru University campus, an urbanized site of New Delhi, India. Suspended particulate matter samples of 24h duration were collected on glass-fiber filter paper for four representative days in each month during January 2002 to December 2003. PAHs were extracted from filter papers using toluene with ultrasonication method and analysed. Quantitative measurements of polycyclic aromatic hydrocarbons (PAHs) were carried out using the gas chromatography technique. The annual average concentration of total PAHs were found to be 668+/-399 and 672+/-388 ng/m3 in the years 2002 and 2003, respectively. The seasonal average concentrations were found to be maximum in winter and minimum during in the monsoon. The results of principal component analysis (PCA) indicate that diesel and gasoline driven vehicles are the principal sources of PAHs in all the seasons. In winter coal and wood combustion also significantly contribute to the PAH levels.     

Evaluation of Catalyzed and Electrically Heated Filters for Removal of Particulate Emissions from Diesel-A- and JP-8-Fueled Engines

Abstract

In-service diesel engines are a significant source of particulate matter (PM) emissions, and they have been subjected to increasingly strict emissions standards. Consequently, the wide-scale use of some type of particulate filter is expected. This study evaluated the effect of an Engelhard catalyzed soot filter (CSF) and a Rypos electrically heated soot filter on the emissions from in-service diesel engines in terms of PM mass, black carbon concentration, particle-bound polycyclic aromatic hydrocarbon concentration, and size distribution. Both filters capture PM. The CSF relies on the engine's exhaust to reach the catalyst regeneration temperature and oxidize soot, whereas the electrically heated filter contains a heating element to oxidize soot. The filters were installed on several military diesel engines. Particle concentrations and compositions were measured before and after installation of the filter and again after several months of operation. Generally, the CSF removed at least 90% of total PM, and the removal efficiency improved or remained constant after several months of operation. In contrast, the electrical filters removed 44-69% of PM mass. In addition to evaluating the soot filters, the sampling team also compared the results of several real-time particle measurement instruments to traditional filter measurements of total mass.