Physicochemical characterisation of diesel exhaust particles: Factors for assessing biological activity

A range of microscopy and analytical techniques have been used to investigate the physicochemical properties of diluted DEP that may be important in determining its biological activity. Transmission electron microscopy demonstrated four basic categories of particle morphology: (1) “spherulites” [individual particles]; (2) “chains” or “clusters” of spherulites; (3) “spherules”, [large bodies of spherulites]; (4) “flake-like bodies”. Image analysis of TEM photomicrographs determined empirical morphological parameters (30 nm mean spherulite diameter, aspect ratio 1.5, mean particle area 0.078 μm, equivalent spherical diameter 0.23 μm, roundness 2.76) and derived parameters (0.313 μm² surface area, 3.7 μm² pg surface area per mass and 0.042 μm³ volume) of DEP. Distributions of the particle sizes by number showed 10.1% were ultrafine (<0.1 μm), 89.5% fine (0.1–2.0 μm), 0.4% coarse (>2.5 μm), but distributions based on a mass value were different (0.01% ultrafine; 52.6% fine, 47.4% coarse). In contrast, impacted DEP contained 60.87% ultrafine, 39.13% fine and 0% coarse particles by number. Field emission scanning electron microscopy of spherulites revealed smooth surfaces and flocculated spherules with large surface areas. Electron probe X-ray micro-analysis demonstrated the presence of C, O, Na, Mg, K, Al, Si, P, S, Cl, Ca along with a range of metals (Ti, Mn, Fe, Zn, Cr), that were heterogeneous in distribution. Inductively coupled plasma mass and atomic emission spectrometry identified Mg, P, Ca, Cr, Mn, Zn, Sr, Mo, Ba, Na, Fe, S, and Si as the mobile sorbed metals readily removed during sonication in water from DEP suspensions. X-ray Diffraction confirmed previous observations of the presence of nanometer sized crystallites of disordered graphite. Comparison of microscopy and analytical results between sonicated and impacted DEP revealed a physicochemical difference that must be taken into account in any toxicological investigations.     

Altered human monocyte/macrophage function after exposure to diesel exhaust particles

The relationship between immune defense mechanisms and environmental pollutants has been a focus of intensive research during the last decade. In animal experiments, diesel exhaust particles (DEP) have been shown to exert adjuvant effects on the IgE response against aeroantigens and to compromise broncho-pulmonary immune defense. Important target cells are monocytes/alveolar macrophages which display the important functions of phagocytosis, antigenpresentation and modulation of inflammatory processes. To further evaluate the influence of DEP upon these cells, we investigated whether exposure to suspended DEP would change the phagocytic capacity and the tumor necrosis factor alpha (TNF-α) release of human peripheral monocytes/alveolar macrophages. Our results demonstrated a dose-dependent reduction of phagocytosis (p < 0.001) and an additional increase of an ongoing TNF-α response (p < 0.005). These findings may help to link exposure to environmental pollutants to such biologic effects as increased susceptibility to broncho-pulmonary disease or facilitated sensitization against aeroallergens.     

Isomer distribution of nitrotriphenylenes in airborne particles, diesel exhaust particles, and the products of gas-phase radical-initiated nitration of triphenylene

The formation of mutagenic nitro-polycyclic aromatic hydrocarbons (NPAHs) 1- and 2-nitrotriphenylene (1- and 2-NTP) via gas-phase OH or NO₃ radical-initiated reactions of triphenylene was demonstrated for the first time using a flow reaction system. In contrast with the results of conventional electrophilic nitration, 2-NTP was formed in larger yield than 1-NTP, but this is consistent with the mechanism proposed for gas-phase radical-initiated nitration of PAH. In diesel exhaust particle (DEP) samples, both 1- and 2-NTP were identified and their concentrations determined, as well as 1-nitropyrene (1-NP), which is a representative combustion-derived NPAH: the mean concentrations of 1-NTP, 2-NTP, and 1-NP were 4.7, 1.9, and 32 pmol mg_DEP^–1, respectively. The mean 2-NTP/1-NTP, 1-NTP/1-NP, and 2-NTP/1-NP ratios in samples of airborne particles collected in a residential area in Osaka, Japan, were>1.55,<0.25, and 0.37, respectively; these values are much higher than those of the DEP samples. This finding indicates that there is another source for airborne NTPs, especially 2-NTP, apart from diesel exhaust. These results strongly suggest that airborne NTPs originate from atmospheric processes such as radical-initiated reactions of triphenylene, and this has a significant influence on the atmospheric occurrence of NTPs.     

Particulate matter in new technology diesel exhaust (NTDE) is quantitatively and qualitatively very different from that found in traditional diesel exhaust (TDE)

Diesel exhaust (DE) characteristic of pre-1988 engines is classified as a "probable" human carcinogen (Group 2A) by the International Agency for Research on Cancer (IARC), and the U.S. Environmental Protection Agency has classified DE as "likely to be carcinogenic to humans." These classifications were based on the large body of health effect studies conducted on DE over the past 30 or so years. However, increasingly stringent U.S. emissions standards (1988-2010) for particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust have helped stimulate major technological advances in diesel engine technology and diesel fuel/lubricant composition, resulting in the emergence of what has been termed New Technology Diesel Exhaust, or NTDE. NTDE is defined as DE from post-2006 and older retrofit diesel engines that incorporate a variety of technological advancements, including electronic controls, ultra-low-sulfur diesel fuel, oxidation catalysts, and wall-flow diesel particulate filters (DPFs). As discussed in a prior review (T. W. Hesterberg et al.; Environ. Sci. Technol. 2008, 42, 6437-6445), numerous emissions characterization studies have demonstrated marked differences in regulated and unregulated emissions between NTDE and "traditional diesel exhaust" (TDE) from pre-1988 diesel engines. Now there exist even more data demonstrating significant chemical and physical distinctions between the diesel exhaust particulate (DEP) in NTDE versus DEP from pre-2007 diesel technology, and its greater resemblance to particulate emissions from compressed natural gas (CNG) or gasoline engines. Furthermore, preliminary toxicological data suggest that the changes to the physical and chemical composition of NTDE lead to differences in biological responses between NTDE versus TDE exposure. Ongoing studies are expected to address some of the remaining data gaps in the understanding of possible NTDE health effects, but there is now sufficient evidence to conclude that health effects studies of pre-2007 DE likely have little relevance in assessing the potential health risks of NTDE exposures.     

Characterization of exhaust particles from military vehicles fueled with diesel,gasoline, and JP-8

Diluted exhaust from selected military aircraft ground-support equipment (AGE) was analyzed for particulate mass, elemental carbon (EC) and organic carbon (OC), SO4(2-), and size distributions. The experiments occurred at idle and load conditions and utilized a chassis dynamometer. The selected AGE vehicles operated on gasoline, diesel, and JP-8. These military vehicles exhibited concentrations, size distributions, and emission factors in the same range as those reported for nonmilitary vehicles. The diesel and JP-8 emission rates for PM ranged from 0.092 to 1.1 g/kg fuel. The EC contributed less and the OC contributed more to the particulate mass than reported in recent studies of vehicle emissions. Overall, the particle size distribution varied significantly with engine condition, with the number of accumulation mode particles and the count median diameter (CMD) increasing as engine load increased. The SO4(2-) analyses showed that the distribution of SO4(2-) mass mirrored the distribution of particle mass.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Measurements of ion concentration in gasoline and diesel engine exhaust

The nanoparticles formed in motor vehicle exhaust have received increasing attention due to their potential adverse health effects. It has been recently proposed that combustion-generated ions may play a critical role in the formation of these volatile nanoparticles. In this paper, we design an experiment to measure the total ion concentration in motor vehicle engine exhaust, and report some preliminary measurements in the exhaust of a gasoline engine (K-car) and a diesel engine (diesel generator). Under the experimental set-up reported in this study and for the specific engines used, the total ion concentration is ca. 3.3×10⁶ cm⁻³ with almost all of the ions smaller than 3 nm in the gasoline engine exhaust, and is above 2.7×10⁸ cm⁻³ with most of the ions larger than 3 nm in the diesel engine exhaust. This difference in the measured ion properties is interpreted as a result of the different residence times of exhaust inside the tailpipe/connecting pipe and the different concentrations of soot particles in the exhaust. The measured ion concentrations appear to be within the ranges predicted by a theoretical model describing the evolution of ions inside a pipe.     

低温等离子体技术及其在柴油机排气处理中的应用

概述了等离子体特点及分类 ,介绍了低温等离子体的产生及其净化柴油机排气的应用进展 ,分析了低温等离子体技术有效处理柴油机排气的机理 ,阐述了未来低温等离子体处理柴油机排气的主要方向与应用前景。     

Transformation of diesel engine exhaust in an environmental chamber

Overnight aging experiments with diesel engine exhaust from a diesel power aggregate, with no or 9 kW load, and from a diesel-fueled vehicle were conducted in an environmental chamber. During a 24 h aging period the volatilities of monodisperse particles at 140, 250 and 360 °C heater temperatures were analyzed with volatility tandem differential mobility analysis (VTDMA). The particulate organic to total carbon ratio and organic carbon subfractions at 120, 250, 450 and 550 °C were analyzed with thermal-optical carbon analysis for samples from fresh, 8 or 18 h aged and 24 h aged aerosol. During the experiment also the particle size distribution, ozone and nitrogen oxide concentration, and temperature, relative humidity and total solar and total ultraviolet radiation in the chamber were monitored.After injection, the geometric mean diameter and number concentration of the particles in the chamber were 66–85 nm and 0.9–4.6×10⁵ cm⁻³, respectively. The particles were seen to grow fast, at a growth rate of 18–47 nm h⁻¹ during the first hour. The fresh particles from the diesel power aggregate contained 37–45% of apparent volume semi-volatile compounds with no load and 10–24% with 9 kW load. The semi-volatile apparent volume fraction at 360 °C for 50 nm particles produced by the diesel power aggregate was 57%. After 24 h of aging, the semi-volatile apparent volume fraction at 360 °C for 100 nm particles was 99%. This suggests that the particles in the 24 h aged aerosol at this size class are no more primary particles but particles that are formed in the chamber through nucleation and subsequent growth.     

Effects of driving conditions on diesel exhaust particulates

Four driving conditions were examined to characterize how speeds and loads of a medium-duty diesel engine affect resultant diesel exhaust particulates (DEPs) in terms of number concentrations (< or =400 nm), size distribution, persistent free radicals, elemental carbon (EC), and organic carbon (OC). At the medium engine load (60%), DEPs surged in number concentrations at around 40-70 nm, whereas DEPs from the full engine load (100%) showed a distinctive bimodal distribution with a large population of 30-50 nm and 100-400 nm. Under the full engine load, engine speeds insignificantly affected resultant DEP number concentrations. When the engine load decreased from 100% to the medium level (60%), DEPs of ultrafine size and 100-400 nm decreased at least 1.4 times (from 5.6 x 10(8) to 4 x 10(8) #/cm3) and more than 3 times (from 2.7 x 10(8) to 0.8 x 10(8) #/cm3), respectively. The same reduction in the engine load significantly decreased persistent free radicals in DEPs up to approximately 30 times (from 123 x 10(16) to 4 x 10(16) #spin/g). Decreasing the engine load from 100 to 60% also concurrently reduced both EC and OC in total DEPs around 2 times, from 27.3 to 13.9 mg/m3, and from 17.6 to 9.2 mg/m3, respectively. For DEPs smaller than 1 microm, under the full engine load, EC and OC consistently peaked at 170-330 nm under an engine speed of 1800 rpm or 94-170 nm under an engine speed of 3000 rpm, reflecting processes of nucleation, cluster-cluster agglomeration, and condensation. Decreasing the engine load from 100 to 60% reduced EC and OC in DEPs (smaller than 1 microm) at least 3 times (0.6 to 0.2 mg/m3) and 2 times (0.4 to 0.2 mg/m3), respectively. Taken together, decreasing the full engine load to a medium (60%) level effectively reduced the number concentrations (< or =400 nm), persistent free radicals, EC, and OC of total DEPs, as well as the concentration of EC and OC in ultrafine and accumulation-mode DEPs.     

柴油机尾气中微粒粒径分布特征的实验研究

柴油机尾气中的微粒粒径大小分布范围广泛,不同直径的微粒所占的比例以及对环境和人身健康造成的危害各不相同,因此对微粒粒径特征进行研究更具有实际意义.本研究分别采用滤膜称重法和光散射法对厦工XG951Ⅲ装载机配置的国Ⅲ柴油发动机怠速工况下的尾气进行测试,研究了微粒的质量浓度分布、数量浓度分布以及质量浓度与数量浓度分布的关系.研究结果表明,从微粒质量上看,可吸入微粒(PM10)占微粒总量(TSP)的74.0%,可入肺微粒(PM2.5)占可吸入微粒的48.1%;2.5 μm以下粒径范围内的微粒质量浓度是2.5~10 μm粒径范围内微粒质量浓度的将近3倍,是10~100 μm粒径范围内微粒质量浓度的52倍;2.5~10 μm粒径范围的微粒质量浓度是10~100 μm粒径范围内微粒质量浓度的18倍.数量上,在不同的数量级上,微粒数量浓度随粒径变化差距很明显,尤其是1 μm以下的微粒较多.另外,质量浓度的粒径分布滞后于数量浓度.因此PM2.5排放标准中应考虑以个数浓度代替质量浓度为标准.     

Evolution of vehicle exhaust particles in the atmosphere

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.     

柴油车排气颗粒物的后处理技术

本文分析探讨了柴油机排气颗粒物的组成、危害及后处理技术。介绍了颗粒捕集器及其消极和积极再生方法、采用氧化催化剂或四效催化剂的催化净化器和低温等离子体 -催化净化技术。     

Comparison of vehicle exhaust emissions from modified diesel fuels

Three diesel fuels, one oil sand-derived (OSD) diesel serving as base fuel, one cetane-enhanced base fuel, and one oxygenate [diethylene glycol dimethyl ether (DEDM)]-blended base fuel, were tested for their emission characterizations in vehicle exhaust on a light-duty diesel truck that reflects the engine technology of the 1994 North American standard. Both the cetane-enhanced and the oxygenate-blended fuels were able to reduce regulated [CO, particulate matter (PM), total hydrocarbon (THC)] and nonregulated [polyaromatic hydrocarbons (PAHs), carbonyls, and other volatile organic chemicals] emissions, except for nitrogen oxides (NO(x)), compared with the base fuel. Although burning a fuel that contains oxygen could conceivably yield more oxygenated compounds in emissions, the oxygenate-blended diesel fuel resulted in reduced emissions of formaldehyde along with hydrocarbons such as benzene, 1,3-butadiene, and PAHs. Reductions in nitro-PAH emissions have been observed in both the cetane-enhanced and oxygenated fuels. This further demonstrates the benefits of using a cetane enhancer and the oxygenated fuel component.     

PCDDs and PCDFs in vehicle exhaust particles in Japan.

Vehicle exhaust particles from gasoline and diesel engine cars were analyzed for PCDDs and PCDFs. The congener patterns of PCDDs and PCDFs in exhaust particles were different between gasoline and diesel engine cars. Suspended particulate matter from electrostatic precipitator connected to a highway tunnel was also analyzed for PCDDs and PCDFs. The congener pattern of suspended particular matter was different from both of gasoline and diesel engine cars. Total amounts of PCDDs/PCDFs sum concentrations in gasoline, diesel and suspended particulate matter were 0.21, 0.87 and 26.0 ng/g, respectively. The I-TEQs levels in gasoline, diesel and suspended particulate matter were 4.2, 11 and 242 pg/g, respectively.     

Generation and characterization of diesel exhaust in a facility for controlled human exposures

An idling medium-duty diesel truck operated on ultralow sulfur diesel fuel was used as an emission source to generate diesel exhaust for controlled human exposure. Repeat tests were conducted on the Federal Test Procedure using a chassis dynamometer to demonstrate the reproducibility of this vehicle as a source of diesel emissions. Exhaust was supplied to a specially constructed exposure chamber at a target concentration of 100 microg x m(-3) diesel particulate matter (DPM). Spatial variability within the chamber was negligible, whereas emission concentrations were stable, reproducible, and similar to concentrations observed on the dynamometer. Measurements of nitric oxide, nitrogen dioxide, carbon monoxide, particulate matter (PM), elemental and organic carbon, carbonyls, trace elements, and polycyclic aromatic hydrocarbons were made during exposures of both healthy and asthmatic volunteers to DPM and control conditions. The effect of the so-called "personal cloud" on total PM mass concentrations was also observed and accounted for. Conventional lung function tests in 11 volunteer subjects (7 stable asthmatic) did not demonstrate a significant change after 2-hr exposures to diesel exhaust. In summary, we demonstrated that this facility can be effectively and safely used to evaluate acute responses to diesel exhaust exposure in human volunteers.     

Quantitation of nitro- and dinitropol ycyclic aromatic hydrocarbons in diesel exhaust particulate matter

A method for routine trace analysis of nitropolycyclic aromatic hydrocarbons (nitro-PAH) in diesel exhaust particulate matter is described. Particle extracts are prefractionated by silica high pressure liquid chromatography and the appropriate band analyzed by capillary electron capture gas chromatography. With on-column injection, three dinitropyrene isomers were recovered in the range of 69–85% for fortifications of 10 ug nitro-PAH/g of soot. The high signal-to-noise ratio suggested detection limits of about 2 ug/g for these analytes. Analysis of the Bureau of Standards SRM 1650 diesel particulate sample demonstrated the methods accuracy for 1-nitropyrene determinations as well.     

In vitro and in vitro toxicity study of diesel exhaust particles using BEAS-2B cell line and the nematode Caenorhabditis elegans as biological models

Environmental Science and Pollution Research - It is well accepted that diesel exhaust particles (DEPs) are highly associated with improper function of organ systems. In this study, DEP toxicity...