Utilization of selected area electron diffraction patterns for characterization of air submicron particulate matter collected by a thermophoretic precipitator

A thermophoretic precipitator (TP) that uses a novelty of direct sampling of ambient air particulate matter (PM) onto transmission electron microscopy (TEM) grids was designed and utilized to determine its potential applicability for the collection and consequent qualitative analyses of representative PM in the air, especially those with aerodynamic diameter less than 1 microm (PM1.0). After a calibration process, preliminary field tests were performed under different weather conditions, locations, and time frames. TEM, selected area electron diffraction (SAED), and electron energy-dispersive X-ray spectrometry (EDS) analyses were performed on individual samples, and chemical species were analyzed. During this investigation, individual air PM with different sizes ranging from 10 microm to 10 nm for TEM analysis was collected. Two observations were made: (1) a large fraction of collected particulates were aggregates of very small particles of both organic and inorganic origin, and (2) a large fraction of the collected particulates were crystalline or polycrystalline. This study has demonstrated, by utilization of SAED patterns from TEM on air particles collected by a TP, the potential to analyze and identify individual air PM in a nanometer regime qualitatively by combining SAED and EDS data.     

Air quality measurements from the Fresno Supersite

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM2.5, PM10, and coarse (PM10 minus PM2.5) mass; 2) PM2.5 SO4(-2), NO3-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to approximately 10 microns; 4) criteria pollutant gases (O3, CO, NOx); 5) reactive gases (NO2, NOy, HNO3, peroxyacetyl nitrate [PAN], NH3); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM2.5 and PM10 mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM2.5 chemical speciation with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM10 and PM2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

Monitoring of sources and atmospheric processes controlling air quality in an urban Mediterranean environment

Different monitoring parameters (PM mass concentrations, number–size distribution, black carbon, gaseous pollutants, and chemical composition, among others) are currently used in air quality studies. Urban aerosols are the result of several sources and atmospheric processes, which suggests that a single monitoring technique is insufficient to quantitatively evaluate all of them.This study assesses the suitability of a number of monitoring techniques (PM mass concentrations, number and size distribution of ultra-fine particles, levels of gaseous pollutants, and a complete chemical characterization of PM₁₀ and PM_2.5) by examining the response of those techniques to the different emission sources and/or atmospheric processes affecting an urban Mediterranean area (Barcelona, NE Spain).The results of this work reveal that the PM mass, the number concentration and the chemical composition give different, but complementary, information. Whereas the mineral matter, a key atmospheric aerosol component across the Mediterranean, is not properly quantitatively assessed by measuring sub-micrometric particles, the monitoring of the number concentration is indispensable to interpret the origin of specific aerosol episodes. Furthermore, the chemical composition yields very relevant information to deduce the causes of specific pollution episodes.The number concentration of ultra-fine particles in urban areas is strongly dependent upon vehicle exhaust emissions, which may cause adverse health impacts. Moreover, urban Mediterranean environments are favourable to produce nucleation-mode particles (<20 nm) with photochemical origin. In those cases, these particles are expected to be of high solubility and consequently their toxicity may differ from that of traffic-generated ultra-fine particles. Thus, the use of a single monitoring parameter to evaluate the health effects seems to be not enough.     

Speciation and Characterization of Heavy Metal-Contaminated Soils Using Computer-Controlled Scanning Electron Microscopy

In the analysis of heavy metal-contaminated soils, particle-by-particle determination of elemental composition (i.e. species or mineral) as well as the characterization of particle size, external and internal morphology, can be used to assess bioavailability, remediation potential and source. The imaging capabilities of the scanning electron microscope (SEM) coupled with the elemental analysis provided by energy dispersive spectroscopy (EDS) can be used to acquire both chemical and physical information. Heavy metal particles can be analyzed automatically using computer-controlled scanning electron microscopy (CCSEM). The analysis first recognizes a particle and determines is periphery and various size measures. An EDS spectrum is obtained, the constituent elements identified and the occurrence classified into a compositional type. A TIFF microimage with spectrum is saved for later off-line review and location coordinates are saved for on-line review.Two examples illustrate the use of this technique in source identification. In one example, elevated levels of arsenic were attributed to a manufactured product rather than a fugitive source. In a second example, the lead-bearing constituents observed, as well as an association with a vuggy aluminosilicate occurrence and unburned coal, identifies coal ash as the probable source.     

Proinflammatory effect of fine and ultrafine particulate matter using size-resolved urban aerosols from Paris

Epidemiological and experimental studies have underlined that exposure to particulate matter (PM) leads mainly to airway inflammation, but the roles of particle size and chemical composition associated to such adverse health outcomes need to be better investigated. This study was performed to validate novel strategies of particle sampling, recovery and cell exposure in order to evaluate the pro-inflammatory potential of fine and ultrafine particles from a fractionated aerosol. Samplings of Paris background aerosols using 13-stage low pressure impactors (0.03-10 microm) gave bimodal mass distributions with an accumulation mode centered on a median diameter of 0.42 microm and a coarse one on 3.25 microm. PM 1 accounted for 70% and PM 0.1 for 12% of PM 10. The latter mainly comprised carbon-chained aggregates. The development of an efficient and reproducible method to recover fine (PM 1-0.1) and ultrafine (PM 0.1-0.03) particulate matter has permitted experimental comparison of the impact of such particles on human bronchial epithelial cells (HBECs). In this study we have compared the relative effects of fine and ultrafine particles at non-cytotoxic concentrations over 24h on the production of the pro-inflammatory cytokine GM-CSF by HBECs. Combining two cell exposure strategies to the size-fraction particles according to either their proportion (isovolume exposure) or their quantity in the aerosol (isomass exposure), we showed that both ultrafine and fine particles induced a concentration-dependent GM-CSF release by HBECs which is significant from 1 microg cm(-2). In conclusion, short duration samplings using 13-stage impactors enable to obtain size-resolved PM in sufficient quantities to carry out toxicological investigations. These findings are promising in view to conduct a more intensive study joining chemical and toxicological assays.     

Particle emissions of a railway line determined by detailed single particle analysis

The goal of this study was to identify and quantify particles emitted from railway traffic. For that purpose PM10 samples were collected near a busy railway line using a wind direction and speed controlled sampling equipment consisting of five devices. Measurements taken perpendicular to the railway lines at 10, 36 and 120 m distance enable an identification and separation of particles caused by the railway traffic from background particles. Morphology and chemistry of more than 11,000 particles were analysed by computer controlled scanning electron microscopy (CCSEM). Based on chemical composition five particle classes are defined and assigned to their sources. The mass of the individual particles is determined by multiplying their volumes, calculated based on their morphology with a density assigned specifically to each particle class. The density of the particle classes is derived from their chemical composition. To estimate the PM10 contributions of the railway lines, the mass of PM10 at 120 m (background, not influenced by the railway lines) is subtracted from the mass of PM10 at 10 m. The emissions of the railway lines are dominated by ‘iron’ particles, which contribute 2.9 μg m⁻³ or 67% to the railway related PM10. In addition, ‘aluminium’ and ‘calcium’ particles contribute also to the railway related PM10 (1.0 μg m⁻³ or 23% for the ‘aluminium’ and 0.4 μg m⁻³ or 10% for the ‘calcium’ particles). These particles are assigned to abrasion of the gravel bed and re-suspension of mineral dust.Long-term gravimetric results of the contribution of iron to the mass of railway related PM10 from a study performed earlier at the same site are in good agreement with the data presented in this study.     

A review of the impact of fireworks on particulate matter in ambient air

To determine the impact of fireworks (FW) and firecrackers (FC) on particulate matter (PM) in ambient air, we reviewed evidence related to ambient PM during FW/FC periods; specifically, PM concentration, size, morphology, chemical components, including water-soluble ions and trace metals, and associated human health risks caused by exposure to FW/FC PM were reviewed. A large body of research suggests that outdoor ambient PM levels increase significantly during FW/FC displays. Furthermore, FW/FC PM remains suspended in the air, contributing to high PM concentrations for a long period. Increased PM from burning FW and FC mainly comprises fine and ultrafine spherical particles. Elevated levels of various trace metals, ions, elemental carbon (EC), organic carbon (OC), and organics in PM are present during FW/FC periods.Implications: Unique physical and chemical properties of ambient PM during short-term FW/FC burning can lead to a substantial increase in adverse health effects compared with during non-FW/FC periods. Further epidemiological and toxicological research into the potential health effects resulting from exposure to various pollutants from FW/FC is vital. Geographical distributions of PM concentrations during FW displays highlight the importance of implementing PM controls at the regional level and formulating stricter protective environmental legislation, particularly in Asian (e.g., India, China, or Taiwan) where festivals are not the only periods celebrated with FW/FC.     

Time-resolved measurements of aerosol elemental concentrations in indoor working environments

We have measured the elemental concentrations in aerosols with a 2-h time resolution in two different types of working environment: a chemistry laboratory dealing with the processing of advanced nanoparticulate materials and a medium-sized machine workshop. Non-stop 10-day and 12-day samplings were performed at each location in order to determine the concentration trends during the non-working/working and weekday/weekend periods. Supplementary measurements of PM10 aerosols with a 2-day sample collection time were performed with a standard Gent PM10 sampler to compare the elemental concentrations with the time-averaged concentrations detected by the 2D step-sampler. The concentrations were determined a posteriori by analyzing the x-ray spectra of aerosol samples emitted after 3-MeV proton bombardment. The PM10 samples collected in the chemistry laboratory were additionally inspected by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) to determine the chemical compositions of the individual particles. In the workshop, a total PM10 mass sampling was performed simultaneously with a minute resolution to compare the signal with typical outdoor PM10 concentration levels. A factor analysis of the time-resolved dataset points to six and eight factors in the chemistry laboratory and the machine workshop, respectively. These factors describe most of the data variance, and their composition in terms of different elements can be related to specific indoor activities and conditions. We were able to demonstrate that the elemental concentration sampling with hourly resolution is an excellent tool for studying the indoor air pollution. While sampling the total PM10 mass concentration with a minute resolution may lack the potential to identify the emission sources in a “noisy” environment, the time averaging on a day time scale is too coarse to cope with the working dynamics, even if elemental sensitivity is an option.     

Individual particle analysis of indoor,outdoor, and community samples from the 1998 Baltimore particulate matter study

The United States Environmental Protection Agency (US EPA) recently conducted the 1998 Baltimore Particulate Matter (PM) Epidemiology-Exposure Study of the Elderly. The primary goal of that study was to establish the relationship between outdoor PM concentrations and actual human PM exposures within a susceptible (elderly) sub-population. Personal, indoor, and outdoor sampling of particulate matter was conducted at a retirement center in the Towson area of northern Baltimore County. Concurrent sampling was conducted at a central community site. The main objective of this work was to use computer-controlled scanning electron microscopy (CCSEM) with individual-particle X-ray analysis to measure the chemical and physical characteristics of geological and trace element particles collected at the various sampling locations in and around the retirement facility.The CCSEM results show that the relative abundances of some geological and trace element particle classes identified at the outdoor and community locations differ from each other and from the indoor location. Particle images acquired during the computer-controlled analyses played a key role in the identification of certain particle types. Review of these images was particularly useful in distinguishing spherical particles (usually indicative of combustion) from non-spherical particles of similar chemical composition. Pollens and spores were also identified through a manual review of the particle images.     

Combustion Aerosols: Factors Governing Their Size and Composition and Implications to Human Health

ABSTRACT

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 μm (PM_2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-tem-perature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Natural and anthropogenic environmental nanoparticulates: Their microstructural characterization and respiratory health implications

A wide range of environmental particulate matter (PM) both indoor and outdoor and consisting of natural and anthropogenic PM was collected by high volume air filters, electrostatic precipitation, and thermophoretic precipitation directly onto transmission electron microscope (TEM) coated grid platforms. These collected PM have been systematically characterized by TEM, energy-dispersive X-ray spectrometry (EDS) and scanning electron microscopy (SEM). In the El Paso, TX, USA/Juarez, Mexico metroplex 93% of outdoor PM₁ is crystalline while 40% of PM₁ is carbonaceous soot (including multiwall carbon nanotubes (MWCNTs) and multiconcentric fullerenes) PM. Multiply-replicated cytotoxicity (in vitro) assays utilizing a human epithelial (lung model) cell line (A549) consistently demonstrated varying degrees of cell death for essentially all PM which was characterized as aggregates of nanoparticulates or primary nanoparticles. Cytokine release was detected for Fe₂O₃, chrysotile asbestos, BC, and MWCNT PM while reactive oxygen species (ROS) production has been detected for Fe₂O₃, asbestos, BC, and MWCNT aggregate PM as well as natural gas combustion PM.Nanoparticulate materials in the indoor and outdoor environments appear to be variously cytotoxic, especially carbonaceous nano-PM such as multiwall carbon nanotubes, black carbon, and soot nano-PM produced by natural gas combustion.     

Design and characterization of a two-stage human subject exposure chamber

A human subject exposure chamber, designed to hold six to eight subjects, coupled to an approximately 30-m3 Teflon reaction bag was designed and built to provide exposures that mimic the production and photochemical oxidation of atmospheric pollutants resulting from the combustion of coal or wood from a stove. The combustion products are introduced into the Teflon bag under atmospheric conditions. Photochemical oxidation of this mixture is accomplished by exposure to tropospheric sun-like radiation from an array of ultraviolet and black lamps. The aerosol in the Teflon reaction bag is then transferred into the exposure room to maintain a constant, lower exposure level. Continuous and semicontinuous monitoring of the gas and particulate matter (PM) pollution in the exposure room and the reaction bag is accomplished using a suite of instruments. This suite of instruments allows for the measurement of the concentrations of total and nonvolatile PM, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, and ozone. The concentration of the particles was monitored by an R&P tapered element oscillating microbalance monitor. The chemical composition of the PM and its morphological characterization is accomplished by collecting samples in filter packs and conducting ion chromatography, elemental X-ray fluorescence, and scanning electron microscopy analyses. The concentration and composition of emissions from combustion of wood and coal is described. The results of this study suggest that although the bulk compositions of particulate emissions from the combustion of coal or wood in a stove have many similarities, the wood smoke aerosol is photochemically reactive, whereas the coal smoke aerosol is not.     

Characterisation of particulate matter and gaseous emissions from a large ship diesel engine

Composition of exhaust from a ship diesel engine using heavy fuel oil (HFO) was investigated onboard a large cargo vessel. The emitted particulate matter (PM) properties related to environmental and health impacts were investigated along with composition of the gas-phase emissions. Mass, size distribution, chemical composition and microphysical structure of the PM were investigated. The emission factor for PM was 5.3 g (kg fuel)^?1. The mass size distribution showed a bimodal shape with two maxima: one in the accumulation mode with mean particle diameter D_P around 0.5 μm and one in the coarse mode at D_P around 7 μm. The PM composition was dominated by organic carbon (OC), ash and sulphate while the elemental carbon (EC) composed only a few percent of the total PM. Increase of the PM in exhaust upon cooling was associated with increase of OC and sulphate. Laser analysis of the adsorbed phase in the cooled exhaust showed presence of a rich mixture of polycyclic aromatic hydrocarbon (PAH) species with molecular mass 178–300 amu while PM collected in the hot exhaust showed only four PAH masses.Microstructure and elemental analysis of ship combustion residuals indicate three distinct morphological structures with different chemical composition: soot aggregates, significantly metal polluted; char particles, clean or containing minerals; mineral and/or ash particles. Additionally, organic carbon particles of unburned fuel or/and lubricating oil origin were observed. Hazardous constituents from the combustion of heavy fuel oil such as transitional and alkali earth metals (V, Ni, Ca, Fe) were observed in the PM samples.Measurements of gaseous composition in the exhaust of this particular ship showed emission factors that are on the low side of the interval of global emission factors published in literature for NO_x, hydrocarbons (HC) and CO.     

Comparison between urban Toronto PM and selected materials: aerosol characterization using laser ablation/ionization mass spectrometry (LAMS)

Laser ablation/ionization mass spectrometry (LAMS) of particulate matter (PM) was undertaken on-line in order to extend and contrast PM characterization. Qualitative on-line LAMS results for certified materials and Toronto source materials demonstrated the versatility and limitations of the technique. The observation of organic and inorganic components of certified materials verified the proper working condition of the in-house on-line LAMS. Organic and inorganic components of Toronto source materials were also observed with the on-line LAMS. Common components identified from both types of materials were Na, Al, Ca, Fe, and K. Other recognized components were compared with marker elements reported for some common PM emission sources. An in-house off-line LAMS was used to analyze urban Toronto PM deposited on glass substrates, while the on-line LAMS analyzed individual urban Toronto PM particles that were introduced directly into the instrument. Scanning electron microscopy (SEM), X-ray spectrometry and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used for confirmatory purposes. Organic and inorganic components of urban Toronto PM at their typical ng/m3 concentrations were successfully observed in mass spectra using both off-line LAMS and on-line LAMS. Identified ions unique to each analyzed material were compared to identified ions of urban Toronto PM. The ability of LAMS to analyze individual respirable PM particles (viz. < 2 microns), both for inorganic trace elements and for organic components, greatly extended our capability to characterize PM and also to achieve estimates of concentration contributions of each material.     

Short-term temporal variation in PM2.5 mass and chemical composition during the Atlanta Supersite Experiment, 1999

Measurements in urban Atlanta of transient aerosol events in which PM2.5 mass concentrations rapidly rise and fall over a period of 3-6 hr are reported. The data are based on new measurement techniques demonstrated at the U.S. Environmental Protection Agency (EPA) Atlanta Supersite Experiment in August 1999. These independent instruments for aerosol chemical speciation of NO3-, SO4(2-), NH4+, and organic and elemental carbon (OC and EC), reconstructed the observed hourly dry PM2.5 mass to within 20% or better. Data from the experiment indicated that transient PM2.5 events were ubiquitous in Atlanta and were typically characterized by a sudden increase of EC (soot) and OC in the early morning or SO4(2-) in the late afternoon. The frequent temporal decoupling of these events provides insights into their origins, suggesting mobile sources in metro Atlanta as the main contributor to early morning PM2.5 and more regionally located point SO2 sources for afternoon PM2.5 events. The transient events may also have health implications. New data suggest that short-term PM2.5 exposures may lead to adverse health effects. Standard integrated filter-based techniques used in PM2.5 compliance monitoring networks and in most past PM2.5 epidemiologic studies collect samples over 24-hr periods and thus are unable to capture these transient events. Moreover, health-effects studies that focus on daily PM2.5 mass alone cannot evaluate the health implications of the unique and variable chemical properties of these episodes.     

Combustion aerosols: factors governing their size and composition and implications to human health

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 microns (PM2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-temperature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Synopsis of the temporal variation of particulate matter composition and size

A synopsis of the detailed temporal variation of the size and number distribution of particulate matter (PM) and its chemical composition on the basis of measurements performed by several regional research consortia funded by the U.S. Environmental Protection Agency (EPA) PM Supersite Program is presented. This program deployed and evaluated a variety of research and emerging commercial measurement technologies to investigate the physical and chemical properties of atmospheric aerosols at a level of detail never before achieved. Most notably these studies demonstrated that systematic size-segregated measurements of mass, number, and associated chemical composition of the fine (PM2.5) and ultrafine (PM0.1) fraction of ambient aerosol with a time resolution down to minutes and less is achievable. A wealth of new information on the temporal variation of aerosol has been added to the existing knowledge pool that can be mined to resolve outstanding research and policy-related questions. This paper explores the nature of temporal variations (on time scales from several minutes to hours) in the chemical and physical properties of PM and its implications in the identification of PM formation processes, and source attribution (primary versus secondary), the contribution of local versus transported PM and the development of effective PM control strategies. The PM Supersite results summarized indicate that location, time of day, and season significantly influence not only the mass and chemical composition but also the size-resolved chemical/elemental composition of PM. Ambient measurements also show that ultrafine particles have different compositions and make up only a small portion of the PM mass concentration compared with inhalable coarse and fine particles, but their number concentration is significantly larger than their coarse or fine counterparts. PM size classes show differences in the relative amounts of nitrates, sulfates, crustal materials, and most especially carbon as well as variations in seasonal and diurnal patterns.     

Threshold Dependence of Mortality Effects for Fine and Coarse Particles in Phoenix,Arizona

ABSTRACT

Daily data for fine (<2.5 um) and coarse (2.5-10 um) particles are available for 1995-1997 from the U.S. Environmental Protection Agency (EPA) research monitor in Phoenix, AZ. Mortality effects on the 65 and over population were studied for both the city of Phoenix and for a region of about 50 mi around Phoenix. Coarse particles in Phoenix are believed to be natural in origin and spatially homogeneous, whereas fine particles are primarily vehicular in origin and concentrated in the city itself. For this reason, it is natural to focus on city mortality data when considering fine particles, and on region mortality data when considering coarse particles, and most of the results reported here correspond to those assignments.

After allowing for seasonality and long-term trend through a nonlinear (B-spline) trend curve, and also for meteorological effects based on temperature and specific humidity, a regression of mortality was performed on PM using several different measures for PM. Based on a linear PM effect, we found a statistically significant coefficient for coarse particles, but not for fine particles, contrary to what is widely believed about the effects of coarse and fine particles. An analysis of nonlinear pollution-mortality relationships, however, suggests that the true picture is more complicated than that. For coarse particles, the evidence for any nonlinear or threshold-based effect is slight. For fine particles, we found evidence of a threshold, most likely with values in the range of 20-25 ug/m³. We also found some evidence of interactions of the PM effects with season and year.

The main effect here is an apparent seasonal interaction in the coarse PM effect. An attempt was made to explain this in terms of seasonal variation in the chemical composition of PM, but this led to another counterintuitive result: the PM effect is highest in spring and summer, when the anthropogenic concentration of coarse PM is lowest as determined by a principal components analysis. There was no evidence of confounding between the fine and coarse PM effects. Although these results are based on one city and should be considered tentative until replicated in other studies, they suggest that the prevailing focus on fine rather than coarse particles may be an oversimplification. The study also shows that consideration of nonlinear effects can lead to real changes of interpretation and raises the possibility of seasonal effects associated with the chemical composition of PM.     

A study of emissions from a Euro 4 light duty diesel vehicle with the European particulate measurement programme

The California Air Resources Board, CARB, has participated in a program to quantify particulate matter (PM) emissions with a European methodology, which is known as the Particulate Measurement Programme (PMP). The essence of the PMP methodology is that the diesel PM from a Euro 4 vehicle equipped with a Diesel Particulate Filter (DPF) consists primarily of solid particles with a size range greater than 23 nm. The PMP testing and the enhanced testing performed by CARB have enabled an increased understanding of both the progress that has been made in PM reduction, and the future remaining challenges for new and improved DPF-equipped diesel vehicles. A comparison of measured regulated emissions and solid particle number emissions with the results obtained by the PMP participating international laboratories was a success, and CARB’s measurements and standard deviations compared well with the other laboratories. Enhanced measurements of the influence of vehicle conditioning prior to testing on PM mass and solid particle number results were performed, and some significant influences were discovered. For example, the influence of vehicle preconditioning on particle number results was significant for both the European and USA test driving cycles. However, the trends for the cycles were opposite with one cycle showing an increase and the other cycle showing a decrease in particle number emissions. If solid particle size distribution and total particle numbers are to be used as proposed in PMP, then a greater understanding of the quality and errors associated with measurement technologies is advisable.In general, particle counting instruments gave results with similar trends, but cycle-to-cycle testing variation was observed. Continuous measurements of particle number concentrations during test cycles have given detailed insight into PM generation. At the present time there is significant variation in the capabilities of the particle counting instruments in terms of particle size and concentration.Current measurements show the existence of a large number of volatile and semi-volatile particles of yet-to-be-resolved chemical composition in diesel exhaust, especially during DPF regeneration, and these particles are not included in the PMP methodology because they are smaller than 20 nm. It will be very challenging to improve our understanding of this class of diesel particulate matter.