Comparison of real-time instruments used to monitor airborne particulate matter

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakersfield, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 microns (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of approximately 3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

New tabletop SEM-EDS-based approach for cost-efficient monitoring of airborne particulate matter

Recent developments in scanning electron microscopy (SEM) have produced tabletop instruments capable of reasonable imaging resolution at less cost compared to conventional equipment. Combining the SEM with energy dispersive spectroscopy (EDS) allows the possibility of elemental analysis through detection of X-rays emitted from interaction between individual particles and the SEM electron beam, revealing their atomic composition. It’s well known that exposure to inhalable particulate matter (PM) poses health risks and routine monitoring of the chemical content of these has been realized. Exposure information is of a general character but by combining the chemical build-up of monitored particles and knowledge of their inherent health effects will allow better risk assessment. An analysis technique using a tabletop SEM with EDS is demonstrated on particles collected onto nucleopore filters from urban, industrial and rural areas. Detailed characterization of the instruments analysis capabilities as applied to PM are described.     

The occurrence of Rovral and Permethrin in airborne particulate matter

A fungicide (Rovral) and an insecticide (Permethrin) were identified by GC/MS in cyclohexane extracts of airborne particulate matter sampled by filtration at Delft (The Netherlands) during 1981.     

A comprehensive particulate matter monitoring system and dosimetry-based ambient particulate matter standards

A numerical particulate matter (PM) measurement model is developed to characterize and evaluate PM sampling methods. Simulations are conducted using the model to evaluate currently widely used PM samplers, including Federal Reference Method (FRM) samplers. The simulations show that current PM samplers are very vulnerable to both changes in measurement target (i.e., natural variability of particle size distribution) and the sampler's design, manufacturing, and operating conditions, potentially resulting in significant errors in the monitoring data. The numerical model is used in conjunction with two types of commercially available PM monitoring devices to form a Comprehensive Particulate Matter Monitoring System (CPMMS). The first type of device can be any mass-based PM monitor with a well-defined sampling efficiency curve. The second type of device is one capable of measuring particle size distribution with a reasonably good relative accuracy between size categories but not necessarily accurate in measuring absolute mass concentrations. This study shows that CPMMS can produce much higher quality PM monitoring data than the current PM samplers under the same conditions. In addition, unlike past and current PM monitoring data such as total suspended particulates, coarse PM (PM10), fine PM (PM2.5), etc., the CPMMS monitoring data will survive changes in PM regulatory definition. A new concept, dosimetry-based PM metrics and standards, is proposed to define ambient PM level based on the deposition fraction of particles in the human respiratory tract. The dosimetry-based PM metrics is more meaningful because it correlates the ambient PM level with the portion that can be deposited in the respiratory tract without an arbitrary cutoff particle diameter. CPMMS makes dosimetry-based PM metrics and standards feasible.     

Environmental occurrence of nitrotriphenylene observed in airborne particulate matter

1- and 2-Nitrotriphenylenes were found in the airborne particulate matter extracts collected in central Tokyo between the winter of 1998 and the winter of 1999. In particular, we have identified and quantified nitrotriphenylenes in the airborne particulate matter extracts collected over four consecutive 6-h periods on 2 December 1999. The concentrations of 1- and 2-nitrotriphenylene ranged from 0.04 to 0.44 and from 0.02 to 0.47 ng/m3, respectively, and the concentrations in the airborne particulate matter extracts collected during the 18:00-24:00 h time period were the highest of the four collection periods. 1-Nitropyrene and 2-nitrofluoranthene were also identified and quantified in the four 6-h samples. Although the concentrations of 1- and 2-nitrotriphenylenes were not higher than that of 2-nitrofluoranthene except during the 18:00-24:00 h time period, the concentrations were much higher than that of 1-nitropyrene during the four collection periods.The higher concentrations of 1- and 2-nitrotriphenylenes during the 18:00-24:00 h time period are presumably responsible for the high reactivity of parent triphenylene with NO2/NO3/N2O5, and high stability of 1- and 2-nitrotriphenylenes toward O3 + O2. In addition, the observed isomer distribution of nitrotriphenylenes suggested that direct emission of nitrotriphenylenes is also a source as well as their atmospheric formation.     

An alternative way to determine the size distribution of airborne particulate matter

We developed and tested a methodology to extract both the size-segregated source apportionment of atmospheric aerosol and the size distribution of each detected element. The experiment is based on the parallel use of a standard low-volume sampler to collect Particulate Matter (PM) and an Optical Particle Counter (OPC). The approach is complementary to size-segregated PM sampling, and it was tested versus a 12-stage cascade impactor. Samples were collected inside the urban area of Genoa (Italy) and their elemental composition was measured by Energy Dispersive-X Ray Fluorescence (ED-XRF). Positive Matrix Factorization (PMF) was applied to time series of elemental concentrations to identify major PM sources, and both PM mass concentration and size-segregated particle number concentration were apportioned. Source profiles and temporal trends extracted by PMF were analyzed together with the OPC data to obtain the size distribution for several elements. The new methodology proved to be reliable for the PM apportionment as well as in providing the elemental concentrations in PM10, PM2.5, and PM1 (PM with aerodynamic diameter, D_ae < 10, 2.5, and 1 μm, respectively). The elemental size distributions are in good agreement with those obtained by the cascade impactor for several elements but some discrepancies, in particular for traffic emissions, are stressed and discussed in the text. The new methodology has two main advantages: it only requires standard semi-automatic sampling equipment and compositional analysis and it provides size-segregated information averaged over quite long periods (typically several months). This is particularly important since campaigns with cascade impactors are generally laborious and thus limited to short periods.     

The wind speed dependence of the concentrations of airborne particulate matter and NOx

The wind speed dependence of concentrations of PM₁₀, chloride, sulphate, nitrate, organic carbon, elemental carbon, particle number and NO_x has been determined at three separate sites, Marylebone Road (kerbside), North Kensington (urban background) and Harwell (rural). The data are best described by a general dilution term multiplied by up to three separate source-related terms which we interpret as representing long-range transport sources, discrete local (including area) sources and marine sources respectively. Using this approach, the various particulate metrics can be quantitatively disaggregated according to the contributions of the three source types. The behaviour of nitrate is anomalous, probably due to an influence of wind speed upon the dissociation of ammonium nitrate.     

Source apportionment of airborne fine particulate matter in an underground mine

The chemical mass balance source apportionment technique was applied to an underground gold mine to assess the contribution of diesel exhaust, rock dust, oil mists, and cigarette smoke to airborne fine (<2.5 microm) particulate matter (PM). Apportionments were conducted in two locations in the mine, one near the mining operations and one near the exit of the mine where the ventilated mine air was exhausted. Results showed that diesel exhaust contributed 78-98% of the fine particulate mass and greater than 90% of the fine particle carbon, with rock dust making up the remainder. Oil mists and cigarette smoke contributions were below detection limits for this study. The diesel exhaust fraction of the total fine PM was higher than the recently implemented mine air quality standards based on total carbon at both sample locations in the mine.     

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.     

The occurrence of plant wax constituents in airborne particulate matter in an urbanized area

Airborne particulate matter was collected by filtration in an urbanized area at Delft (The Netherlands) during 1981. The samples were extracted by means of cyclohexane and analysed by GC/MS. Differences were observed between summer and winter samples. Besides a different n-alkane pattern, the summer samples contained large quantities of long-chain polar aliphatic compounds. The identification of these compounds was carried out by means of electron impact, chemical ionization and high resolution mass spectrometry. These compounds are known plant was constituents. The contribution of the plant wax constituents to the total amount of analysed compounds in the cyclohexane extracts was estimated at about 40 % in the summer.     

The impact of a building implosion on airborne particulate matter in an urban community

In response to community concerns, the air quality impact of imploding a 22-story building in east Baltimore, MD, was studied. Time- and space-resolved concentrations of indoor and outdoor particulate matter (PM) (nominally 0.5-10 microm) were measured using a portable nephelometer at seven and four locations, respectively. PM10 levels varied in time and space; there was no measurable effect observed upwind of the implosion. The downwind peak PM10 levels varied with distance (54,000-589 microg/m3) exceeding pre-implosion levels for sites 100 and 1130 m 3000- and 20-fold, respectively. Estimated outdoor 24-hr integrated mass concentrations varied from 15 to 72 microg/m3. The implosion did not result in the U.S. Environmental Protection Agency (EPA) National Ambient Air Quality Standard (NAAQS) for PM10 being exceeded. X-ray fluorescence analysis indicated that the elemental composition was dominated by crustal elements: calcium (57%), silicon (23%), aluminum (7.6%), and iron (6.1%). Lead was above background but at a low level (0.17 microg/m3). Peak PM10 concentrations were short-lived; most sites returned to background within 15 min. No increase in indoor PM10 was observed even at the most proximate 250 m location. These results demonstrate that a building implosion can have a severe but short-lived impact on community air quality. Effective protection is offered by being indoors or upwind.     

Regional contributions to airborne particulate matter in central California during a severe pollution episode

The externally-mixed source-oriented UCD/CIT air quality model was applied to determine the significance of inter-regional transport for primary and secondary particulate matter (PM) in California's Central Valley during a severe wintertime PM pollution episode from December 15, 2000 to January 7, 2001. The gases and primary PM emitted from eight different geographical sub-regions were tracked separately in a model simulation that included transport, physical and chemical transformation and deposition processes. The model results directly predict the contribution that each sub-region makes to PM concentrations throughout the entire model domain. The boundary layer was relatively stagnant during the simulated 3-week air quality episode, and no consistent transport pattern for primary PM was predicted. Several significant inter-regional transport events were identified that each lasted a few days. Each of these inter-regional events was characterized by transport of gas-phase precursors of nitrate that combined with local emissions of ammonia to produce particulate nitrate. Nitrate already in the particle phase was not transported efficiently due to higher dry deposition rates for particles relative to gas-phase nitrogen oxides. The distinctive pattern of transport for nitrate precursors reflects the relatively long timescales required to convert NO_x emissions to nitrate during winter conditions characterized by low temperatures, weak photolysis rates, and low oxidant concentrations. The equilibrium partitioning of nitrate and ammonia to the particle phase is relatively fast once the nitrate has been produced. The most-likely transport distance for nitrate during the current episode varied from 130–140 km for the northern portion of the Central Valley to 50–60 km in the southern portion of the Central Valley. Sub-regions further south in the Valley have smaller transport distances because of slower wind speeds and the greater abundance of ammonia in these areas, leading to faster conversion of gas-phase reactive nitrogen into particulate nitrate, which has a higher dry deposition rate than the gas-phase species. The most-likely transport distance for primary organic compounds (OC) was found to be less than that for nitrate, varying from 50 to 60 km for the northern portion of the Valley to 20–30 km for southern portion of the Valley. Overall, 68% of the particulate nitrate formed in the most polluted sub-regions of the Central Valley originates from emissions in those same sub-regions. Local emissions controls should therefore provide an effective strategy to reduce airborne particulate matter concentrations to acceptable levels.     

Personal monitoring of exposure to particulate matter with a high temporal resolution

Background

Continuous monitoring of air quality is implemented by government institutions at fixed ambient sites. However, the correlation between fixed site measurements and exposure of individual persons to air contaminants is likely to be weak.

Materials and methods

We measured particulate matter both outdoors and indoors by following the spatial movement of individuals. Sixteen test persons took part and carried a measurement backpack for a 24-h period. The backpack was comprised of a Grimm Aerosol Spectrometer model 1.109, a GPS device, and a video camera for tracking of human behavior. The spectrometer provided information about particle numbers and mass in 32-size classes with a high temporal resolution of 6 s.

Results

The personal exposure of individuals during 24 h could significantly exceed the outdoor particulate matter (PM)₁₀ concentrations measured at the fixed sites. The average 24-h exposure of all test persons for PM₁₀ varied from 27 to 322 ??g m^?3. Environmental tobacco smoke and cooking emissions were among the main indoor sources for PM. The amount of particulate matter a test person was exposed to was highly dependent on the spatial behavior and the surrounding microenvironment conditions.

Discussion

Large-scale experiments including personal measurements might help to improve modeling approaches to approximate the actual exposure on a statistically sound basis.     

Particle size and composition distribution analysis of automotive brake abrasion dusts for the evaluation of antimony sources of airborne particulate matter

Abrasion dusts from three types of commercially available non-steel brake pads were generated by a brake dynamometer at disk temperatures of 200, 300 and 400 °C. The number concentration of the abrasion dusts and their aerodynamic diameters (D_p) were measured by using an aerodynamic particle sizer (APS) spectrometer with high temporal and size resolution. Simultaneously, the abrasion dusts were also collected based on their size by using an Andersen low-volume sampler, and the concentrations of metallic elements (K, Ti, Fe, Cu, Zn, Sb and Ba) in the size-classified dusts were measured by ICP-AES and ICP-MS. The number distributions of the brake abrasion dusts had a peak at D_p values of 1 and 2 μm; this peak shifted to the coarse side with an increase in the disk temperature. The mass distributions calculated from the number distributions have peaks between D_p values of 3 and 6 μm. The shapes of the elemental mass distributions (Ti, Fe, Cu, Zn, Sb and Ba) in size-classified dusts were very similar to the total mass distributions of the brake abrasion dusts. These experimental results indicated that the properties of brake abrasion dusts were consistent with the characteristics of Sb-enriched fine airborne particulate matter. Based on these findings and statistical data, the estimation of Sb emission as airborne particulate matter from friction brakes was also discussed.     

Effects of airborne particulate matter on the acidity of precipitation in Central Missouri

The pH of rainfall in central Missouri was monitored at four sites during the fall of 1983. Several pH values were well above 5.6, the theoretical pH of pure water in equilibrium with ambient levels of CO₂. Most of the higher pHs were measured on rainfall of short duration or rainfall collected during the first few hours of extended rainfall events. Furthermore, the rainfall associated with storm events lasting several days exhibited a trend of decreasing pH with time approaching values as low as 4.0 during the late stages of rainfall. Precipitation pH values above 5.6 apparently reflect neutralization reactions between wet precipitation and various components of airborne dust, especially clays and carbonates. During extended rainfalls, the neutralization effects gradually diminish as suspended dust is washed from the atmosphere yielding more accurate values of the wet precipitation pH. The results of this study suggest that airborne particulate matter generated from the dust bowl region of the U.S. may affect the chemistry of precipitation in areas hundreds of km downwind.     

A study of polycyclic aromatic hydrocarbons in airborne particulate matter in central Taiwan

Two sampling sites in central Taiwan, at Hungkuang University (HKU) and Tunghai University (THU), were chosen to contrast the content of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere from November 2000 to April 2001. PAHs that arise from incomplete combustion of organic materials, especially fossil fuels, are the major toxic pollutants in central Taiwan. This study aimed to analyse PAHs, by using a PS-1 sampler and a gas chromatograph/mass selective detector (GC/MSD), and to identify the major sources of PAHs. At the HKU sampling site, the primary emission sources are probably vehicles and coal burning, and vehicular emissions are the primary contributor at the THU sampling site.     

Theoretical study of the impact of particulate matter gravitational settling on ambient coarse particulate matter monitoring for agricultural emissions

The particle size distributions (PSDs) of particulate matter (PM) in the downwind plume from simulated sources of a cotton gin were analyzed to determine the impact of PM settling on PM monitoring. The PSD of PM in a plume varies as a function of gravitational settling. Gravitational settling has a greater impact on the downwind PSD from sources with PSDs having larger mass median diameters (MMDs). The change in PSD is a function of the source PSD of emitted PM, wind speed, and downwind distance. Both MMD and geometric standard deviation (GSD) in the downwind plume decrease with an increase in downwind distance and source MMD. The larger the source MMD, the greater the change in the downwind MMD and GSD. Also, the greater the distance from the source to the sampler, the greater the change in the downwind MMD and GSD. Variations of the PSD in the downwind plume significantly impact PM10 sampling errors associated with the U.S. Environmental Protection Agency (EPA) PM10 samplers. For the emission sources with MMD > 10 microm, the PM10 oversampling rate increases with an increase in downwind distance caused by the decrease of GSD of the PSD in the downwind plume. Gravitational settling of particles does not help reduce the oversampling problems associated with the EPA PM10 sampler. Furthermore, oversampling rates decrease with an increase of the wind speed.     

Modeling exposure to particulate matter

Exposure assessment, a component of risk assessment, links sources of pollution with health effects. Exposure models are scientific tools used to gain insights into the processes affecting exposure assessment. The purpose of this paper is to review the process and methodology of estimating inhalation exposure to particulate matter (PM) using various types of models. Three types of models are discussed in the paper. Indirect type of models are physical models that employ inventories of outdoor and indoor sources and their emission rates to identify major sources contributing to exposure to PM, and use fate and transport and indoor air quality models to estimate PM concentrations at receptor sites. PM concentrations and time spent by a subject at each receptor site are input variables to the conventional exposure model that estimates the desired exposure levels. Direct type models use measured exposure or exposure concentrations in conjunction with information obtained from questionnaires to formulate exposure regression models. Stochastic models use exposure measurements, estimates can also be used, to formulate exposure population distributions and investigate associated uncertainty and variability. Since models developed using databases from western countries are not necessarily applicable in developing countries, the difference in requirements among western and developing countries is highlighted in the paper. Employment of exposure modeling methods in developing countries requires development of local information. Such information includes local outdoor and indoor source inventories, local or regional meteorological conditions, adjustment of indoor models to reflect local building construction conditions, and use of questionnaires to obtain local time budget and activity patterns of the subject population.     

A new methodological approach: The combined use of two-stage streaker samplers and optical particle counters for the characterization of airborne particulate matter

We describe a new experimental methodology based on the contemporary use of two-stage continuous streaker samplers and optical particle counters. This is a complementary approach to size-segregated particulate matter (PM) sampling, and it is able to give information on the elemental size distribution and to assess the contribution of major PM source to size bins. PM samples in the fine and coarse fraction of PM10 have been collected by a two-stage streaker sampler and analyzed by particle-induced X-ray emission (PIXE) to obtain elemental concentration time series with hourly resolution. PM sources and profiles were singled out by positive matrix factorization (PMF). A multi-linear regression of size-segregated number of particles versus the sources, resolved by PMF, made possible the apportionment of size-segregated particles number in a fast and direct way. Results obtained in three sampling sites, located in different urban districts are discussed.     

Identification and chemical characterization of industrial particulate matter sources in southwest Spain

A detailed physical and chemical characterization of coarse particulate matter (PM10) and fine particulate matter (PM2.5) in the city of Huelva (in Southwestern Spain) was carried out during 2001 and 2002. To identify the major emission sources with a significant influence on PM10 and PM2.5, a methodology was developed based on the combination of: (1) real-time measurements of levels of PM10, PM2.5, and very fine particulate matter (PM1); (2) chemical characterization and source apportionment analysis of PM10 and PM2.5; and (3) intensive measurements in field campaigns to characterize the emission plumes of several point sources. Annual means of 37, 19, and 16 microg/m3 were obtained for the study period for PM10, PM2.5, and PM1, respectively. High PM episodes, characterized by a very fine grain size distribution, are frequently detected in Huelva mainly in the winter as the result of the impact of the industrial emission plumes on the city. Chemical analysis showed that PM at Huelva is characterized by high PO4(3-) and As levels, as expected from the industrial activities. Source apportionment analyses identified a crustal source (36% of PM10 and 31% of PM2.5); a traffic-related source (33% of PM10 and 29% of PM2.5), and a marine aerosol contribution (only in PM10, 4%). In addition, two industrial emission sources were identified in PM10 and PM2.5: (1) a petrochemical source, 13% in PM10 and 8% in PM2.5; and (2) a mixed metallurgical-phosphate source, which accounts for 11-12% of PM10 and PM2.5. In PM2.5 a secondary source has been also identified, which contributed to 17% of the mass. A complete characterization of industrial emission plumes during their impact on the ground allowed for the identification of tracer species for specific point sources, such as petrochemical, metallurgic, and fertilizer and phosphate production industries.