Some Applications of Microscopy to Air Pollution

The microscope as it has been and is now applied to air pollution work is discussed. A summary of the most common particulate sampling equipment is presented and distinctions as to the area of usage (suspended, or settled particulates) are made in each instance. Actual cases are discussed in which the polarizing microscope was used to determine identities and source of particulate pollutants. Particles from such sources as power plants, feed mills, and combustion sources are discussed and photomicrographs of known samples and unknown particles causing complaints are presented and compared as part of the discussion. References are given which deal with sampling equipment and microscopic analysis of various particulates.     

Severe particulate pollution from the deposition practices of the primary materials of a cement plant

Global cement production has increased twofold during the last decade. This increase has been accompanied by the installation of many new plants, especially in Southeast Asia. Although various aspects of pollution related to cement production have been reported, the impact of primary material deposition practices on ambient air quality has not yet been studied. In this study, we show that deposition practices can have a very serious impact on levels of ambient aerosols, far larger than other cement production-related impacts. Analyses of ambient particulates sampled near a cement plant show 1.3–30.4 mg/m³ total suspended particulates in the air and concentrations of particles with a diameter of 10 μm or less at 0.04–3 mg/m³. These concentrations are very high and seriously exceed air quality standards. We unequivocally attribute these levels to outdoor deposition of cement primary materials, especially clinker, using scanning electron microscopy/energy-dispersive X-ray spectroscopy. We also used satellite-derived aerosol optical depth maps over the area of study to estimate the extent of the spatial impact. The satellite data indicate a 33 % decrease in aerosol optical depth during a 10-year period, possibly due to changing primary material deposition practices. Although the in situ sampling was performed in one location, primary materials used in cement production are common in all parts of the world and have not changed significantly over the last decades. Hence, the results reported here demonstrate the dominant impact of deposition practices on aerosol levels near cement plants.     

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.     

Concentration, size distribution, and dry deposition rate of particle-associated metals in the Los Angeles region

Daily averaged atmospheric concentrations and dry deposition fluxes of particulate metals were measured seasonally at six urban sites and one non-urban coastal site in the Los Angeles region using a conventional total suspended particulate matter (TSP) filter, surrogate surface deposition plates, and a Noll Rotary Impactor (NRI), which provides information about particle size distribution in four size ranges above 6 μm. With the exception of the non-urban site, particulate metal concentrations and deposition fluxes were remarkably uniform spatially and temporally. At all sites there were significant metal concentrations on particles greater than 10 μm, a commonly used upper limit for many air quality monitoring studies, and these large particles were estimated to be responsible for most of the deposited mass of metals. Annual averaged values of deposition rates measured with a surrogate surface were in good agreement with values estimated using theoretical deposition velocities in conjunction with measured size-segregated particle concentrations. Image analysis of particles deposited on NRI stage A, which collects all particles greater than 6 μm, indicated nighttime metal concentrations and deposition at the non-urban coastal site was higher than in the day time due to offshore advection of urban air associated with the diurnal land breeze. Measured enrichments of crustal elements and metals were correlated, indicating efficient mixing of natural and anthropogenic material from different sources, hypothesized to be the result of cyclical resuspension and deposition of dust by moving vehicles and wind.     

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.     

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.     

Monitoring of deposited particles in cultural properties: the influence of visitors

Dust deposition has been monitored internally in cultural properties at four different locations for up to one year using horizontally mounted glass slides. The influence of the number of people entering the buildings on internal dust deposition has been examined. The number of people entering a building could be related to the deposition rates near entrances and it was noted that where there was a large volume of air surrounding the monitoring point this effect was not observed. The effect of temperature and relative humidity on dust deposition were of no significance. It is proposed that catastrophic events produce a significant contribution to particulate levels. Suggestions have been made for alternative approaches to the technique.     

An inverse Gaussian plume approach for estimating atmospheric pollutant emissions from multiple point sources

A method is developed for estimating the emission rates of contaminants into the atmosphere from multiple point sources using measurements of particulate material deposited at ground level. The approach is based on a Gaussian plume type solution for the advection–diffusion equation with ground-level deposition and given emission sources. This solution to the forward problem is incorporated into an inverse algorithm for estimating the emission rates by means of a linear least squares approach. The results are validated using measured deposition and meteorological data from a large lead–zinc smelting operation in Trail, British Columbia. The algorithm is demonstrated to be robust and capable of generating reasonably accurate estimates of total contaminant emissions over the relatively short distances of interest in this study.     

Performance of a Steam-Ejector Scrubber

The results of fractional and overall mass efficiency tests of a steam-ejector scrubber are presented. The tests were performed on one of seven modules of a full scale scrubber used for controlling particulate emissions from an open hearth furnace. Total flue gas particulate mass concentrations were determined at the inlet and outlet of the scrubber by conventional (Method 5) techniques. Inlet and outlet particulate concentrations as functions of diameter were determined on a mass basis using cascade impactors for sizes from about 0.3 μm to 5 μm, and on a number basis for diameters smaller than about 1 μm using optical and diffusional methods. Measurements were made under several scrubber operating conditions. The measured efficiencies based on total particulate mass concentrations with the scrubber operating under near optimum conditions ranged from 99.84 to 99.9%. The measured fractional efficiencies ranged from a maximum of 99.99% for particles having diameters of 1 μm to values of 97 and 99.9% for particles having diameters of 0.1, and 5 μm, respectively.     

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.     

Airborne particulate matter around the Cathedral of Burgos (Castilla y León,Spain)

A methodology to collect and analyse atmospheric particulate matter has been developed at the Cathedral of Burgos (Spain). Particles were collected in a portable particle sampler on carbon layers and stone surfaces. The analyses were undertaken under SEM-EDX by means X-ray mapping and Featurescan (a program for the automated characterisation of particles). To determine their possible sources, particles collected in the sampler and on carbon layers were classified according to their composition, mainly by cluster analysis. Then, they were compared with those deposited on stone surfaces. This classification is useful when a plan of preventive conservation for monuments is to be undertaken. In general, no important differences are observed between the chemical composition of particles directly collected from the atmosphere and those deposited on different substrates. Fine particles present the highest sulphur contents (almost 100%), while calcium is the major element in the medium and coarse particles. Other abundant elements are silicon, chlorine and phosphorus. The number of iron-rich particles is small. The study of the material deposited on carbon layers and stone substrates has confirmed the presence of gypsum in all cases.     

Biomonitoring of the distribution of dust emissions by means of a new SEM/EDX technique

A new application of the Scanning Electron Microscope (SEM) equipped with an Energy Dispersive X-ray Microanalyzer (EDX) has been developed to study the distribution of airborne dust emissions. This technique makes it possible to identify the particles and measure the amount of dust deposition on the surface of the biomonitoring material. Pine bark or needles and moss can easily be used as the study material. A map indicating pollution levels and distribution can be drawn on the basis of the measured data.     

Effect of atmospheric electricity on dry deposition of airborne particles from atmosphere

The electric mechanism of dry deposition is well known in the case of unattached radon daughter clusters that are unipolar charged and of high mobility. The problematic role of the electric forces in deposition of aerosol particles is theoretically examined by comparing the fluxes of particles carried by different deposition mechanisms in a model situation. The electric mechanism of deposition appears essential for particles of diameter 10–200 nm in conditions of low wind speed. The electric flux of fine particles can be dominant on the tips of leaves and needles even in a moderate atmospheric electric field of a few hundred V m⁻¹ measured over the plane ground surface. The electric deposition is enhanced under thunderclouds and high voltage power lines. Strong wind suppresses the relative role of the electric deposition when compared with aerodynamic deposition. When compared with diffusion deposition the electric deposition appears less uniform: the precipitation particulate matter on the tips of leaves and especially on needles of top branches of conifer trees is much more intensive than on the ground surface and electrically shielded surfaces of plants. The knowledge of deposition geometry could improve our understanding of air pollution damage to plants.     

Deposition and removal of fugitive dust in the arid southwestern United States: measurements and model results

This work was motivated by the need to better reconcile emission factors for fugitive dust with the amount of geologic material found on ambient filter samples. The deposition of particulate matter with aerodynamic diameter less than or equal to 10 microm (PM10), generated by travel over an unpaved road, over the first 100 m of transport downwind of the road was examined at Ft. Bliss, near El Paso, TX. The field conditions, typical for warm days in the arid southwestern United States, represented sparsely vegetated terrain under neutral to unstable atmospheric conditions. Emission fluxes of PM10 dust were obtained from towers downwind of the unpaved road at 7, 50, and 100 m. The horizontal flux measurements at the 7 m and 100 m towers indicated that PM10 deposition to the vegetation and ground was too small to measure. The data indicated, with 95% confidence, that the loss of PM10 between the source of emission at the unpaved road, represented by the 7 m tower, and a point 100 m downwind was less than 9.5%. A Gaussian model was used to simulate the plume. Values of the vertical standard deviation sigma(z) and the deposition velocity Vd were similar to the U.S. Environmental Protection Agency (EPA) ISC3 model. For the field conditions, the model predicted that removal of PM10 unpaved road dust by deposition over the distance between the point of emission and 100 m downwind would be less than 5%. However, the model results also indicated that particles larger than 10 microm (aerodynamic diameter) would deposit more appreciably. The model was consistent with changes observed in size distributions between 7 m and 100 m downwind, which were measured with optical particle counters. The Gaussian model predictions were also compared with another study conducted over rough terrain and stable atmospheric conditions. Under such conditions, measured PM10 removal rates over 95 m of downwind transport were reported to be between 86% and 89%, whereas the Gaussian model predicted only a 30% removal. One explanation for the large discrepancy between measurements and model results was the possibility that under the conditions of the study, the dust plume was comparable in vertical extent to the roughness elements, thereby violating one of the model assumptions. Results of the field study reported here and the previous work over rough terrain bound the extent of particle deposition expected to occur under most unpaved road emission scenarios.     

Apply appropriate models in the study of dry deposition fluxes of particulate matter and polycyclic aromatic hydrocarbons (PAHs) in Tsukuba, Japan

In this study, plates for downward flux and upward flux were used to measure atmospheric dry deposition fluxes for particulate mass and polycyclic aromatic hydrocarbons (PAHs) in TERC (Tsukuba), Japan. Ambient particles concentrations were also collected using a high-volume air sampler, and ambient particle size distributions between 0.01 μm and 13.1 μm were measured using a low-pressure cascade impactor to characterise the PAHs levels and dry deposition. The results indicated that the average cumulative fraction of dry deposition flux for particles and PAHs which attached with them was caused by the particle size of greater than 1.2-6.3 μm (97%).     

Gas and Particle Emissions from Automobile Tires in Laboratory and Field Studies

This paper is directed to air pollution scientists interested in special mobile emission sources. The purpose was to determine the contribution which automobile tires make to air pollution. The gaseous hydrocarbon and sulfur compounds emitted in laboratory tests were identified. Although these hydrocarbons can participate in smog reactions, their mass emission rate is less than 0.1 % of the current exhaust hydrocarbon emission rate. Hydrocarbons from tires are not measurable near a freeway. The particulate emitted from tires ranges in size from 0.01 μm to more than 30 μm, with the larger particles dominating the total mass. Measurements along a California freeway showed that most of the tire debris had settled within 5 m of the pavement edge. Airborne rubber concentrations were less than 0.5 μg/m³, or less than 5% of the total tire wear. These field measurements confirm the indoor emission pattern and verify that tire wear products are not a significant air pollution problem.     

The uptake of particulates by an urban woodland: site description and particulate composition

Woodlands may improve local air quality by increasing the uptake rates of gaseous, particulate and aerosol pollutants from the atmosphere and can also act as relatively permanent sinks for some pollutants. Rough Wood, Walsall was selected for a study of the material which accumulates on tree foliage because of its location in a densely populated urban area, and its proximity to a motorway with high traffic flow (the M6) and to other pollutant sources. Methods were developed for leaf washing to allow determination of the quantity of dust and the identification of the dust particles present on oak leaves. Elemental analysis of particles was also undertaken using scanning electron microscopy coupled with electron probe microanalysis. A large proportion of particles were organic in origin. Of the inorganic particles, the majority contained silicon and aluminium in varying proportions suggesting that they were soil derived. Some particles were clearly identified as the products of combustion, and sea or road salt was present on leaf surfaces. Some particles contained copper, tin and titanium which may reflect the proximity of Rough Wood to local metal workings. The number of particles counted on leaf surfaces decreased as distance from the motorway increased.     

Dry deposition of sulfate-containing particulate at the highway intersection, coastal and suburban areas

Sulfate-containing aerosol (SCA) dry deposition at the highway intersection, coastal location, and suburban area in Taiwan were analyzed and compared. Sampling was accomplished with a surrogate surface technique. Samples particles were coated with barium chloride (BaCl(2)) in a vacuum evaporator and then exposed to a relative humidity of 85% for 2 h to form distinctive products of SCAs. Treated samples were examined by a scanning electron microscopy. SCA dry deposition fluxes were 10.2, 4.1, 3.4 microgm(-2)s(-1) and nonsulfate-containing aerosol (NSCA) dry deposition fluxes were 23.3, 8.2, 13.5 microgm(-2)s(-1) at the highway intersection, coastal, and suburban areas. At the highway intersection, both SCA and NSCA dry deposition fluxes were much higher than those at the other two sites. The dry deposition of particles was also analyzed with a traditional technique. The number median diameters (NMDs) of SCA were 0.41, 0.82, and 1.2 mum at the highway intersection, coastal, and suburban sites, respectively. The highway intersection site had a small NMD, which showed that most sulfate-containing deposited aerosols existed in fine diameter range. The mass median diameters (MMDs) of SCA were 8.8, 19.5, and 14.9 mum at the highway intersection, coastal, and suburban sites, which were much higher than NMDs. Average numbers of SCAs in total particulate were 33%, 33%, and 22% at the highway intersection, coastal and suburban areas Most deposited particulates were nonsulfate-containing at the three sampling sites. SCAs less than 10 mum contributed 29%, 8%, and 7% to the total dry deposition at the highway intersection, coastal, and suburban areas, respectively. The contribution of fine particulate was significantly higher at the highway intersection site.     

Passive Sampling for Ozone

The Brigham Young University (BYU) organic sampling system (BOSS) and the high flow rate multi-system BYU organic sampling system (BIG BOSS), which use multichannel diffusion denuder sampling techniques, were both used to collect samples of atmospheric fine particulate organic material. Both systems were used at the Meadview sampling site located at the western boundary of the Grand Canyon National Park in northwestern Arizona for the Project MOHAVE summer intensive sampling program in August 1992. The concentrations of total fine particulate carbonaceous material determined by temperature programmed volatilization for BOSS collocated replicate samples were in agreement with an uncertainty of ±14%. A comparable agreement was seen between the BOSS and BIG BOSS samples. Carbonaceous material collected by the second of two sequential quartz filters was shown to have originated from organic material lost from particles during sampling. About one-half of the fine particulate organic material was lost from particles during sample collection. These semi-volatile organic compounds lost from particles during sampling were characterized by GC/MS analysis. The concentrations of n-alkanes, n-fatty acids, n-fatty methyl esters, and phthalic acid as a function of fine particulate size were obtained for compounds both retained by and lost from particles during sampling. The possible sources of fine particulate semi-volatile organic material collected at Meadview, and the particle size distribution of fine particulate organic material, n-alkanes, n-fatty acids, and n-fatty esters are discussed.     

Atmospheric Aerosol Composition and Concentration as a Function of Particle Size and of Time

As a step toward better understanding the reactive Los Angeles air basin atmosphere, a study was undertaken at the University of California—Riverside Campus, to determine the composition and concentration of atmospheric particulate matter as a function of particle size and time. The study involved developing a method for obtaining size-classified, time-fractionated aerosol samples amenable to chemical and physical (including microscopic) analysis. During a 15-day period, samples were obtained over 4-hr periods and subsequently analyzed for nitrate, sulfate, iron, and lead. Concentration of six gaseous pollutantsj total aerosol light-scattering, and several meteorological measurements were simultaneously recorded and averaged over the 4-hr intervals. This data was presented graphically to show the diurnal variation in and relationship between gaseous, particulate, and meteorological measurements. A strong relationship between gaseous peroxyacetyl nitrate, particulate nitrate, and aerosol light-scattering was found. High concentrations of ammonium nitrate particles, mainly in the 0.5-2μ, diameter size range, were found in the atmospheric particulate samples collected on days of very high smog (very limited visibility).