Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Hot Filter/Impinger and Dilution Sampling for Fine Particulate Matter Characterization from Ferrous Metal Casting Processes

Abstract

A study using two stack-sampling methodologies for collecting particulate matter (PM) emissions was conducted using a hot filter followed by a cold impinger sampling train and a dilution sampler. Samples were collected from ferrous iron metal casting processes that included pouring molten iron into a sand mold containing an organic binder, metal cooling, removal of the sand from the cooled casting (shakeout), and postshakeout cooling. The shakeout process contributed more to PM emissions than the metal pouring and cooling processes. Particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) mass emissions for the entire casting cycle ranged from 3.4 to 4.7 lb/t of metal for the hot filter/impinger method and from 0.8 to 1.8 lb/t of metal for the dilution method. Most of the difference was due to PM captured by the impingers, much of which was probably dissolved gases rather than condensable vapors. Of the PM fraction captured by the impingers, 96–98% was organic in nature. The impinger PM fraction contributed 32–38% to the total suspended particle mass and caused a factor of 2–4 positive bias for PM_2.5 emissions. For the pouring and cooling processes only, the factor increased to over seven times.     

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (～30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.     

Sampling Submicrometer Particles Suspended in Near Sonic and Supersonic Free Jets

This paper is concerned with sampling submicrometer particles in perisonic flows. The study employed a high volume (30-45 L/min) condensation aerosol generator to produce stearic acid particles having a mean diameter of 0.8μm and a geometric standard deviation of 1.28. The aerosol was diluted with dry air and accelerated to Mach 0.6, 0.8, 1.26, or 1.47 through a flow nozzle. Aerosol mass concentrations were determined using a small bore probe in the jet and by a large bore probe sampling isokinetically upstream of the jet nozzle. The results of both samples were compared to compute the sampling error associated with I ho high spood jot sample. The mass of stearic acid colloctod on polycarbonate mombrono flltors was determined by gravimoirlc and chromalogrophlc mothods. Studies at Mach 0.8 with four sampling probes having Inlet wall to bore area ratios ranging from 3.8 to 0.28 (a knife edge) demonstrated that probe wall thickness effects are not significant when the sample is extracted isokinetically. Subisokinetic experiments using the knife edged probe showed relative errors of 124 ± 12% when sampling at 2 0% of the isokinetic condition. The subisokinetic results are compared favorably with the extended empirical results of other authors. For the supersonic cases it is shown that the subsonic velocity downstream of the sampling probe bow shock can be used in estimating the sampling error.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Impact and growth phenomena observed with sub-micrometer atmospheric aerosol particles collected on polished silicon at low coverage

The processes occurring during the initial stages of size-selected sampling of atmospheric aerosol matter were explored by means of high-resolution scanning electron microscopy and energy dispersive X-ray spectrometry. The final four stages of a Berner impactor served to collect particles with aerodynamic diameters between 60 nm and 1 μm on polished silicon substrates at sampling times between 10 s and 16 min. In the single-particle impact regime (fractional coverage below 5%), most of the particles produced circular black tracks, of which 15 to 30% contained cores of carbonaceous nanoparticles. At a fractional coverage above about 10%, initially generated deposits became increasingly active as centres of preferred aerosol collection. As a result, the number of black spots remained almost constant, but the area per spot increased rapidly. At this stage of fractional coverage, structured aerosol matter became visible within large black areas of random shape. The deposits showed clear evidence for the onset of phase separation between carbon nanoparticles and material rich in sulphur, probably a mixture of alkaline and alkaline earth sulphates. After some time of sample storage in air the low-coverage sulphate matter tended to attain a fractal pattern. At a fractional coverage of several hundred per cent, large amorphous or crystalline objects had grown, but 30% or more of the nominal impact area still did not contain any aerosol matter. Moreover, carbon nanoparticles were found to be phase separated from the newly grown, very uniform aerosol material. The observations imply that sub-micrometer aerosol matter collected in impactors has lost memory of the original particle morphology.     

Hot filter/impinger and dilution sampling for fine particulate matter characterization from ferrous metal casting processes

A study using two stack-sampling methodologies for collecting particulate matter (PM) emissions was conducted using a hot filter followed by a cold impinger sampling train and a dilution sampler. Samples were collected from ferrous iron metal casting processes that included pouring molten iron into a sand mold containing an organic binder, metal cooling, removal of the sand from the cooled casting (shakeout), and postshakeout cooling. The shakeout process contributed more to PM emissions than the metal pouring and cooling processes. Particulate matter less than 2.5 microm in aerodynamic diameter (PM2.5) mass emissions for the entire casting cycle ranged from 3.4 to 4.7 lb/t of metal for the hot filter/impinger method and from 0.8 to 1.8 lb/t of metal for the dilution method. Most of the difference was due to PM captured by the impingers, much of which was probably dissolved gases rather than condensable vapors. Of the PM fraction captured by the impingers, 96-98% was organic in nature. The impinger PM fraction contributed 32-38% to the total suspended particle mass and caused a factor of 2-4 positive bias for PM2.5 emissions. For the pouring and cooling processes only, the factor increased to over seven times.     

Collection efficiency of a midget impinger for nanoparticles in the range of 3–100 nm

Impingers have been employed for collection of biological particles for a long time and the collection efficiency for submicron particles has been well studied for a few impinger models, like the SKC Biosampler and the AGI 30. These efficiency studies have been limited to particles larger than about 15 nm. The aim of this research is to determine the collection efficiency of ultrafine particles (from 3 to 100 nm) of a 25 ml midget impinger. The effect of different collection parameters (particle type, collection fluid volume and type and flow rate) was studied and results are presented here. All results showed minimum collection efficiencies from 3 to 10% at approximately 40–57 nm. Increasing the volume of the collection liquid and flow rate improved the collection efficiency of the impinger.     

Design and Testing of a New Size Classifying Isokinetic Sequential Aerosol Sampler

Two versions of a size-classifying isokinetic sequential aerosol sampler (SCISAS) have been designed, built, tested, and deployed in a field program in the southwestern United States. The SCISAS units can operate at unattended sites, exposing four or more filter types simultaneously, in two size ranges, for six sampling time Intervals. Design considerations included theoretical estimates of aerosol particle losses in the 0-15 μm size range.

SCISAS prototypes have been tested to evaluate their sampling efficiency as a function of flow rate, the sensitivity of the sampling efficiency to isokinetic matching within the SCISAS sampling stack, the equivalency of their sampling ports, and their passive deposition characteristics. The prototypes were also compared to several other types of aerosol filtration samplers already in common use. These tests show that particle loss mechanisms within the SCISAS usually cause no more than 5 percent losses, and that the SCISAS units agree, within one to two measurement uncertainty intervals, with other types of aerosol samplers.     

Utilisation de techniques spectroscopiques pour l'etude de particules atmospheriques produites par des sources ponctuelles

Secondary Ion Mass Spectrometry (SIMS) is used to study atmospheric particle production by an industrial source responsible for the acid precipitation phenomenon. A sampling network has been put in place at Rouyn-Noranda to collect local aerosols with cascade impactors. Aerosols have also been collected in the plume of the most important source of SO₂ in Quebec. Instruments have been developed and constructed to collect these samples. A multi-analytical technique approach permits physico-chemical analysis of individual aerosol: SIMS using a 1 μm ion probe and Scanning Electron Microscopy (SEM) coupled with an X-ray analyzer (EDAX) perform micro-analysis, whereas bulk analysis is provided by a SIMS using a 200 μm Argon ion probe. Devices used for localization of microparticles permit manipulation of samples without damaging them and allow analysis of individual aerosol particles with a SIMS after analysis with SEM-EDAX. Laser Microprobe Mass Analysis (LAMMA) is also possible. Negative and positive mass spectra, obtained with a SIMS-Ar⁺, have been analyzed with a multivariate statistical technique. Relations between these mass spectra and specific conditions existing during sampling have been determined.     

Sampling and analysis of biological aerosols

The extreme particle size range and enormous heterogeneity of airborne biological particles make sampling a significant challenge. Three major sampler types available include gravity devices, impactors and suction samplers. Gravity methods, while most commonly used, are neither qualitatively or quantitatively accurate and of very limited use. Impaction samplers (rotating, centrifugal) accelerate air by rotating the collecting surface or with a fan. Particles are collected from measured volumes of air but these devices preferentially sample particles larger than 10 μm. Suction samplers, which efficiently collect particles of a wide size range from measured volumes of air, include slit samplers, cascade impactors, filtration devices and liquid impingers. Suction samplers can retrieve viable particles by direct impaction on culture media, or by subsequent culture of impinger fluid or filter eluates. Nonviable particles can often be identified by microscopic examination of slides, filters or filtrates of impinger fluids. Immunoassays and biochemical assays can be used with impinger fluid and filter eluates to assess antigen and toxin levels in measured air samples.     

Comparing field performances of denuder techniques in the high Arctic

A field evaluation between two annular denuder configurations was conducted during the spring of 2003 in the marine Arctic at Ny-Ålesund, Svalbard. The IIA annular denuder system (ADS) employed a series of five single-channel annular denuders, a cyclone and a filter pack to discriminate between gas and aerosol species, while the EPA-Versatile Air Pollution Sampler (VAPS) configuration used a single multi-channel annular denuder to protect the integrity of PM_2.5 sample filters by collecting acidic gases. We compared the concentrations of gaseous nitric acid (HNO₃), nitrous acid (HONO), sulfur dioxide (SO₂) and hydrochloric acid (HCl) measured by the two systems. Results for HNO₃ and SO₂ suggested losses of gas phase species within the EPA-VAPS inlet surfaces due to low temperatures, high relative humidities, and coarse particle sea-salt deposition to the VAPS inlet during sampling. The difference in HNO₃ concentrations (55%) between the two data sets might also be due to the reaction between HNO₃ and NaCl on inlet surfaces within the EPA-VAPS system. Furthermore, we detected the release of HCl from marine aerosol particles in the EPA-VAPS inlet during sampling contributing to higher observed concentrations. Based on this work we present recommendations on the application of denuder sampling techniques for low-concentration gaseous species in Arctic and remote marine locations to minimize sampling biases. We suggest an annular denuder technique without a large surface area inlet device in order to minimize retention and/or production of gaseous atmospheric pollutants during sampling.     

A Cyclone for Size-Selective Sampling of Ambient Air

A cyclone with a 47 mm after-filter has been developed for ambient air size-selective monitoring. It has been extensively evaluated with laboratory-generated aerosol. Variation of the pressure drop and 50% cut point with flow rate show that the cyclone operates in a single flow regime with a vortex in the outlet flow. The particle size cutoff curve is comparable in sharpness to a cascade impactor and is the same for solid or liquid particles. At 21.7 L/min, D ₅₀ is 2.5μm and at 15.4 L/min, D ₅₀ is 3.5 μm. Collection efficiency data for flow rates from 8 to 27 L/min fit a universal curve when plotted vs. the normalized particle diameter, (D-D ₅₀)/D ₅₀ Reentrainment of previously deposited particles is less than 1 % of the loading per day. In field tests the cyclone has proved to be a very satisfactory size-selective sampler.     

Wintertime and summertime São Paulo aerosol source apportionment study

A detailed aerosol source apportionment study was performed with two sampling campaigns, during wintertime and summertime in the heavily polluted metropolitan area of São Paulo, Brazil. In addition to 12 h fine and coarse mode filter sampling, several real time aerosol and trace gas monitors were used. PM₁₀ was sampled using stacked filter units that collects fine (d<2.5 μm) and coarse (2.5<d<10 μm) particulate matter, providing mass, black carbon (BC) and elemental concentration for each aerosol mode. The concentration of about 20 elements was determined using the particle induce X-ray emission technique. Real time aerosol monitors provided PM₁₀ aerosol mass (TEOM), organic and elemental carbon (Carbon Monitor 5400, R&P) and BC concentration (Aethalometer). A complex system of sources and meteorological conditions modulates the heavy air pollution of the urban area of São Paulo. The boundary layer height and the primary emissions by motor vehicles controls the strong pattern of diurnal cycles obtained for PM₁₀, BC, CO, NO_x, and SO₂. Absolute principal factor analysis results showed a very similar source pattern between winter and summer field campaigns, despite the different locations of the sampling sites of both campaigns, pointing that there are no significant change in the main air pollution sources. The source identified as motor vehicle represented 28% and 24% of the PM_2.5 for winter and summer, respectively. Resuspended soil dust accounted for 25% and 30%. The oil combustion source represented 18% and 21%. Sulfates accounts for 23% and 17% and finally industrial emissions contributed with 5% and 6% of PM_2.5, for winter and summer, respectively. The resuspended soil dust accounted for a large fraction (75–78%) of the coarse mode aerosol mass. Certainly automobile traffic and soil dust are the main air pollution sources in São Paulo. The sampling and analytical procedures applied in this study showed that it is possible to perform a quantitative aerosol source apportionment in a complex urban area such as São Paulo.     

A Transition-Flow Reactor Tube for Measuring Trace Gas Concentrations

Dry deposition contributes significantly to the acidification of ecosystems. However, difficulties in measuring dry deposition of reactive gases and fine particles make routine direct monitoring impractical. An alternate approach is to use the “concentration monitoring” method in which dry deposition flux is estimated as the product of measured concentration and estimated deposition velocity. A sampling system that performs over the period of 6 hours to 7 days, depending on atmospheric concentrations, has been developed. It consists of a Teflon cyclone to exclude particles larger than about 2 μm, selective solid adsorption media for reactive gases—some of which are sampled from a transition flow to avoid possible bias from particle evaporation, a particle filter, and a final gas adsorption filter to collect the remaining trace gas. The sampler Is the first reported application of transition flow mass transfer for the collection and quantitative measurement of trace atmospheric gases. Laboratory and field tests have shown that the sampler performs well for HNO₃(g).     

Spatial and temporal variations of PM(2.5) concentration and composition throughout an urban area with high freeway density-the Greater Cincinnati study

The PM(2.5) concentration and its elemental composition were measured in the Cincinnati metropolitan area, which is characterized by intense highway traffic. The spatial and temporal variations were investigated for various chemical elements that contributed to the PM(2.5) fraction during a 1-year-long measurement campaign (December 2001-November 2002). The ambient aerosol monitoring was performed in 11 locations around the city during nine measurement cycles. During each cycle, four Harvard-type impactors were operating in parallel in specific locations to explore various factors affecting the PM(2.5) elemental concentrations. The sampling was performed during business days, thus assuring traffic uniformity. The 24-h PM(2.5) samples were collected on Teflon and quartz filters. Teflon filters were analyzed by X-ray fluorescence (XRF) analysis while quartz filters were analyzed by thermal-optical transmittance (TOT) analysis. In addition to PM(2.5) measurements, particle size-selective sampling was performed in two cycles using micro-orifice uniform deposit impactor; the collected fractionated deposits were analyzed by XRF. It was found that PM(2.5) concentration ranged from 6.70 to 48.3 mug m(-3) and had low spatial variation (median coefficient of variation, CV=11.3%). The elemental concentrations demonstrated high spatial variation, with the median CV ranged from 38.2% for Fe to 68.7% for Ni. For traffic-related trace metals, the highest concentration was detected in the city center site, which was close to a major highway. The particle size selective measurement revealed that mass concentration of the trace metals, such as Zn, Pb, Ni, as well as that of sulfur reach their peak values in the particle size range of 0.32-1.0 mum. Meteorological parameters and traffic intensity were not found to have a significant influence on the PM(2.5) elemental concentrations.     

Composition and mixing state of the urban background aerosol in the Rhein-Main area (Germany)

Size-resolved aerosol particle samples in the size range 0.1–10 μm aerodynamic diameter were collected in the years 2003 and 2004 at an urban background station in Mainz, Germany. Size, morphology, chemical composition and mixing state of more than 5400 individual particles of 7 selected sampling days were analyzed in detail by scanning electron microscopy and energy-dispersive X-ray microanalysis. In addition, transmission electron microscopy, aerosol mass spectrometry and atomic force microscopy were applied to obtain detailed information about the mixing state of the particles. The fine particle fraction (diameter<1 μm) is always dominated by complex secondary aerosol particles (⩾90% by number) independent from air mass origin. These particles are complex internal mixtures of ammonium and sodium sulfates, nitrates, and organic material. Between 20% and 40% of the complex secondary aerosol particles contain soot inclusions. The composition of the coarse particle fraction (>1 μm diameter) is strongly dependant on air mass history with variable abundances of complex secondary aerosol particles, aged sea salt, silicates, silicate mixtures, calcium sulfates, calcium sulfate/carbonate mixtures, calcium nitrate/carbonate mixtures, biological particles, and external soot.The dominance of complex secondary aerosol particles shows that reduction of the precursor gases is a major goal for successful reduction strategies for PM₁₀.     

Variation of Mass Scattering Efficiencies in IMPROVE

Abstract

The Interagency Monitoring of Protected Visual Environments (IMPROVE) equation used to assess compliance under the U.S. Environmental Protection Agency (EPA) Haze Rule assumes that dry mass scattering efficiencies for aerosol chemical components are constant. However, examination of aerosol size distributions and chemical composition during the Big Bend Regional Aerosol and Visibility Observational Study and the Southeastern Aerosol and Visibility Study suggests that volume and mass scattering efficiencies vary directly with increasing particle light scattering and aerosol mass concentration. This is consistent with the observation that particle distributions were shifted to larger sizes under more polluted conditions and appears to be related to aging of the aerosol during transport to remote locations.     

Street level versus rooftop concentrations of submicron aerosol particles and gaseous pollutants in an urban street canyon

Gaseous air pollutants and aerosol particle concentrations were monitored in an urban street canyon for two weeks. The measurements were performed simultaneously at two different heights: at street level (gases 3 m, aerosol particles 1.5 m) and at a rooftop 25 m above the ground. The main objective of the study was to investigate the vertical changes in concentrations of pollutants and the factors leading to the formation of the differences. The physical parameters controlling the concentration gradients (e.g. the flow and micrometeorology) were not directly measured and the conclusions of the study rely mostly on the high time resolution concentration measurements. It was concluded that dilution and dispersion decreases the concentrations of pollutants emitted at street level by a factor of roughly 5 between the two sampling heights. However, for some compounds the chemical reactions were seen to be of more importance when the vertical gradient is formed. In order to determine the processes leading to gradients in aerosol particle concentrations the photochemical formation of submicrometer aerosol particles was investigated using a theoretical expression based on the measured data. It was clearly seen that most of the particles originate from traffic in the vicinity of the measurement site. Also a few events were detected which might have been due to local gas-to-particle conversion.     

An Aerosol Sampler for Determination of Particle Concentration as a Function of Size and Time

A high flow rate four-stage impacfor was developed for the determination of aerosol concentration as a function of both particle size and time. The unit is very useful for long-term sampling intervals (24 hr) and for sampling very dusty atmospheres. Gas-borne particulate matter is collected out on four rotating drums, each with a collection surface area of about 10 sq in.; this allows a large quantity of materials to be collected without danger of particle build-up and blow-off. A particle size-collection efficiency calibration for the unit is presented together with experimental data on wall losses, surface coatings, and other important operational considerations.