Intercomparison of measurement methods for black carbon aerosols

In this study, two method intercomparisons were performed. One thermal and two optical methods for the measurement of black carbon (BC) were applied to laboratory generated aerosols containing only BC. For the optical measurements, an aethalometer (Hansen et al., 1984. Science of Total Environment 36, 191–196) and an integrating sphere technique (Hitzenberger et al., 1996b. Journal of Geophysical Research 101, D14, 19 601–19 606) were used. The thermal method was described by Cachier et al. (1989a. Tellus 41B, 379–390). In an additional comparison, the integrating sphere was compared to a thermal optical technique (Birch and Cary, 1996. Aerosol Science Technology 25, 221–241) on ambient aerosol samples. The absorption coefficients were obtained from transmission measurements on filter samples for both the aethalometer and the integrating sphere. The BC mass concentration for the aethalometer was derived from this absorption measurement. The BC mass concentration for the integrating sphere, however, was obtained using an independent calibration curve. The agreement between the absorption coefficient σ_a obtained for the BC test aerosol on parallel filters with the aethalometer and the integrating sphere was satisfactory. The slope of the regression lines depended on filter type. A comparison between BC mass concentrations, however, showed that the aethalometer values were only 23% of those obtained by the integrating sphere technique indicating that for pure BC aerosols, the standard aethalometer calibration should not be used. Compared to the thermal method, the integrating sphere gave an overestimation of the BC mass concentrations by 21%. For the ambient samples, the integrating sphere and the thermal optical methods for BC mass concentration determination showed agreement within 5% of the 1 : 1 line, although the data were not so well correlated.     

Evaluation of alternative filter media for particulate matter emission testing of residential wood heating devices

The performance of Teflon-coated glass fiber filter media (Pallflex Emfab TX40) is evaluated for particulate matter (PM) sampling of residential wood heating devices in a dilution tunnel. Thirty samples of varying duration and PM loading and concentration were collected from an U.S. Environmental Protection Agency (EPA) Method 28 dilution tunnel using dual Method 5G sample trains with untreated glass fiber and Emfab filters. Filters were weighed soon after the end of sampling and again the next day after equilibration at 35% relative humidity (RH). PM concentrations from both types of filters agreed very well with 1-day equilibration, demonstrating that Emfab filters are appropriate for use in measuring PM from residential wood burning appliances in a dilution tunnel and have performance equal to or better than the glass fiber filter media. Agreement between filter media without equilibration was erratic, with PM from glass fiber filter samples varying from slightly less than the Emfab samples to as much as 2.8 times higher. Some of the glass fiber filters lost substantial mass with equilibration, with the highest percent loss at lower filter mass loadings. Mass loss for Emfab samples was a small percentage of the mass and very consistent across the range of mass loadings. Taken together, these results may indicate water uptake on the glass fiber media that is readily removed with 1-day equilibration at moderate RH conditions.

Implications: EPA regulations now allow the use of either glass fiber or Teflon filter media for wood appliance PM emission testing. Teflon filter media minimizes the potential for acid-gas PM artifacts on glass fiber filters; this is important as EPA moves toward the use of locally sourced cordwood for testing that may have higher sulfur content. This work demonstrates that the use of Teflon-coated glass fiber filters can give similar PM measurement results to glass fiber filters after 1 day of equilibration. With no equilibration, measured PM from glass fiber filters was usually higher than from Teflon-coated glass fiber filters.     

Loss of particle nitrate from teflon sampling filters: effects on measured gravimetric mass in California and in the IMPROVE network

The extent of mass loss on Teflon filters caused by ammonium nitrate volatilization can be a substantial fraction of the measured particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) or 10 microm (PM10) mass and depends on where and when it was collected. There is no straightforward method to correct for the mass loss using routine monitoring data. In southern California during the California Acid Deposition Monitoring Program, 30-40% of the gravimetric PM2.5 mass was lost during summer daytime. Lower mass losses occurred at more remote locations. The estimated potential mass loss in the Interagency Monitoring of Protected Visual Environments network was consistent with the measured loss observed in California. The biased mass measurement implies that use of Federal Reference Method data for fine particles may lead to control strategies that are biased toward sources of fugitive dust, other primary particle emission sources, and stable secondary particles (e.g., sulfates). This analysis clearly supports the need for speciated analysis of samples collected in a manner that preserves volatile species. Finally, although there is loss of volatile nitrate (NO3-) from Teflon filters during sampling, the NO3- remaining after collection is quite stable. We found little loss of NO3- from Teflon filters after 2 hr under vacuum and 1 min of heating by a cyclotron proton beam.     

An evaluation of mass absorption cross-section for optical carbon analysis on Teflon filter media

Black carbon (BC) or elemental carbon (EC) is a by-product of incomplete fuel combustion, and contributes adversely to human health, visibility, and climate impacts. Previous studies have examined nondestructive techniques for particle light attenuation measurements on Teflon® filters to estimate BC. The incorporation of an inline Magee Scientific OT21 transmissometer into the MTL AH-225 robotic weighing system provides the opportunity to perform optical transmission measurements on Teflon filters at the same time as the gravimetric mass measurement. In this study, we characterize the performance of the inline OT21, and apply it to determine the mass absorption cross-section (MAC) of PM_2.5 BC across the United States. We analyzed 5393 archived Teflon® filters from the Chemical Speciation Network (CSN) collected during 2010–2011 and determined MAC by comparing light attenuation on Teflon® filters to corresponding thermal EC on quartz-fiber filters. Results demonstrated the importance of the initial transmission (I₀) value used in light attenuation calculations. While light transmission varied greatly within filter lots, the average I₀ of filter blanks during the sampling period provided an estimate for archived filters. For newly collected samples, it is recommended that filter-specific I₀ measurements be made (i.e., same filter before sample collection). The estimated MAC ranged from 6.9 to 9.4 m²/g and varied by region and season across the United States, indicating that using a default value may lead to under- or overestimated BC concentrations. An analysis of the chemical composition of these samples indicated good correlation with EC for samples with higher EC content as a fraction of total PM_2.5 mass, while the presence of light-scattering species such as crustal elements impacted the correlation affecting the MAC estimate. Overall, the method is demonstrated to be a quick, cost-effective approach to estimate BC from archived and newly sampled Teflon® filters by combining both gravimetric and BC measurements.

Implications: Robotic optical analysis is a valid, cost-effective means to obtain a vast amount of BC data from archived and current routine filters. A tailored mass absorption cross-section by region and season is necessary for a more representative estimate of BC. Initial light transmission measurements play an important role due to the variability in blank filter transmission. Combining gravimetric mass and BC analysis on a single Teflon® filter reduces costs for monitoring agencies and maximizes data collection.     

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.     

Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples

The replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event.

Implications: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.     

Field validation of a semi-continuous method for aerosol black carbon (aethalometer) and temporal patterns of summertime hourly black carbon measurements in southwestern PA

Two methods for measuring aerosol elemental carbon (EC) are compared. Three-hour integrated carbon samples were collected on quartz filters during the summer of 1990 in Uniontown, PA, primarily during episodes of elevated particulate pollution levels. These samples were analyzed for EC and organic carbon (OC) using a thermo/optical reflectance (TOR) method. Aerosol black carbon (BC) was measured using an Aethalometer, a semi-continuous optical absorption method. The optical attenuation factor for ambient BC was supplied by the instrument manufacturer. Three-hour average concentrations were calculated from the semi-continuous BC measurements to temporally match the EC/OC integrated quartz filter samples. BC and EC concentrations are highly correlated over the study period (R²=0.925). The regression equation is BC (μg m^-3)=0.95 (±0.04) EC−0.2 (±0.4). The means of 3 h average measurements for EC and BC are 2.3 and 2.0 μg m^-3, respectively, average concentrations of EC and BC ranged from 0.6 to 9.4 and 0.5 to 9.0 μg m^-3 respectively. TOR OC and EC concentrations were not highly correlated (R²=0.22). The mean OC/EC ratio was 1.85.The 10-week Aethalometer hourly dataset was analyzed for daily and weekly temporal patterns. A strong diurnal BC pattern was observed, with peaks occurring between 7 a.m. and 9 a.m. local time. This is consistent with the increase in emissions from ground level combustion sources in the morning, coupled with poor dispersion before daytime vertical mixing is established. There was also some indication of a day-of-week effect on BC concentrations, attributed to activity of local ground level anthropogenic sources. Comparison of BC concentrations with co-located measurements of coefficient of haze in a separate field study in Philadelphia, PA, during the summer of 1992 showed good correlation between the two measurements (R²=0.82).     

The Magnitude of Bias in the Measurement of PM25 Arising from Volatilization of Particulate Nitrate from Teflon Filters

ABSTRACT

Because the Federal Reference Method for PM₂₅ specifies the collection of ambient particles on Teflon filters, we have examined the loss of a known volatile species, particulate nitrate, during sampling. Data are presented from two studies in southern California for which parallel samples were collected by different methods. Differences in collected nitrate are modeled using an evaporation model based on the work of Zhang and McMurry. The average nitrate obtained from sampling with Teflon filters was 28% lower on average than that measured by denuded nylon filters. In contrast, cascade impactor samples were within 5% of the denuded nylon filter on average. A simple model is presented that accounts for the particulate nitrate loss from Teflon filters either by scavenging nitric acid and ammonia in the sampler inlet or by heating the filter substrate during sampling. The observed magnitude of loss is explained by any of the following situations: (1) 100% nitric acid and ammonia vapor loss in the inlet, (2) 5 °C heating of the filter substrate above ambient temperature during sampling, or (3) a combination of these factors, such as 50% vapor loss in the inlet and 3 °C heating of the filter.     

Analysis of aerosol particles and coarse particulate matter concentrations in Chillán, Chile, 2001-2003

Daily particle samples were collected in Chillán, Chile, at six urban locations from September 1, 2001, through September 30, 2003. Aerosol samples were collected using monitors equipped with a Sierra Andersen 246-b cyclone inlet on Teflon filters. Average concentrations of coarse particulate matter (PM10) for the 2001-2003 period ranged from 43.4 microg/m3 to 81.8 microg/m3 across the six sites. Annual PM10 concentration levels exceeded the European Union concentration limits. Mean PM10 levels during the cold season (April through September) were more than twice as high as those observed in the warm season (October through March). Average contributions to PM10 from organic matter, soil dust, nitrate (NO3-), elemental carbon, ammonium (NH4+), and sulfate (SO4(2-)) were 31%, 27%, 11%, 8%, 7%, and 5%, respectively. The chemical analyses indicated that carbonaceous substances were the most abundant components of PM10 in cold months, whereas crustal material was the most abundant component of PM10 during warm months. Higher concentration levels were observed in the downtown area suggesting a clear anthropogenic origin, whereas in the rural sites the source was mainly natural, such as resuspended soil dust associated with traffic on unpaved roads and agricultural activities.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.     

Identification of haze-creating sources from fine particulate matter in Dhaka aerosol using carbon fractions

Fine particulate matter (PM_2.5) samples were simultaneously collected on Teflon and quartz filters between February 2010 and February 2011 at an urban monitoring site (CAMS2) in Dhaka, Bangladesh. The samples were collected using AirMetrics MiniVol samplers. The samples on Teflon filters were analyzed for their elemental composition by PIXE and PESA. Particulate carbon on quartz filters was analyzed using the IMPROVE thermal optical reflectance (TOR) method that divides carbon into four organic carbons (OC), pyrolized organic carbon (OP), and three elemental carbon (EC) fractions. The data were analyzed by positive matrix factorization using the PMF2 program. Initially, only total OC and total EC were included in the analysis and five sources, including road dust, sea salt and Zn, soil dust, motor vehicles, and brick kilns, were obtained. In the second analysis, the eight carbon fractions (OC1, OC2, OC3, OC4, OP, EC1, EC2, EC3) were included in order to ascertain whether additional source information could be extracted from the data. In this case, it is possible to identify more sources than with only total OC and EC. The motor vehicle source was separated into gasoline and diesel emissions and a fugitive Pb source was identified. Brick kilns contribute 7.9 μg/m³ and 6.0 μg/m³ of OC and EC, respectively, to the fine particulate matter based on the two results. From the estimated mass extinction coefficients and the apportioned source contributions, soil dust, brick kiln, diesel, gasoline, and the Pb sources were found to contribute most strongly to visibility degradation, particularly in the winter.

Implications: Fine particle concentrations in Dhaka, Bangladesh, are very high and cause significant degradation of urban visibility. This work shows that using carbon fraction data from the IMPROVE OC/EC protocol provides improved source apportionment. Soil dust, brick kiln, diesel, gasoline, and the Pb sources contribute strongly to haze, particularly in the winter.     

Measurement of black carbon (BC) by an optical method and a thermal-optical method: Intercomparison for four sites

Comparison of black carbon (BC) measurements obtained by two methods was performed for aerosols samples collected on Whatman 41 (W-41) filters, using an optical method (Magee Scientific Optical Transmissometer Model OT-21) and a thermal-optical method (Sunset Laboratory Thermal-optical analyzer). Samples were collected from four sites: Albany (a small urban site, NY), Antalya (coastal site, Turkey), Whiteface Mountain (remote site, NY) and Mayville (rural site, NY). At Albany, comparison between the two methods showed excellent agreement; a least-squares regression line yielded a slope of 1.02, and r² = 0.88. Similar comparisons at Antalya (slope of 1.02, r² = 0.5) and Whiteface Mountain (slope of 0.92 and r² = 0.58) also gave very good relationship. At Mayville, the relationship between the two methods yielded somewhat lower regression: a slope of 0.75, and r² = 0.44. The data from the four locations, when plotted together, yielded an excellent agreement: a slope of 0.91, and r² of 0.84. Based on our measurements, it appears that optical measurement using the OT-21 can be successfully applied to determination of BC in W-41 filters. However, because of the variability in the chemical composition of BC aerosol at different locations, it is suggested that the calibration of OT-21 when using W-41 filters should be performed with a statistically significant numbers of samples for specific sites.     

Personal exposure to fine particulate matter in elderly subjects: relation between personal, indoor, and outdoor concentrations

The time-series correlation between ambient levels, indoor levels, and personal exposure to PM2.5 was assessed in panels of elderly subjects with cardiovascular disease in Amsterdam, the Netherlands, and Helsinki, Finland. Subjects were followed for 6 months with biweekly clinical visits. Each subject's indoor and personal exposure to PM2.5 was measured biweekly, during the 24-hr period preceding the clinical visits. Outdoor PM2.5 concentrations were measured at fixed sites. The absorption coefficients of all PM2.5 filters were measured as a marker for elemental carbon (EC). Regression analyses were conducted for each subject separately, and the distribution of the individual regression and correlation coefficients was investigated. Personal, indoor, and ambient concentrations were highly correlated within subjects over time. Median Pearson's R between personal and outdoor PM2.5 was 0.79 in Amsterdam and 0.76 in Helsinki. For absorption, these values were 0.93 and 0.81 for Amsterdam and Helsinki, respectively. The findings of this study provide further support for using fixed-site measurements as a measure of exposure to PM2.5 in epidemiological time-series studies.     

Loading effect correction for real-time aethalometer measurements of fresh diesel soot

In this study, a correction was developed for the aethalometer to measure real-time black carbon (BC) concentrations in an environment dominated by fresh diesel soot. The relationship between the actual mass-specific absorption coefficient for BC and the BC-dependent attenuation coefficients was determined from experiments conducted in a diesel exposure chamber that provided constant concentrations of fine particulate matter (PM; PM(2.5); PM < 2.5 microm in aerodynamic diameter) from diesel exhaust. The aethalometer reported BC concentrations decreasing with time from 48.1 to 31.5 microg m(-3) when exposed to constant PM(2.5) concentrations of 55 +/- 1 microg m(-3) and b(scat) = 95 +/- 3 Mm(-1) from diesel exhaust. This apparent decrease in reported light-absorbing PM concentration was used to derive a correction K(ATN) for loading of strong light-absorbing particles onto or into the aethalometer filter tape, which was a function of attenuation of light at 880 nm by the embedded particles.     

Loss of Particle Nitrate from Teflon Sampling Filters: Effects on Measured Gravimetric Mass in California and in the IMPROVE Network

Abstract

The extent of mass loss on Teflon filters caused by ammonium nitrate volatilization can be a substantial fraction of the measured particulate matter with an aerodynamic diameter less than 2.5 μm (PM_2.5)or 10 μm (PM₁₀) mass and depends on where and when it was collected. There is no straightforward method to correct for the mass loss using routine monitoring data. In southern California during the California Acid Deposition Monitoring Program, 30-40% of the gravimetric PM_2.5 mass was lost during summer daytime. Lower mass losses occurred at more remote locations. The estimated potential mass loss in the Interagency Monitoring of Protected Visual Environments network was consistent with the measured loss observed in California. The biased mass measurement implies that use of Federal Reference Method data for fine particles may lead to control strategies that are biased toward sources of fugitive dust, other primary particle emission sources, and stable secondary particles (e.g., sulfates). This analysis clearly supports the need for speciated analysis of samples collected in a manner that preserves volatile species. Finally, although there is loss of volatile nitrate (NO₃ ^?) from Teflon filters during sampling, the NO₃ ^? remaining after collection is quite stable. We found little loss of NO₃ ^? from Teflon filters after 2 hr under vacuum and 1 min of heating by a cyclotron proton beam.     

Feasibility of soil dust source apportionment by the pyrolysis-gas chromatography/mass spectrometry method

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM10) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with approximately 0.4 mg of PM10 dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 degrees C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 degrees C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/ optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.     

Particle size distributions and elemental composition of atmospheric particulate matter in southern Italy

Three 2-wk seasonal field campaigns were performed in 2003 and 2004 at a sampling site on the southern Tyrrhenian coast of Italy with the aim to investigate the dynamics and characteristics of particle-bound pollutants in the Mediterranean area. Fine (PM(2.5)) and coarse particulate matter (PM(10-2.5)) size fractions were collected by a manual dichotomous sampler on 37-mm Teflon filters over a 24-hr sampling period. On average, 70% of the total PM(10) (PM(2.5) + PM(10-2.5)) mass was associated with the coarse fraction and 30% with the fine fraction during the three campaigns. The ambient concentrations of Pb, Ni, Cr, Zn, Mn, V, Cd, Fe, Cu, Ca, and Mg associated with both size fractions were determined by atomic absorption spectrometry. Ambient concentrations showed differences in their absolute value, ranging from few ng x m(-3) to microg x m(-3), as well as in their variability within the PM(2.5) and PM(10-2.5) size fractions. PM(10) levels were well below the European Union (EU) limit value during the study period with the exception of three events during the first campaign (fall) and five events during the third campaign (spring). Two main sources were identified as the major contributors including mineral dust, transported from North Africa, and sea spray from the Tyrrhenian Sea. Comparing the results with backward trajectories, calculated using the Hybrid Single-Particle Lagrangian Integrated Trajectory Model (HYSPLIT) and Total Ozone Mapping Spectrometer-National Aeronautics and Space Administration (TOMS-NASA) maps, it was observed that in central and eastern Europe, the Tyrrhenian Sea and North Africa were the major emission source regions that affected the temporal variations and daily averages of PM(2.5) and PM(10-2.5) concentrations.     

Boiler briquette coal versus raw coal: Part I--Stack gas emissions

Stack gas emissions were characterized for a steam-generating boiler commonly used in China. The boiler was tested when fired with a newly formulated boiler briquette coal (BB-coal) and when fired with conventional raw coal (R-coal). The stack gas emissions were analyzed to determine emission rates and emission factors and to develop chemical source profiles. A dilution source sampling system was used to collect PM on both Teflon membrane filters and quartz fiber filters. The Teflon filters were analyzed gravimetrically for PM10 and PM2.5 mass concentrations and by X-ray fluorescence (XRF) for trace elements. The quartz fiber filters were analyzed for organic carbon (OC) and elemental carbon (EC) using a thermal/optical reflectance technique. Sulfur dioxide was measured using the standard wet chemistry method. Carbon monoxide was measured using an Orsat combustion analyzer. The emission rates of the R-coal combustion (in kg/hr), determined using the measured stack gas concentrations and the stack gas emission rates, were 0.74 for PM10, 0.38 for PM2.5, 20.7 for SO2, and 6.8 for CO, while those of the BB-coal combustion were 0.95 for PM10, 0.30 for PM2.5, 7.5 for SO2, and 5.3 for CO. The fuel-mass-based emission factors (in g/kg) of the R-coal, determined using the emission rates and the fuel burn rates, were 1.68 for PM10, 0.87 for PM2.5, 46.7 for SO2, and 15 for CO, while those of the BB-coal were 2.51 for PM10, 0.79 for PM2.5, 19.9 for SO2, and 14 for CO. The task-based emission factors (in g/ton steam generated) of the R-coal, determined using the fuel-mass-based emission factors and the coal/steam conversion factors, were 0.23 for PM10, 0.12 for PM2.5, 6.4 for SO2, and 2.0 for CO, while those of the BB-coal were 0.30 for PM10, 0.094 for PM2.5, 2.4 for SO2, and 1.7 for CO. PM10 and PM2.5 elemental compositions are also presented for both types of coal tested in the study.     

Effect of VOC loading on the ozone removal efficiency of activated carbon filters

Activated carbon (AC) filters are used widely in air cleaning to remove volatile organic compounds (VOCs) and ozone (O(3)). This paper investigates the O(3) removal efficiency of AC filters after previous exposure to VOCs. Filter performance was tested using coconut shell AC and two common indoor VOCs, toluene and d-limonene, representing low and high reactivities with O(3). AC dosed with low, medium and high loadings (28-100% of capacity) of VOCs were exposed to humidified and ozonated air. O(3) breakthrough curves were measured, from which O(3) removal capacity and parameters of the Elovich chemisorption equation were determined. VOC-loaded filters were less efficient at removing O(3) and had different breakthrough behavior than unloaded filters. After 80 h of exposure, VOC-loaded AC samples exhibited 75-95% of the O(3) removal capacity of unloaded samples. O(3) breakthrough and removal capacity were not strongly influenced by the VOC-loading rate. Toluene-loaded filters showed rapid O(3) breakthrough due to poisoning of the AC, while pseudo-poisoning (initially higher O(3) adsorption rates that rapidly decrease) is suggested for limonene-loaded filters. Overall, VOC loadings provide an overall reduction in chemisorption rates, a modest reduction in O(3) removal capacity, and sometimes dramatic changes in breakthrough behavior, important considerations in filter applications in environments where both O(3) and VOCs are present.     

Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.