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.     

Artifact particulate sulfate and nitrate formation on filter media

Laboratory and atmospheric sampling studies were performed to evaluate glass fiber, quartz and Teflon filters for their abilities to form artifact particulate sulfate and nitrate with SO₂and HNO₃, respectively. The glass fiber filters were the types employed by the U.S. EPA as well as many State and local agencies for hi-vol particle sampling in the period 1977–1982.In 24-h laboratory trials, the sulfate artifact with the glass fiber filters ranged from 32 to 59μgcm⁻² (8–15μg m⁻³ at simulated hi-vol sampling rates). With the exception of Whatman QMA, the ‘quartz’ and Teflon filters collected very low levels of SO₂. At nitric acid dosages representative of those in atmospheric sampling, the glass fiber filters retained > 94% of the HNO₃; the ‘quartz’ filters, 33 to > 99%; and Teflon filters, <2 % of the HNO₃,. Because of competing acidic species in ambient air, these represent upper limits to the values to be expected in atmospheric sampling. Over the dosage range evaluated, artifact particulate sulfate and nitrate formation on ‘quartz’ and Teflon filters were highly correlated to each other from one filter to another, with a 4:1 molar ratio of nitrate: sulfate.The sulfate artifact in atmospheric sampling with Pallflex ‘quartz’ filters was consistent with laboratory findings while the nitrate artifact was much lower than predicted.     

Efficiency of filter sampling for arsenic in the atmosphere

The efficiency of hi-vol samplers with glass fiber filters for collection of atmospheric arsenic was assessed by parallel sampling with a technique able to retain both particle and gas-phase arsenic trioxide. Sampling was done adjacent to the Kennecott copper smelter in Magna, Utah during the winter of 1981. Arsenic concentrations up to 0.2 μg m⁻³ (24-h average) were observed. The hi-vol sampler retained, on average, 83% of the As retained by the parallel sampler, implying at least 17% As penetration through the glass fiber filter. Laboratory evaluations of the sampling and analytical method are also presented.     

Planning A State-Wide Air Pollution Advisory Service

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM₁₀ Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon® impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22°C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at ?70°C to ?80°C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set. Results indicate that the sample handling variations and collection period variables had no significant effect on recovery of organics or mutagens. However, a filter type difference was observed. The sonication extraction of organics and mutagens was significantly greater for TIGF filters than for glass fiber or quartz. Results from a second phase of study indicated differences in extracted organics and mutagens for these filter types.     

High-volume Impactor for Sampling Fine and Coarse Particles

Final design, calibration, and field testing have been completed for a new 1.13 m³/min (40 cfm) High-volume Virtual Impactor (HVVI). Field tests have demonstrated that the new classifier/collector works well as an accessory to the existing PM10 Size Selective Inlet high-volume samplers. The HVVI provides two fractions of PM10 mass, both of which are collected by filtration. The fine fraction (0-2.5 μm aero. dia.) Is collected on the standard 20.3 × 25.4 cm (8- × 10-in) high-volume filter; the coarse fraction (2.5-10 μm aero. dia.) is collected on a 5.1 × 15.2 cm (2- × 6-in) filter. Coarse flow through the receiver tubes is limited to 0.057 m³/min (2 cfm), 5 percent of the total flow.

The operating pressure drop across the HVVI stages Is sufficiently high to make changes In pressure across the collection filters Insignificant. The HVVI filter holder assembly facilitates loading/ unloading samples in the laboratory, thus eliminating damage due to handling filters in the field. Size separation characteristics of the HVVI agree well with those for the 16.7 L/min commercially available dichotomous sampler with the 50 percent effectiveness (cut-point) occurring at 2.5 μm. Applying laboratory-determined particle losses to the typical ambient particle mass size distribution described In Federal Register 49, 40 CFR, Part 53, Table D-3, the HVVI fine fraction total mass loss is less than 0.8 percent for liquid particles and less than 0.1 percent for solid particles; coarse fraction total mass loss is less than 2.5 percent for liquid particles, and less than 0.2 percent for solid particles.     

Sampling of carbonaceous particles in the atmosphere—II

A laboratory study was conducted to test the ability of various sorbents to remove vapor-phase atmospheric carbonaceous materials otherwise retained by sorption on quartz filters, a ‘positive artifact’ in sampling atmospheric particulate C. A dual quartz filter strategy, in which the C recovered from the after-filter is used to correct for the positive artifact, was also assessed. Sorbents such as activated Al₂O₃ and quartz fiber can reduce by up to 60% the positive artifact in sampling at 20 ℓ min⁻ with 47-mm Pallflex 2500 QAO quartz filters. On the assumption, defended herein, that a quartz fiber profilier was unlikely to influence the ratio of C retained by sorption on downstream tandem quartz filters, the dual filter strategy permitted correction for this positive artifact within, on average, 12%. Conclusions from an initial study suggesting extensive loss by volatilization of previously collected particulate C are reassessed.     

Simultaneous Sampling of Gas- and Aerosol-Phase TDI with a Triple Filter System

Abstract

A new triple filter system sampler/model is proposed for the precise and accurate simultaneous sampling and determination of gas- and aerosol-phase 2,4-toluene diisocyanate (TDI). The system consists of two front Teflon filters for sampling aerosol-phase TDI and a final coated glass fiber filter to collect gas-phase TDI. The aerosol-phase TDI is collected on the first Teflon filter, while the second Teflon filter is used to estimate gaseous TDI adsorbed by the first. According to the gas adsorption test of two Teflon filters in series, the TDI gas adsorption fraction of the two filters is almost the same. Results of the evaporation test using pure TDI aerosols collected on the Teflon filter show that significant evaporation of the compound does not occur during sampling. These two findings allow the use of a model to estimate accurate gasand aerosol-phase TDI concentrations. The comparison test with an annular denuder shows that the triple filter system can minimize the TDI sampling bias between the dual filter and the annular denuder systems.     

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)     

SARA Title III,Section 313 —Looking Ahead

This study performed a workplace evaluation of emission control using available air sampling filters and characterized the emitted particles captured in filters. Characterized particles were contained in the exhaust gas released from carbon nanotube (CNT) synthesis using chemical vapor deposition (CVD). Emitted nanoparticles were collected on grids to be analyzed using transmission electron microscopy (TEM). CNT clusters in the exhaust gas were collected on filters for investigation. Three types of filters, including Nalgene surfactant-free cellulose acetate (SFCA), Pall A/E glass fiber, and Whatman QMA quartz filters, were evaluated as emission control measures, and particles deposited in the filters were characterized using scanning transmission electron microscopy (STEM) to further understand the nature of particles emitted from this CNT production. STEM analysis for collected particles on filters found that particles deposited on filter fibers had a similar morphology on all three filters, that is, hydrophobic agglomerates forming circular beaded clusters on hydrophilic filter fibers on the collecting side of the filter. CNT agglomerates were found trapped underneath the filter surface. The particle agglomerates consisted mostly of elemental carbon regardless of the shapes. Most particles were trapped in filters and no particles were found in the exhaust downstream from A/E and quartz filters, while a few nanometer-sized and submicrometer-sized individual particles and filament agglomerates were found downstream from the SFCA filter. The number concentration of particles with diameters from 5 nm to 20 µm was measured while collecting particles on grids at the exhaust piping. Total number concentration was reduced from an average of 88,500 to 700 particle/cm³ for the lowest found for all filters used. Overall, the quartz filter showed the most consistent and highest particle reduction control, and exhaust particles containing nanotubes were successfully collected and trapped inside this filter.

Implications: As concern for the toxicity of engineered nanoparticles grows, there is a need to characterize emission from carbon nanotube synthesis processes and to investigate methods to prevent their environmental release. At this time, the particles emitted from synthesis were not well characterized when collected on filters, and limited information was available about filter performance to such emission. This field study used readily available sampling filters to collect nanoparticles from the exhaust gas of a carbon nanotube furnace. New agglomerates were found on filters from such emitted particles, and the performance of using the filters studied was encouraging in terms of capturing emissions from carbon nanotube synthesis.     

Effects of acid-washing filter treatment on quantification of aerosol organic compounds

The tests of standard mixtures and four sets of atmospheric particulate samples showed that an acid-wash (AW) pretreatment of fluorocarbon-coated glass fiber filters prior to aerosol sampling enhanced the quantifiable organic compounds for more than 29% (or 66 ng m⁻³); in particular, 47–273 ng m⁻³ (21–366%) more water-soluble organic compounds (WSOCs) were measured. When the acid-pretreated filters were employed, up to nine more organic species were measured in the individual daily samples. Because the acid pretreatment reduced the metal contaminants in the glass fiber filters, using the AW filters for aerosol sampling allows higher extraction recoveries of organic compounds. Since the fingerprinting compounds were more accurately determined when the aerosol samples were collected on the AW filters, better assessment of emission sources and toxicity of air pollutants can be obtained.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.     

High Volume Sampling: Errors Incurred during Passive Sample Exposure Periods

The current Federal EPA reference method for the determination of total suspended particulate matter (TSP) in the atmosphere is the high volume method (hi-vol).¹ The hi-vol sampler is normally operated for a 24 hr period by drawing air through an 8 X 10 in. glass fiber filter at an air sampling flow rate of between 40-60 cfm. TSP samples are presently collected in this manner every 6th day (61 samples/year). Results are used to determine compliance with existing National Primary Ambient Air Quality Standards for TSP (i.e., 260 µg/m³, maximum 24 hr average, not to be exceeded more than once a year; 75 µg/m³, annual geometric mean). However, when the sampling frequency is diminished to only 61 out of a possible 365 measurements each year, the degree of certainty associated with meeting these air quality standards is also decreased.^2,3 This partial sampling schedule also introduces other sampling errors. One such error caused by the exposure of the collection filter both prior and subsequent to the desired sampling day is the subject of the following discussion.     

Polycyclic aromatic hydrocarbons in Los Angeles air from samples collected on teflon,glass and quartz filters

Levels of ambient particulate polycyclic aromatic hydrocarbons (PAH) have been measured at seven locations in the Los Angeles area using quartz, glass and Teflon filters operated in parallel at the same sampling face velocities. Daytime and night-time samples (12 h each) were collected during summer and winter. Thirteen PAH, from anthracene to coronene, were quantitated in these samples. The measured concentrations (e.g. mean values of 1.62, 0.97, 0.64 and 3.6 ng m⁻³ for pyrene, chrysene, benzo(a)pyrene and coronene, respectively) suggest that PAH levels in Los Angeles air have not significantly changed during the last decade. For all but one PAH, concentrations measured on glass and quartz filters were lower in 85–90 % of the total number of observations than those measured in samples collected on Teflon filters. On average, glass/Teflon and quartz/Teflon ratios ranged from 0.25 for pyrene to 0.80 for coronene. These observations are of concern since virtually all information available to date concerning airborne PAH has been derived from samples collected on glass filters.     

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.     

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.     

Simultaneous sampling of gas- and aerosol-phase TDI with a triple filter system

A new triple filter system sampler/model is proposed for the precise and accurate simultaneous sampling and determination of gas- and aerosol-phase 2,4-toluene diisocyanate (TDI). The system consists of two front Teflon filters for sampling aerosol-phase TDI and a final coated glass fiber filter to collect gas-phase TDI. The aerosol-phase TDI is collected on the first Teflon filter, while the second Teflon filter is used to estimate gaseous TDI adsorbed by the first. According to the gas adsorption test of two Teflon filters in series, the TDI gas adsorption fraction of the two filters is almost the same. Results of the evaporation test using pure TDI aerosols collected on the Teflon filter show that significant evaporation of the compound does not occur during sampling. These two findings allow the use of a model to estimate accurate gas- and aerosol-phase TDI concentrations. The comparison test with an annular denuder shows that the triple filter system can minimize the TDI sampling bias between the dual filter and the annular denuder systems.     

Flexibility of X-Ray Emission Spectrography as Adapted to Microanalysis of Air Pollutants

Methods previously published by this laboratory for analyzing thin dust coatings of airborne particulates have been further evaluated, as applied to vast air pollution surveys. It was demonstrated that choice of glass fiber filters adapted to high-volume samplers restricts the analysis to a limited number of elements, such as lead. More flexibility and versatility are attained through the use of organic membrane filters mounted in small plastic monitors which permit multi-elemental analysis at least as accurately as with other popular but time-consuming techniques. These qualities of speed and accuracy allow shorter intervals of sampling which are normally required for better statistical assessment of broad air pollution surveys. Sensitivity of the technique reaches a value close to 0.05 μg/m³, while time of analysis required is about five minutes per element after receipt of the sample.     

The Recovery of Selenious Acid Aerosols on Glass Fiber Filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, In the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols In our study were formed by volatilizing selenium dioxide (≈3 mg) Into a stream of moist ambient air (relative humidity, >50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonlcally extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 ± 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 ± 6 percent.