Reduction of the Positive Organic Artifact on Quartz Filters

Quartz fiber filters are routinely used to collect particulate matter for organic analysis. Such collections may be subject to filtration artifacts: enhancement due to the adsorption of gas-phase organic species or diminishment caused by the volatilization of organic particulate matter. The magnitudes of these competing processes are usually difficult to evaluate separately, although significant amounts of organic carbon on second quartz fiber filters (back filters) downstream of the primary sampling filter indicate that these sampling artifacts are present. In an experiment to reduce the enhancement when sampling organic particulate matter, a diffusive denuder consisting of separated layers of quartz fiber filter was used under the hypothesis that it would selectively remove only those gaseous organic species that normally are retained by the filter medium. This denuder reduced the organic carbon on the back filter by more than a factor of four, to levels comparable to those of the filter blank; the organic carbon on the front filter was reduced by the same absolute amount. The conclusion is that a quartz fiber filter denuder nearly eliminates the enhancement artifact.     

High-Volume Diffusion Denuder Sampler for the Routine Monitoring of Fine Particulate Matter: II. Field Evaluation of the PC-BOSS

The high-volume Brigham Young University organic sampling system with a particle concentrator (PC-BOSS) has been field evaluated for the determination of airborne fine particulate matter including semivolatile chemical species during 3 intensive sampling programs in 1997: Tennessee Valley Authority (TVA), Lawrence County, TN; Riverside, CA; and Provo, UT. The PC-BOSS precision was tested using 2 collocated PC-BOSS samplers. In addition, the PC-BOSS results were compared with results from a prototype PM 2.5 U.S. EPA federal reference method (FRM sampler), a filter pack sampler (quartz and charcoal sorbent filters), the BIG BOSS, an annular denuder sampler, and the ChemSpec sampler for the determination of major fine particulate species. Fine particulate mass, sulfate, nitrate, and organic carbonaceous material (OC) determined by 2 PC-BOSS samplers agreed within - 10%. Possibly due to absorption of SO 2 by a quartz filter, the sulfate concentrations determined by the filter pack sampler and the BIG BOSS were higher (by 10 - 3%) than concentrations obtained with the other samplers. No absorption of SO 2 (g) by the quartz filters of the PC-BOSS occurred due to the high efficiency (>99%) of its denuder. The PC-BOSS, annular denuder, and ChemSpec samplers agreed with each other (to within - 0.5 w g/m 3 , - 17%, with no bias) for the determination of fine particulate nitrate concentrations, including volatilization losses. The prototype PM 2.5 FRM sampler collected only particle-retained nonvolatile mass. The mass concentrations determined by the PM 2.5 FRM agreed with those collected by the post-denuder Teflon filters of the PC-BOSS (to within - 1.1 w g/m 3 , - 10%, with no bias). The overall loss of material from particles and the resultant underestimation of the particulate mass concentrations by the PM 2.5 FRM depended on the fine particle composition and the ambient temperature.     

Continuous Measurement of Semivolatile Fine Particulate Mass in Provo,Utah

Ambient particles contain substantial quantities of material that can be lost from the particles during sample collection on a filter, including ammonium nitrate and semivolatile organic compounds. The real-time ambient mass sampler (RAMS) described in this paper has been developed for the accurate continuous monitoring of fine particulate material. The previously published version of the RAMS had significant problems with a variable blank correction. A series of experiments conducted in Provo, UT, during December, 1998, indicated that nitrogen oxides and water were the major contributors to a high morning blank. This blank was minimized by heating the Brigham Young University Organic Sampling System (BOSS) charcoal diffusion denuder and adding multichannel annular denuders coated with triethanolamine (TEA) to remove NO 2 . This new configuration of the RAMS was used to collect samples on 5 consecutive days in Provo, UT. These results were compared to measurements made in both 6 h and 24 h integrated samples using the Particle Concentrator-BOSS (PC-BOSS). An average of 1% of the Provo fine particulate material was present as ammonium nitrate and 15% as semivolatile organic material, which were lost from a filter during sampling for samples collected over 24 h and 6 h average periods. These species were correctly determined by the RAMS.     

Estimating ambient particulate organic carbon concentrations and partitioning using thermal optical measurements and the volatility basis set

We introduce a new method to estimate the mass concentration of particulate organic carbon (POC) collected on quartz filters, demonstrating it using quartz-filter samples collected in greater Pittsburgh. This method combines thermal-optical organic carbon and elemental carbon (OC/EC) analysis and the volatility basis set (VBS) to quantify the mass concentration of semi-volatile POC on the filters. The dataset includes ambient samples collected at a number of sites in both summer and winter as well as samples from a highway tunnel. As a reference we use the two-filter bare-Quartz minus Quartz-Behind-Teflon (Q-QBT) approach to estimate the adsorbed gaseous fraction of organic carbon (OC), finding a substantial fraction in both the gas and particle phases under all conditions. In the new method we use OC fractions measured during different temperature stages of the OC/EC analysis for the single bare-quartz (BQ) filter in combination with partitioning theory to predict the volatility distributions of the measured OC, which we describe with the VBS. The effective volatility bins are consistent for data from both ambient samples and primary organic aerosol (POA)-enriched tunnel samples. Consequently, with the VBS model and total OC fractions measured over different heating stages, particulate OC can be determined by using the BQ filter alone. This method can thus be applied to all quartz filter-based OC/EC analyses to estimate the POC concentration without using backup filters.

© 2016 American Association for Aerosol Research     

Evaluation of the Performance of Annular Denuder Samplers

Two annular denuder samplers were evaluated for the determination of atmospheric nitric acid, SO 2 , and fine particulate sulfate and nitrate. One, the University Research Glassware (URG) sampler, used an elutriator-impactor to remove coarse particles prior to sampling the aerosol through the denuder sections for the removal of acid gases. The second, the Rupprecht and Patashnick (R&P) ChemSpec, removes the acid gases in diffusion denuder sections and then removes coarse particles prior to the collection of fine particles. Possible sampling artifacts examined included the removal of HNO 3 (g) by the inlet of the URG sampler before the collection of this gas-phase species by the diffusion denuder, resulting in the underestimation of HNO 3 (g) and the deposition of some coarse particles in the R&P denuders prior to the removal of these larger particles, and the collection of fine particles on a filter, resulting in the overestimation of HNO 3 (g) and SO 2 (g). Samples were collected in Riverside, CA, Bakersfield, CA, and Provo, UT. Both sampling artifacts were found to be present. However, the effect on the determination of HNO 3 (g) by the URG sampler and on the determination of particulate-phase sulfate and nitrate by the R&P ChemSpec were both small, on the order of a few tenths of a microgram per cubic meter.     

Sampling artifacts in denuders during phase partitioning measurements of semi-volatile organic compounds

The partitioning of semi-volatile organic compounds (SVOCs) between the gas and particle phase plays an important role in understanding the formation of secondary organic aerosols (SOAs) in the atmosphere. There are uncertainties and problems associated with measurements during the simultaneous sampling of both gas and particle phases. In recent studies, diffusion denuders have been used for separate sampling of gas and particle phases of organic compounds. The removal of the gaseous species in the denuder distorts the gas–particle equilibrium and leads to the dissociation of the particulate phase during the sampling. This phenomenon is particularly true for volatile organic species and leads to significant error in determining gas-to-particle phase partitioning of organic aerosols due to underestimation of the particle phase. In this study, a model for simultaneous gas diffusion and aerosol decomposition/evaporation in the parallel plate denuder was developed to investigate the effects of sampling artifacts on gas–particle partitioning measurements of SVOCs. The model equations were cast into dimensionless form for generalization, and the effects of governing dimensionless groups on the denuder sampling artifacts were evaluated by performing a sensitivity analysis. Also, regression correlations for denuder sampling artifacts as the function of governing dimensionless groups were obtained. It was observed that the sampling of SVOCs could result in substantial particulate phase loss due to evaporation in the denuder, resulting in significant errors in the phase partitioning measurements. Also, the operating conditions for the denuder, so that the denuder sampling artifacts lie within tolerable limits, were evaluated.

Copyright © 2018 American Association for Aerosol Research     

Use of the RAMS to Measure Semivolatile Fine Particulate Matter at Riverside and Bakersfield,California

Fine particles in urban environments contain substantial quantities of material that can be lost from the particles during sample collection on a filter. This materials include ammonium nitrate and semivolatile organic compounds. Methods for the accurate determination of these species in integrated samples have been developed using diffusion denuder samplers. However, it is often desirable to determine fine particulate matter on a continuous basis. The real-time ambient mass sampler (RAMS), a continuous monitor using diffusion denuder and tapered element oscillating microbalance (TEOM) technologies, has been evaluated by monitoring fine particulate species in Riverside, CA during August and September, 1997, and in Bakersfield, CA during February and March, 1998. The results are compared to measurements made in 1 h integrated samples in Riverside and in 2 h integrated samples in Bakersfield with a diffusion denuder sampler, the particle concentrator-Brigham Young University organic sampling system (PC-BOSS). An average of 5% of the Riverside fine particulate matter was present as semivolatile ammonium nitrate and 33% as semivolatile organic material that was lost from a PC-BOSS filter during sampling. In Bakersfield the fraction of PM 2.5 lost from a PC-BOSS filter averaged 3% as semivolatile ammonium nitrate and 15% as semivolatile organic material. These species were correctly determined by the RAMS. However, the usefulness of the RAMS as a continuous monitor is limited by the blank variability with the design presented here.     

Effect of Semivolatile Material on PM 2.5 Measurement by the PM 2.5 Federal Reference Method Sampler at Bakersfield,California

The chemical composition of fine particulate material was determined for samples collected in Bakersfield, CA, during February-March, 1998 using several diffusion denuder samplers, including the PC-BOSS, which measures both semivolatile fine particulate nitrate and organic material. An average of 56% of the fine particulate carbonaceous material was lost from the filters of the Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS). A comparable amount of fine particulate semivolatile organic material was also lost from collected particles with single filter samplers, such as the PM 2.5 Federal Reference Method. The fraction of nitrate lost from collected particles was a function of temperature and humidity, with the biggest effect being due to temperature. The fraction of nitrate lost was comparable for conventional annular denuder samplers and the PM 2.5 FRM, averaging 33%. The nitrate loss from particles for the PC-BOSS was smaller, averaging 11%, possibly due to the concentration of particulate material prior to collection with this sampler. The loss of nitrate and semivolatile organic material during sample collection resulted in the PM 2.5 FRM sampler giving PM 2.5 mass that was an average of 30% (7.3 w g/m 3 ) lower than the true value and different from the true value from negligible to 20 w g/m 3 .     

Thermal/optical reflectance equivalent organic and elemental carbon determined from federal reference and equivalent method fine particulate matter samples using Fourier transform infrared spectrometry

A fine particulate matter (PM_2.5) monitoring network of filter-based federal reference methods and federal equivalent methods (FRM/FEMs) is used to assess local ambient air quality by comparison to National Ambient Air Quality Standards (NAAQS) at about 750 sites across the continental United States. Currently, FRM samplers utilize polytetrafluoroethylene (PTFE) filters to gravimetrically determine PM_2.5 mass concentrations. At most of these sites, sample composition is unavailable. In this study, we present the proof-of-principle estimation of the carbonaceous fraction of fine aerosols on FRM filters using a nondestructive Fourier transform infrared (FT-IR) method. Previously, a quantitative FT-IR method accurately determined thermal/optical reflectance equivalent organic and elemental carbon (a.k.a., FT-IR organic carbon [OC] and elemental carbon [EC]) on filters collected from the chemical speciation network (CSN). Given the similar configuration of FRM and CSN aerosol samplers, OC and EC were directly determined on FRM filters on a mass-per-filter-area basis using CSN calibrations developed from nine sites during 2013 that have collocated CSN and FRM samplers. FRM OC and EC predictions were found to be comparable to those of the CSN on most figures of merit (e.g., R²) when the type of PTFE filter used for aerosol collection was the same in both networks. Although prediction accuracy remained unaffected, FT-IR OC and EC determined on filters produced by a different manufacturer show marginally increased prediction errors suggesting that PTFE filter type influences extending CSN calibrations to FRM samples. Overall, these findings suggest that quantifying FT-IR OC and EC on FRM samples appears feasible.

© 2018 American Association for Aerosol Research     

PM 2.5 Semivolatile Organic Material at Riverside,California: Implications for the PM 2.5 Federal Reference Method Sampler

Particulate semivolatile organic compounds can be lost from particles on a filter during sample collection and storage, resulting in a negative artifact. Gas-phase organic compounds can adsorb on a quartz filter to cause a positive artifact. A sampler (Particle Concentrator-Brigham Young University Organic Sampling System: PC-BOSS) has been developed that uses a cyclone and virtual impactor (particle concentrator) inlet to provide a concentrated stream of 0.1-2.5 w m particles. The concentrator is followed by a BOSS diffusion denuder to remove interfering gas-phase compounds and filter packs to collect particles, including any semivolatile species lost from the particles during sampling. The sampler can be used for the determination of both fine particulate nitrate and semivolatile organic material without significant "positive" or "negative" sampling artifacts. The sampler has been evaluated at Riverside, CA. The collection efficiency of the particle concentrator was stable, being 65% - 2% and 61% - 1% for particulate sulfate and soot, respectively. Results obtained with the PC-BOSS for the determination of PM 2.5 organic material including semivolatile components agreed with results from a BOSS, but not with filter pack results. The precision of the PC-BOSS results for particulate organic material was - 8%. An average of 50% of the particulate organic material was lost from the particles during sampling for all samplers used. As a result of the loss of semivolatile organic material and nitrate, the PM 2.5 Federal Reference Method sampler underdetermined PM 2.5 by an average of 34% with the under measurement varying from negligible to 27 w g/m 3 , averaging 8.9 w g/m 3 .     

Determination of the Fractional Efficiencies of Fibrous Filter Media By Optical In Situ Measurements

ABSTRACT

An experimental setup is introduced to determine the fractional efficiency of fibrous filters. The device includes two optical particle counters for the in situ measurement of the particle flux and size upstream and downstream of a test filter. The simultaneous measurement in the raw and clean gas by a counting method allows a rapid determination of the fractional efficiencies of various filter media within a few minutes. In the first experiments performed with different aerosols (latex spheres, bacterial aerosol, limestone dust) the apparatus proved to be a reliable instrument for the investigation of the collection behaviour of fibrous filters influenced by various parameters.

The fractional efficiency yields more information about the filter performance, i.e., respirable fraction, collection minimum, particle bouncing off etc., than the total collection efficiency. Thus it is possible to compare different filter media of the same or different filter class and determine their optimum operational conditions.     

Gas/Particle Partition Measurements of PAH at Hazelrigg,U.K.

During September and October, 1998, the new Integrated Organic Gas and Particle Sampler (IOGAPS), was operated at Hazelrigg, UK, the field measurement station of the University of Lancaster. Gas/particle partition ratios of twenty-two 2–5 ring PAH were determined using both the IOGAPS (in which the gas phase is collected before the particle phase) and a low flow sampler which utilized the traditional filter-sorbent geometry. For compounds of intermediate volatility, less partitioning to the gas phase was observed when the denuder was used. The denuder (8- channel, 60 cm, 16.7 L min^?1 air sampling rate) trapped small amounts of several non-volatile PAH. This result is consistent with particle diffusion losses of 5 to 10% for particles less than 0.05 μm under the flow conditions in the denuder. The 60-cm denuder was probably longer than necessary for the flow rate used. During the sampling, both glass fiber and Teflon-coated glass fiber filters were used. Without a denuder in front of a glass fiber filter, the fine particulate mass (PM 2.5) measurements showed a major positive bias that has been attributed to adsorption of gases by the filter. Teflon-coated glass fiber filters were not subject to this artifact problem, and equal masses were collected on filters from the denuded and non-denuded air flows.     

Influence of volatilization from mainstream tobacco smoke particles on the gas-particle distribution in annular denuders

The influence of volatilization from mainstream tobacco smoke particles in annular denuders on the gas-particle distribution was investigated by using multiple annular denuders coupled with a filter pack method (multiple-AD-FP method) under low flow volume conditions (1.05 and 1.65 L/min). Smoking experiments and model experiments using poly styrene latex (PSL) particles and generated gases were conducted to measure the particle loss ratio and gas collection efficiency in the denuders. In this research, we focused on the influence of XAD-4 slurry concentrations and particle volatility including tobacco smoke from a cigarette and vapor products on the volatilization from particles in the denuders, and have proposed a measurement method for considering volatilization. Our experimental results showed that volatilization depends on the particle volatility, targeted components, denuder length, particle concentration, and adsorbent amount, thereby suggesting the importance of selecting the proper measurement conditions and taking volatilization into account, so as to evaluate the appropriate gas-particle distribution. The gas-phase nicotine ratio obtained from calculating the volatilization rate in the multiple-AD-FP method agreed with previous research. This means that the calculation method was appropriate for the evaluation of gas-particle distribution. Furthermore, the gas-particle ratio determined through the multiple-AD-FP method was compared to that determined through a filter-impinger method that uses a glass fiber filter. The results revealed that most of the gases in the filter-impinger method were not collected in the impinger due to the condensation of gases on the surface of the filter fibers and collected particles.

© 2017 American Association for Aerosol Research     

Atmospheric Carbonaceous Species Measurement Methods Comparison Study: General Motors Results

The General Motors Research Laboratories participated in both the field sampling and round-robin portions of the Carbonaceous Species Intercomparison study that was held in Glendora, CA, during the summer of 1986. Five samplers were operated during the field study. The average particulate elemental carbon (EC) concentrations determined from the five samplers agreed to within 12%. Large differences were observed in the concentrations of particulate organic carbon (OC) determined from the five samplers. Some of the differences are attributed to losses of OC from the filters due to volatilization during the collection period. The amount of volatilization varies with the length of the sampling time and the filter face velocity. In addition, the adsorption of gas-phase organic compounds caused a significant positive interference in the determination of OC. Our OC and EC results for the round-robin samples were compared to the values obtained by the other participating laboratories. The average ratio of our results to the mean of the other laboratories was 0.97 for all the OC data and 1.23 for EC from all but the ambient wood-burning and organic aerosol samples. The ratios for the latter samples were 1.9 or greater. It is concluded that EC can be collected and analyzed with high precision; however, the accuracy of the measurements is unknown since standards for EC in atmospheric particulate do not exist.     

Comparison of Sampling Methods for Carbonaceous Aerosols in Ambient Air

Measurement methods for fine particle carbon were compared under field sampling conditions. Sampling methods included filtration, impaction, and adsorption-corrected filtration. Systems were operated side-by-side for nine consecutive days in the Los Angeles Basin. Analytical methods were compared separately. For organic carbon and total carbon, ambient measurements showed greater variability than could be accounted for by differences in analytical methods, and these differences are attributed to sampling methodology. The highest reported concentrations were obtained by quartz filter sampling; the lowest were from the sum of the impactor stages (excluding the quartz afterfilters). Positive artifact from the adsorption of gaseous vapors on quartz fiber filters was significant. However, correction for vapor adsorption by subtraction of the carbon value on the second of two filters in series did not completely eliminate the dependence of the apparent total aerosol carbon concentration on filter face velocity or sample duration     

Development and Laboratory Performance Evaluation of a Personal Multipollutant Sampler for Simultaneous Measurements of Particulate and Gaseous Pollutants

A personal multipollutant sampler has been developed. This sampler can be used for measuring exposures to particulate matter and criteria gases. The system uses asingle personalsampling pump that operates at a flow rate of 5.2 l/min. The basic unit consists of two impaction-based samplers for PM_2.5 and PM₁₀ attached to a single elutriator. Two mini PM_2.5 samplers are also attached to the elutriator for organic carbon (OC), elemental carbon (EC), sulfate, and nitrate measurements. For the collection of nitrate and sulfate, the minisampler includes a miniaturized honeycomb glass denuder that is placed upstream of the filter to remove nitric acid and sulfur dioxide and to minimize artifacts. Two passive samplers can also be attached to the elutriator for measurements of gaseous copollutants such as O₃, SO₂, and NO₂. The performance of the multipollutant sampler was examined through a series of laboratory chamber tests. The results showed a good agreement between the multipollutant sampler and the reference methods. The overall sampler performance demonstrates its suitability for personal exposure assessment studies.     

Analysis of Carbon Particle Deposition on Teflon Filters Using Fourier Transform Infrared Spectroscopy

Fourier transform infrared absorption measurements of particulate elemental carbon are compared with results obtained using a thermal combustion method of analysis. Ambient air samples were collected on Teflon and quartz filters on each day during the sampling study. The quartz filters were analyzed for elemental and organic carbon using a thermal combustion method of analysis. The Teflon filters were analyzed for elemental carbon by infrared transmission in the region 650–666 cm^?1. Good correlation was found between the infrared absorbance on the Teflon filters and the elemental carbon determined from analysis of the quartz filters. Calibration methods for the infrared technique are discussed