Laboratory characterization of modified tapered element oscillating microbalance samplers

Laboratory tests with generated aerosols were conducted to test the efficacy of two recent design modifications to the well-established tapered element oscillating microbalance (TEOM) continuous particulate matter (PM) mass monitor. The two systems tested were the sample equilibration system-equipped TEOM monitor operating at 30 degrees C, which uses a Nafion dryer as part of the sample inlet, and the differential TEOM monitor, which adds a switched electrostatic precipitator and uses a self-referencing algorithm to determine "true PM mass." Test aerosols included ammonium sulfate, ammonium nitrate, sodium chloride, copper (II) sulfate, and mixed aerosols. Aerosols were generated with an atomizer or a vibrating orifice generator and were equilibrated in a 450-L slow flow chamber before being sampled. Relative humidity in the chamber was varied between 10 and 90%, and step changes in humidity were executed while generating aerosol to test the response of the instruments. The sample equilibration system-equipped TEOM monitor does reduce, but not totally eliminate, the sensitivity of the TEOM mass monitor to changes in humidity. The differential TEOM monitor gives every indication of being a very robust technique for the continuous real-time measurement of ambient aerosol mass, even in the presence of semi-volatile particles and condensable gases.     

Continuous determination of fine particulate matter mass in the Salt Lake City Environmental Monitoring project: a comparison of real-time and conventional TEOM monitor results

Fine particulate matter (PM2.5) mass was determined on a continuous basis at the Salt Lake City Environmental Protection Agency Environmental Monitoring for Public Awareness and Community Tracking monitoring site in Salt Lake City, UT, using three different monitoring techniques. Hourly averaged PM2.5 mass data were collected during two sampling periods (summer 2000 and winter 2002) using a real-time total ambient mass sampler (RAMS), sample equilibration system (SES)-tapered element oscillating microbalance (TEOM), and conventional TEOM monitor. This paper compares the results obtained from the various monitoring systems, which differ in their treatment of semivolatile material (SVM; particle-bound water, semivolatile ammonium nitrate, and semivolatile organic compounds). PM2.5 mass results obtained by the RAMS were consistently higher than those obtained by the SES-TEOM and conventional TEOM monitors because of the RAMS ability to measure semivolatile ammonium nitrate and semivolatile organic material but not particle-bound water. The SES-TEOM monitoring system was able to account for an average of 28% of the SVM, whereas the conventional TEOM monitor loses essentially all of the SVM from the single filter during sampling. Occasional mass readings by the various TEOM monitors that are higher than RAMS results may reflect particle-bound water, which, under some conditions, is measured by the TEOM but not the RAMS.     

Development of a Sample Equilibration System for the TEOM Continuous PM Monitor

ABSTRACT

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile.

The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM₁₀ equivalent method (EQPM-1090-079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

While using this monitor, it is desirable to maintain as low an operating temperature as practical and to remove unwanted particle-bound water. A new sample equilibration system (SES) has been developed to allow conditioning of the PM sample stream to a lower humidity and temperature level. The SES incorporates a special low-particle-loss Nafion dryer. This paper discusses the configuration and theory of the SES. Performance results include high time-resolved PM_2.5 data comparison between a 30 °C sample stream TEOM monitor with SES and a standard 50 °C TEOM monitor. In addition, 24-hr integrated data are compared with data collected using an EPA PM_2.5 Federal Reference Method (FRM)-type sampler. The SES is a significant development because it can be applied easily to existing TEOM monitors.     

APCA Financial Statements for FY 1979-80

The U.S. Environmental Protection Agency (EPA) has proposed a new secondary standard based on visibility in urban areas. The proposed standard will be based on light extinction, calculated from 24-hr averaged measurements. It would be desirable to base the standard on a shorter averaging time to better represent human perception of visibility. This could be accomplished by either an estimation of extinction from semicontinuous particulate matter (PM) data or direct measurement of scattering and absorption. To this end we have compared 1-hr measurements of fine plus coarse particulate scattering using a nephelometer, along with an estimate of absorption from aethalometer measurements. The study took place in Lindon, UT, during February and March 2012. The nephelometer measurements were corrected for coarse particle scattering and compared to the Filter Dynamic Measurement System (FDMS) tapered element oscillating microbalance monitor (TEOM) PM_2.5 measurements. The two measurements agreed with a mass scattering coefficient of 3.3 ± 0.3 m²/g at relative humidity below 80%. However, at higher humidity, the nephelometer gave higher scattering results due to water absorbed by ammonium nitrate and ammonium sulfate in the particles. This particle-associated water is not measured by the FDMS TEOM. The FDMS TEOM data could be corrected for this difference using appropriate IMPROVE protocols if the particle composition is known. However, a better approach may be to use a particle measurement system that allows for semicontinuous measurements but also measures particle bound water. Data are presented from a 2003 study in Rubidoux, CA, showing how this could be accomplished using a Grimm model 1100 aerosol spectrometer or comparable instrument.

Implications: Visibility is currently based on 24-hr averaged PM mass and composition. A metric that captures diurnal changes would better represent human perception. Furthermore, if the PM measurement included aerosol bound water, this would negate the need to know particulate composition and relative humidity (RH), which is currently used to estimate visibility. Methods are outlined that could accomplish both of these objectives based on use of a PM monitor that includes aerosol-bound water. It is recommended that these techniques, coupled with appropriate measurements of light scattering and absorption by aerosols, be evaluated for potential use in the visibility based secondary standard.     

Long-term field characterization of tapered element oscillating microbalance and modified tapered element oscillating microbalance samplers in urban and rural New York State locations

Long-term field comparisons of continuous and integrated filter measurements of mass concentrations of particulate matter (PM) with an aerodynamic diameter less than or equal to 2.5 microm (PM2.5) were performed at rural and urban sites in New York State. Two versions of the continuous tapered element oscillating microbalance (TEOM) mass monitor are deployed at each site, in addition to Federal Reference Method filter samplers. Data are grouped into monthly averages to retain and demonstrate seasonal differences. Strong seasonal dependence is observed-the TEOM monitors with the heated sensors are biased systematically low with respect to the Federal Reference Method measurements during the cold season. For the rural site, the average bias for the sample equilibration system (SES)-equipped and standard TEOM monitors is 14 and 24%, respectively. At this location, the TEOM monitor measurements were biased low for all 34 months. For the urban site, the average bias for the SES and standard TEOM monitors is 8 and 18%, respectively. At this location, the TEOM monitor measurements are as likely to be biased high as low during the warm-season months. The hour averaged data from the two versions of the TEOM monitor are also compared, and also indicate that the SES-equipped version of the TEOM monitor captures 7-11% more PM2.5 mass at these locations.     

Development and evaluation of a continuous coarse (PM10-PM2.5) particle monitor

In this paper, we describe the development and laboratory and field evaluation of a continuous coarse (2.5-10 microm) particle mass (PM) monitor that can provide reliable measurements of the coarse mass (CM) concentrations in time intervals as short as 5-10 min. The operating principle of the monitor is based on enriching CM concentrations by a factor of approximately 25 by means of a 2.5-microm cut point round nozzle virtual impactor while maintaining fine mass (FM)--that is, the mass of PM2.5 at ambient concentrations. The aerosol mixture is subsequently drawn through a standard tapered element oscillating microbalance (TEOM), the response of which is dominated by the contributions of the CM, due to concentration enrichment. Findings from the field study ascertain that a TEOM coupled with a PM10 inlet followed by a 2.5-microm cut point round nozzle virtual impactor can be used successfully for continuous CM concentration measurements. The average concentration-enriched CM concentrations measured by the TEOM were 26-27 times higher than those measured by the time-integrated PM10 samplers [the micro-orifice uniform deposit impactor (MOUDI) and the Partisol] and were highly correlated. CM concentrations measured by the concentration-enriched TEOM were independent of the ambient FM-to-CM concentration ratio, due to the decrease in ambient coarse particle mass median diameter with an increasing FM-to-CM concentration ratio. Finally, our results illustrate one of the main problems associated with the use of real impactors to sample particles at relative humidity (RH) values less than 40%. While PM10 concentrations obtained by means of the MOUDI and Partisol were in excellent agreement, CM concentrations measured by the MOUDI were low by 20%, and FM concentrations were high by a factor of 5, together suggesting particle bounce at low RH.     

Long-Term Field Characterization of Tapered Element Oscillating Microbalance and Modified Tapered Element Oscillating Microbalance Samplers in Urban and Rural New York State Locations

Abstract

Long-term field comparisons of continuous and integrated filter measurements of mass concentrations of par-ticulate matter (PM) with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) were performed at rural and urban sites in New York State. Two versions of the continuous tapered element oscillating microbalance (TEOM) mass monitor are deployed at each site, in addition to Federal Reference Method filter samplers. Data are grouped into monthly averages to retain and demonstrate seasonal differences. Strong seasonal dependence is observed—the TEOM monitors with the heated sensors are biased systematically low with respect to the Federal Reference Method measurements during the cold season. For the rural site, the average bias for the sample equilibration system (SES)-equipped and standard TEOM monitors is 14 and 24%, respectively. At this location, the TEOM monitor measurements were biased low for all 34 months. For the urban site, the average bias for the SES and standard TEOM monitors is 8 and 18%, respectively. At this location, the TEOM monitor measurements are as likely to be biased high as low during the warm-season months. The hour averaged data from the two versions of the TEOM monitor are also compared, and also indicate that the SES-equipped version of the TEOM monitor captures 7-11% more PM_2.5 mass at these locations.     

Comparison of real-time instruments used to monitor airborne particulate matter

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakersfield, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 microns (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of approximately 3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

Development of a sample equilibration system for the TEOM continuous PM monitor

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile. The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM10 equivalent method (EQPM-1090079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.     

Characterization of chemical species in atmospheric aerosols in a metropolitan basin

Ambient PM10 aerosol samples were collected from Taiwan's Taichung metropolitan basin between October 1997 and January 1998, and their chemical characteristics studied. The average mass concentration of PM10 was 109.0 +/- 54.1 microg/m3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. On average, 64% of the PM10 was made up of fine particles. During PM10 episodes, average wind speed was 0.7 m/s and relative humidity was high, 83% on average, probably giving rise to stagnation of air pollutants and their entrapment close to the surface. With relative humidity < 70%, NO3-, NH4+, SO4(2-), carbonaceous materials, and PM10 mass showed high correlation with maximum hourly average ozone (O3M). Variation in atmospheric humidity may affect the gas-to-particle interactions of S and N species. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.     

Field evaluation of particulate matter measurements using tapered element oscillating microbalance in a layer house

The tapered element oscillating microbalance (TEOM) is one type of continuous ambient particulate matter (PM) monitor. Adsorption and desorption of moisture and semivolatile species may cause positive or negative artifacts in TEOM PM mass measurement. The objective of this field study was to investigate possible uncertainties associated with TEOM measurements in the poultry operation environment. For comparisons of TEOM with filter-based gravimetric method, four instruments (TEOM-PM10, low-volume PM10 sampler TEOM-PM2.5, and PM2.5 speciation sampler) were collocated and tested inside a poultry house for PM2.5 and PM10 (PM with aerodynamic equivalent diameter < or =2.5 and < or =10 microm, respectively) measurements. Fifteen sets of 24-hr PM10 concentrations and 13 sets of 24-hr PM2.5 measurements were obtained. Results indicate that compared with filter-based gravimetric method, TEOM gave significantly lower values of both PM10 and PM2.5 mass concentrations. For PM10, the average ratio of TEOM to the gravimetric method was 0.936. For PM2.5, the average ratio of TEOM to the gravimetric method was 0.738. Particulate matter in the poultry houses possibly contains semivolatile compounds and moisture due to high levels of relative humidity (RH) and gas pollutants. The internal heating mechanism of the TEOM may cause losses in mass through volatilization. To investigate the effects of TEOM settings on concentration measurements, the heaters of two identical TEOMs were set at 50 degrees C, 30 degrees C, or no heating at all. They were collocated and tested for total suspended particle (TSP), PM10, and PM25 measurements in layer house for 6 weeks. For all TSR PM10, and PM2.5 measurements, the internal TEOM temperature setting had a significant effect (P < 0.05). Significantly higher PM mass concentrations were measured at lower temperature settings. The effects of environmental (i.e., temperature, RH, NH3 and CO2 concentrations) and instrumental (i.e., filter loading and noise) parameters on PM measurements were also assessed using regression analysis.     

Air quality measurements from the Fresno Supersite

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM2.5, PM10, and coarse (PM10 minus PM2.5) mass; 2) PM2.5 SO4(-2), NO3-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to approximately 10 microns; 4) criteria pollutant gases (O3, CO, NOx); 5) reactive gases (NO2, NOy, HNO3, peroxyacetyl nitrate [PAN], NH3); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM2.5 and PM10 mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM2.5 chemical speciation with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM10 and PM2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

Comparison of Real-Time Instruments Used To Monitor Airborne Particulate Matter

ABSTRACT

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakers-field, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 μm (PM_2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of ~3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH₄NO₃ observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM_2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

Development and Evaluation of a Continuous Coarse (PM10–PM25) Particle Monitor

ABSTRACT

In this paper, we describe the development and laboratory and field evaluation of a continuous coarse (2.5-10 um) particle mass (PM) monitor that can provide reliable measurements of the coarse mass (CM) concentrations in time intervals as short as 5-10 min. The operating principle of the monitor is based on enriching CM concentrations by a factor of ~25 by means of a 2.5-um cut point round nozzle virtual impactor while maintaining fine mass (FM)—that is, the mass of PM_{2 5} at ambient concentrations. The aerosol mixture is subsequently drawn through a standard tapered element oscillating microbalance (TEOM), the response of which is dominated by the contributions of the CM, due to concentration enrichment. Findings from the field study ascertain that a TEOM coupled with a PM₁₀ inlet followed by a 2.5-um cut point round nozzle virtual impactor can be used successfully for continuous CM concentration measurements. The average concentration-enriched CM concentrations measured by the TEOM were 26-27 times higher than those measured by the time-integrated PM₁₀ samplers [the micro-orifice uniform deposit     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system

The effect of relative humidity (RH) on aerosol formation by the semi-volatile oxidation products of the α-pinene/O₃ system has been comprehensively studied. Experiments were performed in the presence of ammonium sulfate (aqueous, dry), ammonium bisulfate seed (aqueous, dry), and aqueous calcium chloride seed aerosols to ascertain their effect on the partitioning of the oxidation products. The yield of organic aerosol varies little with RH, and is not affected by the presence of dry inorganic salt aerosols. Aqueous salt aerosols reduce the yield of organic aerosol compared to that under seed-free or dry seed conditions. The degree of reduction is electrolyte dependent, with aqueous ammonium sulfate leading to the largest reduction and aqueous calcium chloride the smallest. Hygroscopic growth of the organic aerosol from <2% to 85% RH was also monitored, and could be satisfactorily represented as the sum of the individual contributions of the organic and inorganic fractions. The implications of the growth factor measurements for concentration/activity relationships of the condensed phase organic material (assuming a liquid solution) was explored. The formation of the organic aerosol was investigated using a simple two component model, and also one including the 12 product compounds identified in a previous study. The experimental results for <2% and 50% RH (without salt seed aerosols) could be satisfactorily predicted. However, the aqueous salt seed aerosols are predicted to increase the overall yield due to the dissolution of the organic compounds into the water associated with the seed aerosol—the opposite effect to that observed. The implications of two distinct phases existing the aerosol phase were investigated.     

Characterization of PM2.5 aerosols dominated by local pollution and Asian dust observed at an urban site in Korea during aerosol characterization experiments (ACE)--Asia Project

Daily fine particulate matter (PM2.5) samples were collected at Gwangju, Korea, during the Aerosol Characterization Experiments (ACE)-Asia Project to determine the chemical properties of PM2.5 originating from local pollution and Asian dust (AD) storms. During the study period, two significant events occurred on April 10-13 and 24-25, 2001, and a minor event occurred on April 19, 2001. Based on air mass transport pathways identified by back-trajectory calculation, the PM2.5 dataset was classified into three types of aerosol populations: local pollution and two AD aerosol types. The two AD types were transported along different pathways. One originated from Gobi desert area in Mongolia, passing through Hunshandake desert in Northern Inner Mongolia, urban and polluted regions of China (AD1), and the other originated in sandy deserts located in the Northeast Inner Mongolia Plateau and then flowed southward through the Korean peninsula (AD2). During the AD2 event, a smoke plume that originated in North Korea was transported to our study site. Mass balance closures show that crustal materials were the most significant species during both AD events, contributing -48% to the PM2.5 mass; sulfate aerosols (19.1%) and organic matter (OM; 24.6%) were the second greatest contributors during the AD1 and AD2 periods, respectively, indicating that aerosol properties were dependent on the transport pathway. The sulfate concentration constituted only 6.4% (4.5 microg/m3) of the AD2 PM2.5 mass. OM was the major chemical species in the local pollution-dominated PM2.5 aerosols, accounting for 28.7% of the measured PM2.5 mass, followed by sulfate (21.4%), nitrate (15%), ammonium (12.8%), elemental carbon (8.9%), and crustal material (6.5%). Together with substantial enhancement of the crustal elements (Mg, Al, K, Ca, Sc, Ti, Mn, Fe, Sr, Zr, Ba, and Ce), higher concentrations of pollution elements (S, V, Ni, Zn, As, Cd, and Pb) were observed during AD1 and AD2 than during the local pollution period, indicating that, in addition to crustal material, the AD dust storms also had a significant influence on anthropogenic elements.     

The measurement of fine particulate semivolatile material in urban aerosols

Ammonium nitrate and semivolatile organic material (SVOM) are significant components of fine particles in urban atmospheres. These components, however, are not properly determined with methods such as the fine particulate matter (PM2.5) Federal Reference Method (FRM) or other single filter samplers because of significant losses of semivolatile material (SVM) from particles collected on the filter during sampling. The R&P tapered element oscillating microbalance (TEOM) monitor also does not measure SVM, because this method heats the sample to remove particle bound water, which also results in evaporation of SVM. Recent advances in monitoring techniques have resulted in samplers for both integrated and continuous measurement of total PM2.5, including the particle concentrator-Brigham Young University organic sampling system (PC-BOSS), the real-time total ambient mass sampler (RAMS), and the R&P filter dynamics measurement system (FDMS) TEOM monitor. Results obtained using these samplers have been compared with those obtained with either a PM2.5 FRM sampler or a TEOM monitor in studies conducted during the past five years. These studies have shown the following: (1) the PC-BOSS, RAMS, and FDMS TEOM are all comparable. Each instrument measures both the nonvolatile material and the SVM. (2) The SVM is not retained on the heated filter of a regular TEOM monitor and is not measured by this sampling technique. (3) Much of the SVM is also lost during sampling from single filter samplers such as the PM2.5 FRM sampler. (4) The amount of SVM lost from single filter samplers can vary from less than one-third of that lost from heated TEOM filters during cold winter conditions to essentially all during warm summer conditions. (5) SVOM can only be reliably collected using an appropriate denuder sampler. (6) A PM2.5 speciation sampler can be easily modified to a denuder sampler with filters that can be analyzed for semivolatile organic carbon (OC), nonvolatile OC, and elemental carbon using existing OC/elemental carbon analytical techniques. The research upon which these statements are based for various urban studies are summarized in this paper.     

New York State urban and rural measurements of continuous PM2.5 mass by FDMS, TEOM, and BAM

Field evaluations and comparisons of continuous fine particulate matter (PM2,5) mass measurement technologies at an urban and a rural site in New York state are performed. The continuous measurement technologies include the filter dynamics measurement system (FDMS) tapered element oscillating microbalance (TEOM) monitor, the stand-alone TEOM monitor (without the FDMS), and the beta attenuation monitor (BAM). These continuous measurement methods are also compared with 24-hr integrated filters collected and analyzed under the Federal Reference Method (FRM) protocol. The measurement sites are New York City (the borough of Queens) and Addison, a rural area of southwestern New York state. New York City data comparisons between the FDMS TEOM, BAM, and FRM are examined for bias and seasonality during a 2-yr period. Data comparisons for the FDMS TEOM and FRM from the Addison location are examined for the same 2-yr period. The BAM and FDMS measurements at Queens are highly correlated with each other and the FRM. The BAM and FDMS are very similar to each other in magnitude, and both are approximately 25% higher than the FRM filter measurements at this site. The FDMS at Addison measures approximately 9% more mass than the FRM. Mass reconstructions using the speciation trends network filter data are examined to provide insight as to the contribution of volatile species of PM2.5 in the FDMS mass measurement and the fraction that is likely lost in the FRM mass measurement. The reconstructed mass at Queens is systematically lower than the FDMS by approximately 10%.     

Evaluation of the RAMS continuous monitor for determination of PM2.5 mass including semi-volatile material in Philadelphia,PA

The real-time ambient mass sampler (RAMS) is a continuous monitor based on particle concentrator, denuder, drier, and tapered element oscillating microbalance (TEOM) monitor technology. It is designed to measure PM2.5 mass, including the semi-volatile species NH4NO3 and semi-volatile organic material, but not to measure PM2.5 water content. The performance of the RAMS in an urban environment with high humidity was evaluated during the July 1999 NARSTO-Northeast Oxidant and Particles Study (NEOPS) intensive study at the Baxter water treatment plant in Philadelphia, PA. The results obtained with the RAMS were compared to mass measurements made with a TEOM monitor and to constructed mass obtained with a Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) sampler designed to determine the chemical composition of fine particles, including the semi-volatile species. An average of 28% of the fine particulate material present during the study was semi-volatile organic material lost from a filter during particle collection, and 1% was NH4NO3 that was also lost from the particles during sampling. The remaining mass was dominantly nonvolatile (NH4)2SO4 (31%) and organic material (37%), with minor amounts of soot, crustal material, and nonvolatile NH4NO3. Comparison of the RAMS and PC-BOSS results indicated that the RAMS correctly monitored for fine particulate mass, including the semivolatile material. In contrast, the heated filter of the TEOM monitor did not measure the semi-volatile material. The comparison of the RAMS and PC-BOSS data had a precision of +/-4.1 microg/m3 (+/-9.6%). The precision of the RAMS data was limited by the uncertainty in the blank correction for the reversible adsorption of water by the charcoal-impregnated cellulose sorbent filter of the RAMS monitor. The precision of the measurement of fine particulate components by the PC-BOSS was +/-6-8%.