A Re-Examination of Ambient Air Ozone Monitor Interferences

Abstract

Attaining the National Ambient Air Quality Standard (NAAQS) for ozone (O₃) could cost billions of dollars nationwide. Attainment of the NAAQS is judged on O₃ measurements made by the Federal Reference Method (FRM), ethylene chemiluminescence, or a Federal Equivalent Method (FEM), predominantly ultraviolet (UV) absorption. Starting in the 1980s, FRM monitors were replaced by FEMs so that today virtually all monitoring in the United States uses the UV methodology. This report summarizes a laboratory and collocated ambient air monitoring study of interferences in O₃ monitors. Potential interferences examined in the laboratory included water vapor, mercury, o-nitrophenol, naphthalene, p-tolualdehyde, and mixed reaction products from smog chamber simulations of urban atmospheric photochemistry. UV absorption O₃ monitors modi?ed for humidity equilibration were also collocated with UV FEM O₃ monitors at six sites in Houston, TX, during the 2007 summer O₃ season. The results suggest that humidity and interfering species can positively bias (overestimate) O₃ measured by FEM monitors used to determine compliance with the O₃ standards. The results also suggest that humidity equilibration can mitigate this bias.     

Potential interference bias in ozone standard compliance monitoring

The U.S. Environmental Protection Agency has established a federal reference method (FRM) for ozone (O3) and allowed for designation of federal equivalent methods (FEMs). However, the ethylene-chemiluminescence FRM for O3 has been replaced by the UV photometric FEM by most state and local monitoring agencies because of its relative ease of operation. Accumulating evidence indicates that the FEM is prone to bias under the hot, humid, and stagnant conditions conducive to high O3 formation. This bias may lead to overreporting hourly O3 concentrations by as much as 20-40 ppb. Measurement bias is caused by contamination of the O3 scrubber, a problem that is not detected by dry air calibration. An adequate wet test has not been codified, although a procedure has been proposed for agency consideration. This paper includes documentation of laboratory tests quantifying specific interferant responses, collocated ambient FRM/FEM monitoring results, and smog chamber comparisons of the FRM and FEMs with alternative scrubber designs. As the numbers of reports on monitor interferences have grown, interested parties have called for agency recognition and correction of these biases.     

Nonlinear regression adjustments of multiple continuous monitoring methods produce effective characterization of short-term fine particulate matter

This study comprehensively characterizes hourly fine particulate matter (PM(2.5)) concentrations measured via a tapered element oscillating microbalance (TEOM), beta-gauge, and nephelometer from four different monitoring sites in U.S. Environment Protection Agency (EPA) Region 5 (in U.S. states Illinois, Michigan, and Wisconsin) and compares them to the Federal Reference Method (FRM). Hourly characterization uses time series and autocorrelation. Hourly data are compared with FRM by averaging across 24-hr sampling periods and modeling against respective daily FRM concentrations. Modeling uses traditional two-variable linear least-squares regression as well as innovative nonlinear regression involving additional meteorological variables such as temperature and humidity. The TEOM shows a relationship with season and temperature, linear correlation as low as 0.7924 and nonlinear model correlation as high as 0.9370 when modeled with temperature. The beta-gauge shows no relationship with season or meteorological variables. It exhibits a linear correlation as low as 0.8505 with the FRM and a nonlinear model correlation as high as 0.9339 when modeled with humidity. The nephelometer shows no relationship with season or temperature but a strong relationship with humidity is observed. A linear correlation as low as 0.3050 and a nonlinear model correlation as high as 0.9508 is observed when modeled with humidity. Nonlinear models have higher correlation than linear models applied to the same dataset. This correlation difference is not always substantial, which may introduce a tradeoff between simplicity of model and degree of statistical association. This project shows that continuous monitor technology produces valid PM(2.5) characterization, with at least partial accounting for variations in concentration from gravimetric reference monitors once appropriate nonlinear adjustments are applied. Although only one regression technically meets new EPA National Ambient Air Quality Standards (NAAQS) Federal Equivalent Method (FEM) correlation coefficient criteria, several others are extremely close, showing optimistic potential for use of this nonlinear adjustment model in garnering EPA NAAQS FEM approval for continuous PM(2.5) sampling methods.     

A Simple Methodology for the Determination of Back Trajectories

Abstract

This study comprehensively characterizes hourly fine particulate matter (PM_2.5) concentrations measured via a tapered element oscillating microbalance (TEOM), β-gauge, and nephelometer from four different monitoring sites in U.S. Environment Protection Agency (EPA) Region 5 (in U.S. states Illinois, Michigan, and Wisconsin) and compares them to the Federal Reference Method (FRM). Hourly characterization uses time series and autocorrelation. Hourly data are compared with FRM by averaging across 24-hr sampling periods and modeling against respective daily FRM concentrations. Modeling uses traditional two-variable linear least-squares regression as well as innovative nonlinear regression involving additional meteorological variables such as temperature and humidity. The TEOM shows a relationship with season and temperature, linear correlation as low as 0.7924 and nonlinear model correlation as high as 0.9370 when modeled with temperature. The β-gauge shows no relationship with season or meteorological variables. It exhibits a linear correlation as low as 0.8505 with the FRM and a nonlinear model correlation as high as 0.9339 when modeled with humidity. The nephelometer shows no relationship with season or temperature but a strong relationship with humidity is observed. A linear correlation as low as 0.3050 and a nonlinear model correlation as high as 0.9508 is observed when modeled with humidity. Nonlinear models have higher correlation than linear models applied to the same dataset. This correlation difference is not always substantial, which may introduce a tradeoff between simplicity of model and degree of statistical association. This project shows that continuous monitor technology produces valid PM_2.5 characterization, with at least partial accounting for variations in concentration from gravimetric reference monitors once appropriate nonlinear adjustments are applied. Although only one regression technically meets new EPA National Ambient Air Quality Standards (NAAQS) Federal Equivalent Method (FEM) correlation coefficient criteria, several others are extremely close, showing optimistic potential for use of this nonlinear adjustment model in garnering EPA NAAQS FEM approval for continuous PM_2.5 sampling methods.     

Potential Interference Bias in Ozone Standard Compliance Monitoring

Abstract

The U.S. Environmental Protection Agency has established a federal reference method (FRM) for ozone (O₃) and allowed for designation of federal equivalent methods (FEMs). However, the ethylene‐chemiluminescence FRM for O₃ has been replaced by the UV photometric FEM by most state and local monitoring agencies because of its relative ease of operation. Accumulating evidence indicates that the FEM is prone to bias under the hot, humid, and stagnant conditions conducive to high O₃ formation. This bias may lead to overreporting hourly O₃ concentrations by as much as 20–40 ppb. Measurement bias is caused by contamination of the O₃ scrubber, a problem that is not detected by dry air calibration. An adequate wet test has not been codified, although a procedure has been proposed for agency consideration. This paper includes documentation of laboratory tests quantifying specific interferant responses, collocated ambient FRM/FEM monitoring results, and smog chamber comparisons of the FRM and FEMs with alternative scrubber designs. As the numbers of reports on monitor interferences have grown, interested parties have called for agency recognition and correction of these biases.     

Evaluation and comparison of continuous fine particulate matter monitors for measurement of ambient aerosols

To provide a scientific basis for the selection and use of continuous monitors for exposure and/or health effects studies, and for compliance and episode measurements at strategic locations in the State of New Jersey, we evaluated the performance of seven continuous fine particulate matter (PM2.5) monitors in the present study. Gravimetric samplers, as reference methods, were collocated with realtime instruments in both laboratory and field tests. The results of intercomparison of real-time monitors showed that the two nephelometers used in this study correlated extremely well (r2 approximately 0.97), and two tapered element oscillating monitors (TEOM 1400 and TEOM filter dynamics measurement system [FDMS]) correlated well (r2 > 0.85), whereas two beta gauges displayed a weaker correlation (r2 < 0.6). During a summertime controlled (laboratory) evaluation, the measurements made with the gravimetric method correlated well with the 24-hr integrated measurements made with the real-time monitors. The SidePak nephelometer overestimated the particle concentration by a factor of approximately 3.4 compared with the gravimetric method. During a summertime field evaluation, the TEOM FDMS monitor reported approximately 30% higher mass concentration than the Federal Reference Method (FRM); and the difference could be explained by the loss of semi-volatile materials from the FRM sampler. Results also demonstrated that 24-hr average PM2.5 mass concentrations measured by beta gauges and TEOM (50 degrees C) in winter correlated well with the integrated gravimetric method. Seasonal differences were observed in the performance of the TEOM (50 degrees C) monitor in measuring the particle mass attributed to the higher semi-volatile material loss in the winter weather. In applying the realtime particulate matter monitoring data into Air Quality Index (AQI) reporting, the Conroy method and the 8-hr end-hour average method were both found to be suitable.     

Collocated comparisons of continuous and filter-based PM2.5 measurements at Fort McMurray,Alberta, Canada

Collocated comparisons for three PM_2.5 monitors were conducted from June 2011 to May 2013 at an air monitoring station in the residential area of Fort McMurray, Alberta, Canada, a city located in the Athabasca Oil Sands Region. Extremely cold winters (down to approximately ?40°C) coupled with low PM_2.5 concentrations present a challenge for continuous measurements. Both the tapered element oscillating microbalance (TEOM), operated at 40°C (i.e., TEOM₄₀), and Synchronized Hybrid Ambient Real-time Particulate (SHARP, a Federal Equivalent Method [FEM]), were compared with a Partisol PM_2.5 U.S. Federal Reference Method (FRM) sampler. While hourly TEOM₄₀ PM_2.5 were consistently ~20–50% lower than that of SHARP, no statistically significant differences were found between the 24-hr averages for FRM and SHARP. Orthogonal regression (OR) equations derived from FRM and TEOM₄₀ were used to adjust the TEOM₄₀ (i.e., TEOM_adj) and improve its agreement with FRM, particularly for the cold season. The 12-year-long hourly TEOM_adj measurements from 1999 to 2011 based on the OR equations between SHARP and TEOM₄₀ were derived from the 2-year (2011–2013) collocated measurements. The trend analysis combining both TEOM_adj and SHARP measurements showed a statistically significant decrease in PM_2.5 concentrations with a seasonal slope of ?0.15 μg m^?3 yr^?1 from 1999 to 2014.Implications: Consistency in PM_2.5 measurements are needed for trend analysis. Collocated comparison among the three PM_2.5 monitors demonstrated the difference between FRM and TEOM, as well as between SHARP and TEOM. The orthogonal regressions equations can be applied to correct historical TEOM data to examine long-term trends within the network.     

Improving the correlations of ambient tapered element oscillating microbalance PM2.5 data and SHARP 5030 Federal Equivalent Method in Ontario: A multiple linear regression analysis

Tapered element oscillating microbalances equipped with sample equilibration system (TEOM-SES) used by the province of Ontario for the ambient monitoring of PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 µm) in its air quality index (AQI) network were collocated with the Synchronized Hybrid Ambient Real-time Particulate monitor (SHARP 5030) at two monitoring sites for a period spanning approximately 2 years to determine the similarities and differences between the measurement outputs of both instrumental systems. Due mainly to mass loss observed with the TEOM-SES in cooler months, the province has recently switched its PM_2.5 instrumentation at all stations in its monitoring network from the TEOM-SES to the SHARP 5030, which has the U.S. Environmental Protection Agency (EPA) Federal Equivalent Method (FEM) Class III designation. Thus, it has become imperative to develop corrections for historical and future TEOM measurements for the purpose of making them more agreeable to the new FEM method. This work details the authors’ multiple linear regression analyses (MLRAs) of particulate matter data from both instrumental monitors, with the inclusion of operational parameters of physicochemical relevance for both cases of transformations of historical TEOM and TEOM measurements to be made in the future. For historical TEOM data, it was observed that the transformations only benefited winter and fall months. Furthermore, comparisons of the transformed historical TEOM data with PM_2.5 concentrations determined from the Federal Reference Method (FRM) sampler at seven locations within the province showed marked improvements over the observed TEOM-FRM comparisons.

Implications:This work provides a path to correcting the historically observed underreporting of particulate mass in winter and fall in Ontario by making the TEOM-based continuous data resemble the new FEM outputs (in this case, more SHARP-like). It is possible that the transformation of mainly winter TEOM data as detailed in this work may potentially lead to revisions in historical annual composite mean PM_2.5 concentrations and total annual number of days PM_2.5 exceeded the Canada-wide Standard (CWS) metric across the province.     

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.     

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.     

Chemical composition of fine particles in the Tennessee Valley region

Fine particles in the atmosphere have elicited new national ambient air quality standards (NAAQS) because of their potential role in health effects and visibility-reducing haze. Since April 1997, Tennessee Valley Authority (TVA) has measured fine particles (PM2.5) in the Tennessee Valley region using prototype Federal Reference Method (FRM) samplers, and results indicate that the new NAAQS annual standard will be difficult to meet in this region. The composition of many of these fine particle samples has been determined using analytical methods for elements, soluble ions, and organic and elemental carbon. The results indicate that about one-third of the measured mass is SO4(-2), one-third is organic aerosol, and the remainder is other materials. The fraction of SO4(-2) is highest at rural sites and during summer conditions, with greater proportions of organic aerosol in urban areas throughout the year. Additional measurements of fine particle mass and composition have been made to obtain the short-term variability of fine mass as it pertains to human exposure. Measurements to account for semi-volatile constituents of fine mass (nitrates, semi-volatile organics) indicate that the FRM may significantly under-measure organic constituents. The potentially controllable anthropogenic fraction of organic aerosols is still largely unknown.     

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.     

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.     

Chemical Composition of Fine Particles in the Tennessee Valley Region

ABSTRACT

Fine particles in the atmosphere have elicited new national ambient air quality standards (NAAQS) because of their potential role in health effects and visibility-reducing haze. Since April 1997, Tennessee Valley Authority (TVA) has measured fine particles (PM_2.5) in the Tennessee Valley region using prototype Federal Reference Method (FRM) samplers, and results indicate that the new NAAQS annual standard will be difficult to meet in this region. The composition of many of these fine particle samples has been determined using analytical methods for elements, soluble ions, and organic and elemental carbon. The results indicate that about one-third of the measured mass is SO₄ ^-2, one-third is organic aerosol, and the remainder is other materials. The fraction of SO₄ ^-2 is highest at rural sites and during summer conditions, with greater proportions of organic aerosol in urban areas throughout the year. Additional measurements of fine particle mass and composition have been made to obtain the short-term variability of fine mass as it pertains to human exposure. Measurements to account for semi-volatile constituents of fine mass (nitrates, semi-volatile organics) indicate that the FRM may significantly under-measure organic constituents. The potentially controllable anthropogenic fraction of organic aerosols is still largely unknown.     

Adjusting tapered element oscillating microbalance data for comparison with Federal Reference Method PM2.5 measurements in region 5

Continuous monitoring of particulate matter (PM) with a diameter less than 2.5 microm (PM2.5) is quickly gaining acceptance as an alternative means of measuring fine PM in the United States. For this project, data were taken from all monitoring sites within Region 5 that used the tapered element oscillating microbalance (TEOM) for PM2.5 and had a collocated Federal Reference Method (FRM) monitor. Scatter plots of TEOM versus FRM show that for a significant fraction of the observations, an independent factor causes the TEOM to underestimate the FRM value. This underestimation appears to increase as temperature decreases. For this analysis, a linear relationship was fit to the TEOM versus FRM data, allowing a break or knot in the relationship, modeled as a change of slope, at a site-specific temperature. To test whether the models are adequate for adjusting future measurements, models were also developed using the first year of data only, and the remaining observations were used to test the durability of the relationships. For all but one monitor in Minnesota, the models developed for each site had consistently high R2s, were predictive of future measurements, and could be used to derive "FRM-like" results from the TEOM measurements. The temperature knots fitted by the model for individual sites ranged from 12.9 to 20.6 degrees C. Data from all six sites in the state of Michigan were also combined to determine if a single model could be developed for the entire state. While the single model for the state of Michigan worked reasonably well, some of the predicted concentrations at individual sites were systematically underestimating the observed concentrations on more polluted days. The same conclusion was drawn for a Region 5-wide model. This approach was also found to work very well for six individual TEOM monitors in New York State.     

An assessment of the sensitivity and reliability of the relative reduction factor approach in the development of 8-hr ozone attainment plans

The updated regulatory framework for demonstrating that future 8-hr ozone (O3) design values will be at or below the National Ambient Air Quality Standards (NAAQS) provides guidelines for the development of a State Implementation Plan (SIP) that includes methods based on photochemical modeling and analytical techniques. One of the suggested approaches is the relative reduction factor (RRF) for estimating the efficacy of emission reductions. In this study, the sensitivity of model-predicted responses towards emission reductions to the choice of meteorology and chemical mechanisms was examined. While the different modeling simulations generally were found to be in agreement on whether predicted future-year design values would be above or below the NAAQS for 8-hr O3 at a majority of the monitoring locations in the eastern United States, differences existed for a small percentage of monitors (approximately 6.4%). Another issue investigated was the ability of the attainment demonstration procedure to predict changes in monitored O3 design values. A retrospective analysis was performed by comparing predicted O3 design values from model simulations using emission estimates for 1996 and 2001 with monitored O3 design values for 2001. Results indicated that an average gross error of approximately 5 ppb was present between modeled and observed design values and that, at approximately 27% of all sites, model-predicted and observed design values disagreed as to whether the design value was above or below the NAAQS. Retrospective analyses such as the one presented in this study can provide valuable insights into the strengths and limitations of modeling and analysis techniques used to predict future design values over time periods of a decade or more for the purpose of developing SIPs. Furthermore, such analyses could provide avenues for improvement and added confidence in the use of the RRF approach for addressing attainment of the NAAQS.     

A comparison of four gravimetric fine particle sampling methods.

A study was conducted to compare four gravimetric methods of measuring fine particle (PM2.5) concentrations in air: the BGI, Inc. PQ200 Federal Reference Method PM2.5 (FRM) sampler; the Harvard-Marple Impactor (HI); the BGI, Inc. GK2.05 KTL Respirable/Thoracic Cyclone (KTL); and the AirMetrics MiniVol (MiniVol). Pairs of FRM, HI, and KTL samplers and one MiniVol sampler were collocated and 24-hr integrated PM2.5 samples were collected on 21 days from January 6 through April 9, 2000. The mean and standard deviation of PM2.5 levels from the FRM samplers were 13.6 and 6.8 microg/m3, respectively. Significant systematic bias was found between mean concentrations from the FRM and the MiniVol (1.14 microg/m3, p = 0.0007), the HI and the MiniVol (0.85 microg/m3, p = 0.0048), and the KTL and the MiniVol (1.23 microg/m3, p = 0.0078) according to paired t test analyses. Linear regression on all pairwise combinations of the sampler types was used to evaluate measurements made by the samplers. None of the regression intercepts was significantly different from 0, and only two of the regression slopes were significantly different from 1, that for the FRM and the MiniVol [beta1 = 0.91, 95% CI (0.83-0.99)] and that for the KTL and the MiniVol [beta1 = 0.88, 95% CI (0.78-0.98)]. Regression R2 terms were 0.96 or greater between all pairs of samplers, and regression root mean square error terms (RMSE) were 1.65 microg/m3 or less. These results suggest that the MiniVol will underestimate measurements made by the FRM, the HI, and the KTL by an amount proportional to PM2.5 concentration. Nonetheless, these results indicate that all of the sampler types are comparable if approximately 10% variation on the mean levels and on individual measurement levels is considered acceptable and the actual concentration is within the range of this study (5-35 microg/m3).     

Estimation of ambient PM2.5 concentrations in Maryland and verification by measured values

In 1997, Maryland had no available ambient Federal Reference Method data on particulate matter less than 2.5 microm in aerodynamic diameter (PM23), but did have annual ambient data for PM smaller than 10 microm (PM10) at 24 sites. The PM10 data were analyzed in conjunction with local annual and seasonal zip-code-level emission inventories and with speciated PM2.5 data from four nearby monitors in the IMPROVE network (located in the national parks, wildlife refuges, and wilderness areas) in an effort to estimate annual average and seasonal high PM2.5 concentrations at the 24 PM10 monitor sites operating from 1992 to 1996. All seasonal high concentrations were estimated to be below the 24-hr PM2.5 National Ambient Air Quality Standards (NAAQS) at the sites operating in Maryland between 1992 and 1996. The estimates also indicated that 12 monitor sites might exceed the 3-year annual average PM2.5 NAAQS of 15 microg/m3, but Maryland's air quality shows signs that it has been improving since 1992. The estimates also were compared with actual measurements after the PM2.5 monitor network was installed. The estimates were adequate for describing the chemical composition of the PM2.5, forecasting compliance status with the 24-hr and annual standards, and determining the spatial variations in PM2.5 across central Maryland.     

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%.