Human Exposure to Sulfates from Coal-Fired Power Plants

Abstract

Increased interest in the health effects of ambient par–ticulate mass (PM) has focused attention on the evaluation of existing mass measurement methodologies and the definition of PM in ambient air. The Rupprecht and Patashnick Tapered Element Oscillating MicroBalance (TEOM^®) method for PM is compared with time–integrated gravimetric (manual) PM methods in large urban areas during different seasons. Comparisons are conducted for both PM₁₀ and PM_2.5 concentrations.

In urban areas, a substantial fraction of ambient PM can be semi–volatile material. A larger fraction of this component of PM₁₀ may be lost from the TEOM–heated filter than the Federal Reference Method (FRM). The observed relationship between TEOM and FRM methods varied widely among sites and seasons. In East Coast urban areas during the summer, the methods were highly correlated with good agreement. In the winter, correlation was somewhat lower, with TEOM PM concentrations generally lower than the FRM. Rubidoux, CA, and two Mexican sites (Tlalnepantla and Merced) had the highest levels of PM₁₀ and the largest difference between TEOM and manual methods.

PM_2.5 data from collocation of 24–hour manual samples with the TEOM are also presented. As most of the semi–volatile PM is in the fine fraction, differences between these methods are larger for PM_2.5 than for PM₁₀.     

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.     

Errors in coarse particulate matter mass concentrations and spatiotemporal characteristics when using subtraction estimation methods

In studies of coarse particulate matter (PM_10-2.5), mass concentrations are often estimated through the subtraction of PM_2.5 from collocated PM₁₀ tapered element oscillating microbalance (TEOM) measurements. Though all field instruments have yet to be updated, the Filter Dynamic Measurement System (FDMS) was introduced to account for the loss of semivolatile material from heated TEOM filters. To assess errors in PM_10-2.5 estimation when using the possible combinations of PM₁₀ and PM_2.5 TEOM units with and without FDMS, data from three monitoring sites of the Colorado Coarse Rural–Urban Sources and Health (CCRUSH) study were used to simulate four possible subtraction methods for estimating PM_10-2.5 mass concentrations. Assuming all mass is accounted for using collocated TEOMs with FDMS, the three other subtraction methods were assessed for biases in absolute mass concentration, temporal variability, spatial correlation, and homogeneity. Results show collocated units without FDMS closely estimate actual PM_10-2.5 mass and spatial characteristics due to the very low semivolatile PM_10-2.5 concentrations in Colorado. Estimation using either a PM_2.5 or PM₁₀ monitor without FDMS introduced absolute biases of 2.4 µg/m³ (25%) to –2.3 µg/m³ (–24%), respectively. Such errors are directly related to the unmeasured semivolatile mass and alter measures of spatiotemporal variability and homogeneity, all of which have implications for the regulatory and epidemiology communities concerned about PM_10-2.5. Two monitoring sites operated by the state of Colorado were considered for inclusion in the CCRUSH acute health effects study, but concentrations were biased due to sampling with an FDMS-equipped PM_2.5 TEOM and PM₁₀ TEOM not corrected for semivolatile mass loss. A regression-based model was developed for removing the error in these measurements by estimating the semivolatile concentration of PM_2.5 from total PM_2.5 concentrations. By estimating nonvolatile PM_2.5 concentrations from this relationship, PM_10-2.5 was calculated as the difference between nonvolatile PM₁₀ and PM_2.5 concentrations.

Implications: Errors in the estimation of PM_10-2.5 concentrations using subtraction methods were shown to be related to the unmeasured semivolatile mass when using certain combinations of TEOM instruments. For the northeastern Colorado region, the absolute bias associated with this error significantly affects mean and 95th percentile values, which would affect assessment of compliance if PM_10-2.5 is regulated in the future. Estimating PM_10-2.5 mass concentrations using nonvolatile mass concentrations from collocated PM₁₀ and PM_2.5 TEOM monitors closely estimates the total PM_10-2.5 mass concentrations. A corrective model that removes the described error was developed and applied to data from two sites in Denver.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Regional Transport and Urban Contributions to Fine Particle Concentrations in Southeastern Canada

Abstract

The impact of various atmospheric transport directions on ambient fine particle (PM_2.5) concentrations at several sites in southeastern Canada was estimated (for May-September) using back-trajectory analysis. Three-day back trajectories (four per day) were paired with 6-hr average PM_2.5 mass concentrations measured using tapered element oscillating microbalances (TEOM). PM_2.5 concentrations at rural locations in the region were affected by nonlocal sources originating in both Canada and the United States. Comparison of sites revealed that, on average, the local contribution to total PM_2.5 in the greater Toronto area (GTA) is approximately 30–35%. At each location, average PM_2.5 concentrations under south/southwesterly flow conditions were 2–4 times higher than under the corresponding northerly flow conditions. The chemical composition of both urban and rural PM_2.5 was determined during two separate 2-week spring/summer measurement campaigns. Components identified included SO₄ ^2?, NO₃ ^?, NH₄+, black carbon and organic carbon (OC), and trace elements. Higher particle mass at the urban Toronto site was composed of a higher proportion of all components. However, black carbon, NO₃ ^?, NaCl, and trace elements were found to be the most enriched over the rural/regional background levels.     

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.     

Evaluation of Time-Resolved PM2.5 Data in Urban/Suburban Areas of New Jersey

ABSTRACT

Time-resolved data is needed for public notification of unhealthful air quality and to develop an understanding of atmospheric chemistry, including insights important to control strategies. In this research, continuous fine particulate matter (PM_2.5) mass concentrations were measured with tapered element oscillating microbalances (TEOMs) across New Jersey from July 1997 to June 1998. Data features indicating the influence of local sources and long-distance transport are examined, as well as differences between 1-hr maxima and 24-hr average concentrations that might be relevant to acute health effects. Continuous mass concentrations were not significantly different from filter-collected gravimetric mass concentrations with 95% confidence intervals during any season. Annual mean PM_2.5 concentrations from July 1997 to June 1998 were 17.3, 16.4, 14.1, and 15.3 μg/m³ at Newark, Elizabeth, New Brunswick, and Camden, NJ, respectively. Monthly averaged 24- and 1-hr daily maximum PM_2.5 concentrations suggest the existence of a high PM_2.5 (May-October) and a low PM_2.5 (November-April) season.

PM_2.5 magnitudes and temporal trends were very similar across the state during high PM_2.5 events. In fact, the between-site coefficients of determination (R²) for daily PM_2.5 measurements were 84-98% for June and July. Additionally, during the most pronounced PM_2.5 episode, PM_2.5 concentrations closely tracked the daily maximum 1-hr O₃ concentrations. These observations suggest the importance of transport and atmospheric chemistry (i.e., secondary formation) to PM_2.5 episodes in New Jersey. The influence of local sources was observed in diurnal concentration profiles and annual average between-site differences. Urban wintertime data illustrate that high 1-hr maximum PM_2.5 concentrations can occur on low 24-hr PM_2.5 days.     

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.     

Development and validation of the volatile correction model for PM10 – An empirical method for adjusting TEOM measurements for their loss of volatile particulate matter

EU Directives stipulate that PM₁₀ should be measured using the gravimetric reference method as laid out in EN12341 [CEN, 1998. Air Quality – Determination of the PM₁₀ Fraction of Suspended Particulate Matter – Reference Method and Field Test Procedure to Demonstrate Reference Equivalence of Measurement Methods. European Committee for Standardisation], or an equivalent method as demonstrated using EC guidance [EC, 2005. Demonstration of Equivalence of Ambient Air Monitoring Methods. European Commission Working Group on Guidance for the Demonstration of Equivalence]. There is however a conflict between the requirement to measure PM₁₀ using the gravimetric reference method and the need for rapid public reporting, and many member states, including the UK, rely on non-gravimetric techniques to measure PM₁₀. In the UK the majority of PM₁₀ measurements are made using the Tapered Element Oscillating Microbalance (TEOM), which does not meet the equivalence criteria [Harrison, D., 2006. UK Equivalence Programme for Monitoring of Particulate Matter. Defra, London]. The implied need to upgrade or replace TEOMs with an equivalent automated measurement technique has significant cost implications. The model described in this paper was based on analysis of daily mean measurements of PM₁₀ by the Filter Dynamics Measurement System (FDMS) and the TEOM at UK sites. It uses the FDMS measurement of the volatile component of PM₁₀ (referred to here as FDMS purge) to correct for differences in the sensitivity to volatile PM₁₀ between the TEOM and the EU gravimetric reference method. The model equation for the correction of TEOM PM₁₀ measurements is: TEOM_VCM = TEOM ? 1.87 FDMS purge due to the regional homogeneity of volatile PM, the FDMS purge concentration may be measured at a site distant to the TEOM, allowing the possibility of using a single FDMS instrument to correct PM₁₀ measurements made by several TEOMs in a defined geographical area. The model was assessed against the criteria for the EC Working Group's Guidance for the Demonstration of Equivalence of Ambient Air Monitoring Methods [EC, 2005. Demonstration of Equivalence of Ambient Air Monitoring Methods. European Commission Working Group on Guidance for the Demonstration of Equivalence]. The model satisfies the equivalence criteria using remote FDMS purge measurements for distances up to 200 km (in 22 out of 23 data sets). These data provide strong evidence that the model is a viable tool for correcting measurements from TEOM instruments on the national and local government networks.     

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     

The Influence of Human Activity Patterns on Personal PM Exposure: A Comparative Analysis of Filter-Based and Continuous Particle Measurements

ABSTRACT

Particulate matter (PM) exposure data from the U.S. Environmental Protection Agency (EPA)-sponsored 1998 Baltimore and 1999 Fresno PM exposure studies were analyzed to identify important microenvironments and activities that may lead to increased particle exposure for select elderly (>65 years old) subjects. Integrated 24-hr filter-based PM_2.5 or PM₁₀ mass measurements [using Personal Environmental Monitors(PEMs)] included personal measurements, indoor and outdoor residential measurements, and measurements at a central indoor site and a community monitoring site. A subset of the participants in each study wore passive nephelometers that continuously measured (1-min averaging time) particles ranging in size from 0.1 to ~10 um. Significant activities and locations were identified by a statistical mixed model (p < 0.01) for each study population based on the measured PM_2.5 or PM₁₀ mass and time activity data. Elevated PM concentrations were associated with traveling (car or bus), commercial locations (store, office, mall, etc.), restaurants, and working.

The modeled results were compared to continuous PM concentrations determined by the nephelometers while participants were in these locations. Overall, the nephelometer data agreed within 6% of the modeled PM_2.5 results for the Baltimore participants and within ~20% for the Fresno participants (variability was due to zero drift associated with the nephelometer). The nephelom-eter did not agree as well with the PM₁₀ mass measurements, most likely because the nephelometer optimally responds to fine particles (0.3–2 um). Approximately one-half (54 ± 31%; mean ± standard deviation from both studies) of the average daily PM_2.5 exposure occurred inside residences, where the participants spent an average of 83 ± 10% of their time. These data also showed that a significant portion of PM_2.5 exposure occurred in locations where participants spent only 4–13% of their time.     

Particulate Air Pollution in Mexico City: A Collaborative Research Project

ABSTRACT

PM₁₀, PM₂₅, precursor gas, and upper-air meteorological measurements were taken in Mexico City, Mexico, from February 23 to March 22, 1997, to understand concentrations and chemical compositions of the city's particulate matter (PM). Average 24-hr PM₁₀ concentrations over the period of study at the core sites in the city were 75 H g/m³. The 24-hr standard of 150 μ g/m³ was exceeded for seven samples taken during the study period; the maximum 24-hr concentration measured was 542 μ g/m³. Nearly half of the PM₁₀ was composed of fugitive dust from roadways, construction, and bare land. About 50% of the PM₁₀ consisted of PM_2.5, with higher percentages during the morning hours. Organic and black carbon constituted up to half of the PM_2.5. PM concentrations were highest during the early morning and after sunset, when the mixed layers were shallow. Meteorological measurements taken during the field campaign show that on most days air was transported out of the Mexico City basin during the afternoon with little day-to-day carryover.     

Particulate Matter in California: Part 1—Intercomparison of Several PM2.5, PM10–2.5, and PM10 Monitoring Networks

Abstract

It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 [H9262]m (PM_2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM_2.5 and its major constituents have been routinely collected in California for the past 20 years. The California Air Resources Board operated as many as 20 dichotomous (dichot) samplers for PM_2.5 and coarse PM (PM_10–2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM_2.5 and PM₁₀ from 1988 to 1995 at ten urban and rural sites and 24-h-average PM_2.5 at five urban sites since 1995. Beginning in 1994, the Children’s Health Study collected 2-week averages of PM_2.5 in 12 communities in southern California using the Two-Week Sampler (TWS). Comparisons of collocated samples establish relationships between the dichot, CADMP, and TWS samplers and the 82-site network of PM_2.5 FRM samplers deployed since 1999 in California. PM mass data from the different monitoring programs have modest to high correlation to FRM mass data, fairly small systematic biases and negative proportional biases ranging from 7 to 22%. If the biases are taken into account, all of the programs should be considered comparable with the FRM program. Thus, historical data can be used to develop long-term PM trends in California.     

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.     

Analysis of Temporal and Spatial Dichotomous PM Air Samples in the El Paso-Cd. Juarez Air Quality Basin

ABSTRACT

This paper presents and discusses the results obtained from the gravimetric and chemical analyses of the 24-hr average dichotomous samples collected from five sites in the El Paso-Cd. Juarez air quality basin between August 1999 and March 2000. Gravimetric analysis was performed to determine the temporal and spatial variations of PM_2.5 (particulate matter less than 2.5 um in diameter) and PM2.5-10 (particulate matter less than 10 μm but greater than 2.5 μm in diameter) mass concentrations. The results indicate that ~25% of the PM10 (i.e., PM2.5 + PM2.5-10) concentration is composed of PM2.5. Concurrent measurements of hourly PM concentrations and wind speed showed strong diurnal patterns of the regional PM pollution. Results of X-ray fluorescence (XRF) elemental analyses were compared to similar but limited studies performed by the Texas Natural Resource Conservation Commission (TNRCC) in 1990 and 1997. Major elements from geologic sources—Al, Si, Ca, Na, K, Fe, and Ti—accounted for 35% of the total mass concentrations in the PM2.5-10 fraction, indicating that geologic sources in the area are the dominant PM sources. Levels of toxic trace elements, mainly considered as products of anthropogenic activities, have decreased significantly from those observed in 1990 and 1997.     

Techniques for High-Quality Ambient Coarse Particle Mass Measurements

ABSTRACT

Several recent studies have shown associations between ambient concentrations of particle mass (PM) and rates of morbidity and mortality in the general population. These studies have raised the issue of quality of coarse mass (CM, PM between 2.5 and 10 µm) data used for these purposes. CM data may have precision three or more times worse than the associated PM _2.5 or PM₁₀ data, depending on the measurement method, PM _2.5 to PM ₁₀ ratios, and CM concentrations. CM is measured either as the difference between collocated _PM10 and _PM2.5 samplers or more directly with a dichotomous (virtual impactor) sampler. CM precision for the difference method is degraded due to the increased errors inherent with using the difference between two independent measurements, as well as the high PM_2.5 to PM₁₀ ratios (and low CM concentrations) typical of the eastern United States. The dichotomous sampler (dichot) makes a more direct measurement of CM, but there is a potential for significant postexposure loss of particles from unoiled CM dichot filters, as well as uncertainties in the dichot’s CM channel enrichment factor. Compared to the dichot, low-volume inertial impactor samplers such as the Harvard Impactor (HI) or PM2.5 Federal Reference Method (FRM) are simpler to operate and maintain, provide sharper cut points, and do not require oiled filters to prevent loss of CM from the filter during transport. With the recent interest in CM spatial and temporal variability with respect to PM health effects, we have developed modifications to the HI PM method to provide measurements of 24-hour PM with estimated CM precision of better than 5% CV and r² higher than 0.95, primarily by lowering field blank variability and increasing gravimetric analytical precision. These high-precision PM techniques are not limited to the HI sampler; they can also be applied to the _PM2.5 FRM sampler. The measurement methods described here can be applied to future PM studies to avoid the potential problems with exposure assessment caused by CM measurements that have poor precision.     

Characterization and contribution to PM2.5 of semi-volatile aerosols in Paris (France)

Collocated PM_2.5 measurements using a conventional R&P TEOM (model 1400a) and a TEOM-FDMS were performed at a Paris urban background site during winter/summer field experiments. Results showed that conventional TEOM underestimates PM_2.5 mass concentrations by about 50% in winter and 35% in summer. They also confirmed that this negative sampling artifact, due to the volatilization of semi-volatile material (SVM) inside the instrument, cannot be accurately accommodated by a single correction factor because of SVM routine fluctuations. A basic filter-based investigation of the SVM chemical composition also indicated that SVM, measured by the TEOM–FDMS, is mainly formed by ammonium nitrate in winter while significant contributions of semi-volatile organic matter were observed in summer. The latter species was found to possibly account for more than 50% of secondary organic aerosol formed during summer afternoons. These findings call for more investigation of the SVM chemical composition, particularly during the summer season, in Paris and in Europe.     

Air Quality Measurements from the Fresno Supersite

ABSTRACT

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) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, 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 PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 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.     

Regional transport and urban contributions to fine particle concentrations in southeastern Canada

The impact of various atmospheric transport directions on ambient fine particle (PM2.5) concentrations at several sites in southeastern Canada was estimated (for May-September) using back-trajectory analysis. Three-day back trajectories (four per day) were paired with 6-hr average PM2.5 mass concentrations measured using tapered element oscillating microbalances (TEOM). PM2.5 concentrations at rural locations in the region were affected by nonlocal sources originating in both Canada and the United States. Comparison of sites revealed that, on average, the local contribution to total PM2.5 in the greater Toronto area (GTA) is approximately 30-35%. At each location, average PM2.5 concentrations under south/southwesterly flow conditions were 2-4 times higher than under the corresponding northerly flow conditions. The chemical composition of both urban and rural PM2.5 was determined during two separate 2-week spring/summer measurement campaigns. Components identified included SO4(2-) NO3-, NH4+, black carbon and organic carbon (OC), and trace elements. Higher particle mass at the urban Toronto site was composed of a higher proportion of all components. However, black carbon, NO3-, NaCl, and trace elements were found to be the most enriched over the rural/regional background levels.     

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.     

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.