Association between ionic composition of fine and coarse aerosol soluble fraction and peak expiratory flow of asthmatic patients in São Paulo city (Brazil)

Air pollutants are associated with adverse respiratory effects mainly in susceptible groups. This study was designed to assess the impact of the ionic composition of particulate matter on asthmatic respiratory functions in São Paulo city. From May to July 2002, fine and coarse particulate matter fractions were collected and their respective chemical composition with respect to major ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, NH₄⁺, Cl⁻, NO₃⁻ and SO₄²⁻) were determined in each aqueous-extract fraction. The results showed predominant concentrations of SO₄²⁻ (48.4%), NO₃⁻ (19.6%) and NH₄⁺ (12.5%) in the fine fraction, whereas NO₃⁻ (35.3%), SO₄²⁻ (29.1%), Ca²⁺ (13.1%) and Cl⁻ (12.5%) were the predominant species in the coarse fraction. The association between the chemical components of both fractions and the daily peak expiratory flow (PEF) measurements (morning and evening) of the 33 asthmatic individuals were assessed through a linear mixed-effects model. The results showed a significant negative correlation (decrease of PEF) between morning PEF and coarse chloride (3-day moving average) and between evening PEF and coarse Na⁺ (3-day moving average), coarse Mg²⁺ (3-day moving average) and coarse NH₄⁺ (2- and 3-day moving average). A significant negative correlation has also been observed between morning and evening PEF and Mg²⁺ in the fine fraction. These results suggest that some particle chemical constituents may increase the responsiveness of airways and that coarse particles that deposit in the upper airways may be more relevant for asthmatic response and irritation. However, the results do not prove a clear causal relationship.     

Study of size distribution of atmospheric aerosol at Agra

Measurements on size distribution of atmospheric aerosol were made at Dayalbagh, Agra during July to September 1998. A 4-stage cascade particle sampler (CPS - 105) which fractionates particles in sizes ranging between 0.7 and >10.9 μm, was used. Samples were collected on Whatman 41 filters. The filters were analyzed for the major water-soluble ions. The anions (F, Cl, NO₃ and SO₄) were analyzed by Dionex DX-500 ion chromatograph while atomic absorption and colorimetric techniques were used for the analysis of cations (Na, K, Ca and Mg) and NH₄, respectively. The average mass of aerosol was found to be 131.6 μg m⁻³ and aerosol composition was found to be influenced by terrigeneous sources. The mass size distribution of total aerosol and the ions NH₄, Cl, NO₃, K, Ca, Mg, SO₄ and Na was bimodal while that of F was unimodal. SO₄, F, K and NH₄ dominated in the fine mode while Ca, Mg, Cl and NO₃ were in abundance in coarse fraction. Na was found in both coarse as well as fine mode. Coarse mode SO₄ and NO₃ have been ascribed to contribution from re-suspension of soil and formation by heterogeneous oxidation on soil derived particles. Preponderance of K in fine mode is attributed to emissions from vegetation and from burning of plant materials. Ca, Mg, Cl and NO₃ are largely soil derived and hence dominate in coarse fraction. Equivalent ratios of NH₄/(SO₄+NO₃) were calculated for both fine and coarse aerosols. The coarse mode ratio varied between 0.7 and 1.4 while in fine mode it ranged between 1.4 and 1.9. It shows that aerosol is basic, the basicity of coarse mode is due to higher concentration of soil-derived alkaline components while the basicity in fine mode is due to neutralization of acidity by NH₃.     

Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation

A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM_2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH₄⁺), nitrate (NO₃^?), and sulfate (SO₄^2-) standards. For ambient samples, however, positive deviations are found for SO₄^2-, compensated by negative deviations for NO₃^?, at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH₄⁺, NO₃^?, and SO₄^2- signals was highly correlated with the carbon content of oxalic acid (C?H?O?) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa.

Implications: Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM_2.5 mass concentration.     

Characterization of Major Chemical Components of Fine Particulate Matter in North Carolina

Abstract

This paper presents measurements of daily sampling of fine particulate matter (PM_2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM_2.5 is organic matter, and the major soluble components are sulfate (SO₄ ^2?), ammonium (NH₄ ⁺), and nitrate (NO₃ ^?). NH₄ ⁺ is neutralized mainly by SO₄ ^2? rather than by NO₃ ^?, except in winter when SO₄ ^2? concentration is relatively low, whereas NO₃ ^? concentration is high. The equivalent ratio of NH₄ ⁺ to the sum of SO₄ ^2? and NO₃ ^? is <1, suggesting that SO₄ ^2?and NO₃ ^?are not completely neutralized by NH₄ ⁺. At both rural and urban sites, SO₄ ^2?concentration displays a maximum in summer and a minimum in winter, whereas NO₃ ^?displays an opposite seasonal trend. Mass ratio of NO₃ ^? to SO₄ ^2?is consistently <1 at all sites, suggesting that stationary source emissions may play an important role in PM_2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM_2.5 mass concen trations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM_2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM_2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Visibility as related to atmospheric aerosol constituents

A laboratory and field study was performed to assess the contribution to visibility reduction of both light scattering and absorption by air pollutant particles and gases. Gaseous precursors to important visibility-reducing aerosol species were measured. Emphasis was placed on minimizing sampling artifacts for nitrate and sulfate since previous visibility studies were generally subject to substantial errors from these sources. Optical techniques for measuring the particle absorption coefficient and elemental carbon were evaluated. The aerosol species measured were fine and coarse particulate mass, sulfate, nitrate and elemental carbon, plus organic carbon and ammonium ion. The gases measured were nitric acid, NH₃, SO₂, NO₂ and O₃. Sampling was done at San Jose, Riverside and downtown Los Angeles. The light-scattering efficiency of fine particulate nitrate appeared to be higher than that of sulfate, in contrast to the findings of most prior studies. At all sites light scattering by sulfate, nitrate and elemental carbon particles contributed more than half of the light extinction. Light absorption by particles, due almost exclusively to elemental carbon, contributed 10–20% of the extinction.     

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.     

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.     

Characterization of the major chemical species in PM2.5 in the Kaohsiung City,Taiwan

The concentrations and characteristics of the major components in ambient fine particles in the urban city of Kaohsiung, Taiwan were measured and evaluated. PM_2.5 samples were collected using a dichotomous sampler from November 1998 to April 1999 and analyzed for water-soluble ion species using ion chromatography and for carbonaceous species using an elemental analyzer. It was found that SO₄²⁻, NO₃⁻, and NH₄⁺ dominated the identifiable components, and occupied 42.2% and 90.0% of PM_2.5 mass and total dissolved ionic concentrations. Carbonaceous species (organic and elemental carbon) accounted for 20.8% of PM_2.5. The secondary aerosol formed through the NO₂/SO₂ gas-to-particle conversion was estimated based on the sulfur/nitrogen oxidation ratio (SOR/NOR), i.e., sulfate sulfur/nitrate nitrogen to total sulfur/total nitrogen. The average SOR and NOR values were 0.25 and 0.07 for PM_2.5. The high SOR and NOR values obtained in this study suggested that there existed a secondary formation of SO₄²⁻ from SO₂ along with NO₃⁻ from NO₂ in the atmosphere. The secondary organic carbon formed through the volatile organic compound gas-to-particle conversion was estimated from the minimum ratio between organic and elemental carbon obtained in this study, and was found to constitute 40.0% of the total organic carbon for PM_2.5 (6.6% of the particle mass). The results obtained in this study suggest that the formation of secondary aerosols due to conversion from gaseous precursors is significant and important in urban locations.     

Spatial differences in ambient coarse and fine particles in the Monterrey metropolitan area,Mexico: Implications for source contribution

The ambient air of the Monterrey Metropolitan Area (MMA) in Mexico frequently exhibits high levels of PM₁₀ and PM_2.5. However, no information exists on the chemical composition of coarse particles (PM_c = PM₁₀ – PM_2.5). A monitoring campaign was conducted during the summer of 2015, during which 24-hr average PM₁₀ and PM_2.5 samples were collected using high-volume filter-based instruments to chemically characterize the fine and coarse fractions of the PM. The collected samples were analyzed for anions (Cl^–, NO₃^–, SO₄^2–), cations (Na⁺, NH₄⁺, K⁺), organic carbon (OC), elemental carbon (EC), and 35 trace elements (Al to Pb). During the campaign, the average PM_2.5 concentrations did not showed significance differences among sampling sites, whereas the average PM_c concentrations did. In addition, the PM_c accounted for 75% to 90% of the PM₁₀ across the MMA. The average contribution of the main chemical species to the total mass indicated that geological material including Ca, Fe, Si, and Al (45%) and sulfates (11%) were the principal components of PM_c, whereas sulfates (54%) and organic matter (30%) were the principal components of PM_2.5. The OC-to-EC ratio for PM_c ranged from 4.4 to 13, whereas that for PM_2.5 ranged from 3.97 to 6.08. The estimated contribution of Secondary Organic Aerosol (SOA) to the total mass of organic aerosol in PM_2.5 was estimated to be around 70–80%; for PM_c, the contribution was lower (20–50%). The enrichment factors (EF) for most of the trace elements exhibited high values for PM_2.5 (EF: 10–1000) and low values for PM_c (EF: 1–10). Given the high contribution of crustal elements and the high values of EFs, PM_c is heavily influenced by soil resuspension and PM_2.5 by anthropogenic sources. Finally, the airborne particles found in the eastern region of the MMA were chemically distinguishable from those in its western region.

Implications: Concentration and chemical composition patterns of fine and coarse particles can vary significantly across the MMA. Public policy solutions have to be built based on these observations. There is clear evidence that the spatial variations in the MMA’s coarse fractions are influenced by clearly recognizable primary emission sources, while fine particles exhibit a homogeneous concentration field and a clear spatial pattern of increasing secondary contributions. Important reductions in the coarse fraction can come from primary particles’ emission controls; for fine particles, control of gaseous precursors—particularly sulfur-containing species and organic compounds—should be considered.     

Characterization of the winter atmospheric aerosols in Kyoto and Seoul using PIXE,EAS and IC

Characteristics of atmospheric aerosols in Kyoto, Japan and Seoul, Korea were investigated using particle-induced X-ray emission (PIXE), elemental analysis system (EAS) and ion chromatograph (IC). Atmospheric aerosols were collected into fine and coarse fractions using a two-stage filter pack sampler in Kyoto and Seoul in winter of 1998. PIXE was applied to analyze the middle and heavy elements with atomic number greater than 14 (Si), and EAS was applied to analyze the light elements such as H, C and N. The total mass concentration in Seoul was about two times higher than in Kyoto and the concentration of Ca, Si, and Ti that are mainly originated from soil were remarkably higher in Seoul. During an Asian dust storm event, the concentration of soil components increased dramatically and amounted to about 15 times higher than average concentration. The fine/coarse ratios of NH₄⁺, NO₃⁻, and SO₄²⁻ were extremely high in both sites. The fact that nearly 70% of fine particles in both Kyoto and Seoul consist of the light elements (N, C, and H) suggests the importance of light elements measurement. Good mass closure for fine particles with light element data was achieved.     

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.     

Source Identification of Atlanta Aerosol by Positive Matrix Factorization

Abstract

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles ≤2.5 µm in aerodynamic diameter) samples (PM_2.5 ), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 µm in aerodynamic diameter) samples (PM_10–2.5 ). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO₄ ^2?-rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO₃ ^?-rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO₄ ^2?-rich and NO₃ ^?-rich secondary aerosols were associated with NH₄ ⁺. The SO₄ ^2?-rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO₃ ^?-rich secondary aerosol (16%), SO₄ ^2?-rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

Determination of Source Contributions to Ambient PM2.5 in Kaohsiung,Taiwan, Using a Receptor Model

ABSTRACT

Ambient particulates of PM_2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM_2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM_2.5.

The mean concentration of ambient PM_2.5 was 42.6953.68 μj.g/m³ for the sampling period. The abundant species in ambient PM_2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO₄ ^2- (12.8-15.1%), NO₃ ^- (8.110.3%), NH₄+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM_2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO₄ ^2- and NO₃ ^-), and outdoor burning of agriculture wastes (13-17%).     

Determination of Atmospheric Nitrogen Input to Lake Greenwood,South Carolina: Part 2—Gaseous Measurements and Modeling

Abstract

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO₃; 31%), followed by nitrogen dioxide (NO₂; 23%), fine ammonium (NH₄ ⁺; 20%), coarse nitrate (NO₃ ^?; 16%), fine NO₃ ⁺ (5%), and coarse NH₄ ⁺ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO₂ and 40% HNO₃). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH₄ ⁺ concentrations.     

Seasonal variation in atmospheric aerosol concentration and composition at urban and rural sites in northern England

Seasonal variations in atmospheric aerosol concentration and composition have been determined at two nearby sites, one urban and one rural, near Leeds, W. Yorkshire. Aerosols, sampled on a daily basis and collected in the size ranges < 2.5 μm and 2.5−15 μm, were analysed for total mass, SO²⁻₄, NO⁻₃, Cl⁻ and NH⁺₄. Dark smoke and SO₂ were also measured at both sites. Results are given covering the period October 1982–September 1983. The average concentration of particles was higher at the urban site. The urban-rural difference in coarse particle concentration, which was about a factor of 2, was more significant than the difference in the fine particle concentration, which was only 1.3. Smoke and SO₂ concentrations showed strong wintertime maxima and summertime minima. Fine NO⁻₃ and Cl⁻ concentrations also had pronounced wintertime maxima and summertime minima attributed to the variation in volatility of their ammonium salts. Total mass, SO²⁻₄ and NH⁺₄ did not show any clear seasonal variations. Anti-cyclonic conditions in summer resulted in elevated mass concentrations of secondary pollutants, e.g. SO²⁻₄. The fine fraction contained ca 50% water-soluble inorganic ions at Leeds and slightly more at the rural site. These proportions showed little seasonal variation.     

Compositions of Particles from Selected Sources in Philadelphia for Receptor Modeling Applications

As a part of a receptor model study of the Philadelphia, PA atmosphere, particulate samples were collected from seven air pollution sources in the area: two oil-fired power plants, a coal-fired power plant, a fluidized catalytic cracker, a refuse incinerator, a secondary aluminum smelter and an antimony ore roaster. Samples were collected In two size fractions with a dilution source sampler connected to a modified dichotomous sampler. Masses of collected material were determined gravlmetrlcally. Samples were analyzed for elements by x-ray fluorescence followed by Instrumental neutron activation analysis of some samples. Other samples were analyzed by chemical methods for volatile and nonvolatile carbon, SO₄ ^2? and NH₄ ⁺. Data are presented for up to 46 elements and species on fine (<2.5-μm aerodynamic equivalent diameter) and coarse (2.5 μm < diam < 7-10 μm) particles from each source. Although the data were collected for use in Philadelphia, they should be of value for receptor modeling of other areas having similar sources. The most unexpected results were the large amounts of rare earth elements on particles from the catalytic cracker (e.g., 0.31 percent La In fine fraction) and the oil-fired power plants (120 and 420 ppm La in fine fraction). Substantial amounts of primary SO₄ ^2? are released from the oil-fired plants, the SO₄ ^2? concentrations accounting for 40-45 percent of the fine particulate mass.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Evaluation of the RAMS Continuous Monitor for Determination of PM2.5 Mass Including Semi-Volatile Material in Philadelphia,PA

Abstract

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 PM_2.5 mass, including the semi-volatile species NH₄NO₃ and semi-volatile organic material, but not to measure PM_2.5 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 semi-volatile 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 μg/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 par-ticulate components by the PC-BOSS was ±6-8%.     

The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Application of Computer Controlled High Resolution Mass Spectrometry to the Analysis of Air Pollutants

An AEI-MS9 high resolution mass spectrometer interfaced with a PDP-12 digital computer has been adapted for the multicomponent analysis of air pollutants. Air sampling techniques for particulate and gaseous pollutants have been developed which are compatible with the mass spectrometric system. A single stage impactor has been designed for sampling particulate matter of particle diameters greater than 1–2 μm. The remainder of the particulate matter is collected on a glass fiber filter. Gaseous pollutants are collected on a styrene-divinylbenzene copolymer (Chromosorb 102).

The particulate samples are introduced directly into the mass spectrometer utilizing a temperature programed insertion probe. Gaseous pollutants are desorbed from the copolymer directly into the mass spectrometer by heating. Analysis of composite mass spectral data is facilitated through the use of a digital computer utilizing newly developed computer programs. Final computer output yields qualitative and quantitative results for up to 300 pollutants. Organic pollutants identified in particulate matter include polycyclic aromatic compounds, alkyl chlorides, polychlorinated aromatics, substituted benzenes and organic acids. Composite quantitative results are reported for alkanes and alkenes in the following groups: C₁₅-C₃₀, C₃₀-C₅₀ and Cso-polymeric. Inorganic pollutants identified include As₄O₆, H₂SO_4/ (NH₄)₂SO₄, (NH₄)₂SO₃, NaHSO₄, NH₄NO_3/ NaNO₃, NH₄CI, SeO₂, I₂, elemental sulfur, and elemental cadmium.