Particulate matter in California: part 2--Spatial, temporal, and compositional patterns of PM2.5, PM10-2.5, and PM10

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM2.5 and PM10 concentrations range from 3 to 10 microg/m3 and from 5 to 18 microg/m3, respectively. In the urban areas of California, annual-averages for PM2.5 range from 7 to 30 microg/m3, with observed 24-hr peaks reaching levels as high as 160 microg/m3. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM2.5 concentrations that are more prolonged and regional in nature. PM2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO4(2-)) and nitrate (NO3-) components of PM2.5 and PM10) and correlate with reductions in ambient levels of oxides of sulfur (SOx) and oxides of nitrogen (NOx). Annual averages for PM10-2.5 and PM10 exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Spatial and temporal variability in outdoor,indoor, and personal PM2.5 exposure

Outdoor, indoor and personal PM_2.5 measurements were made in a population of nonsmoking adults from three communities in the Minneapolis–St. Paul metropolitan area between April and November 1999. Thirty-two healthy adult subjects (23 females, 9 males; mean age 42±10, range: 24–64 yr) were monitored for 2–15 days during the spring, summer, and fall monitoring seasons. Twenty-four hour average gravimetric PM_2.5 samples were collected using a federal reference monitor (Anderson RAAS2.5-300) located at outdoor (O) central sites in the Battle Creek (BCK), East St. Paul (ESP) and Phillips (PHI) communities. Concurrent 24-h average indoor (I) and personal (P), and a limited number of outdoor-at-home (O@H) samples were collected using inertial impactors (PEM™ Model 200, MSP, Inc). The O (geometric mean {GM}=8.6; n=271; range: 1.0–41 μg/m³) were lower than I concentrations (GM=10.7; n=294; range 1.3–131 μg/m³), which were lower than P concentrations (GM=19.0; n=332; range 2.2–298 μg/m³). Correlation coefficients between O concentrations in the three communities were high and measured GM O levels in BCK were significantly lower than ESP, most likely because of local sources, but GM concentrations in PHI were not significantly different from BCK or ESP. On days with paired samples (n=29), O concentrations were significantly lower (mean difference 2.9 μg/m³; p=0.026) than O@H measurements (GM=11.3; range: 3.5–33.8 μg/m³), likely due to local sources in communities. Observed I and P concentrations were more variable, probably because of residential central air conditioning and hours of household ventilation for I and P, and occupational and environmental tobacco smoke exposures outside the residence for P. Across all individuals and days the median PM_2.5 “personal cloud” was 5.7 μg/m³, but the mean of the average for each participant was 15.7 μg/m³, with very low values in participants who did not work outside the home and much higher values in subjects with active lifestyles. Across all households and individuals the correlation between P and O concentrations was not significant, but the overall I–O correlation (0.27) and P–I correlation (0.51) were significant (p<0.05). Relatively little spatial variability was observed in O PM_2.5 concentrations across the three communities compared to the variability associated with I and P samples, and the measured O levels were relatively low compared to other large metropolitan areas in the United States.     

Particulate matter in California: part 1--Intercomparison of several PM2.5, PM10-2.5, and PM10 monitoring networks

It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM2.5 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 PM2.5 and coarse PM (PM10-2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM2.5 and PM10 from 1988 to 1995 at ten urban and rural sites and 24-h-average PM2.5 at five urban sites since 1995. Beginning in 1994, the Children's Health Study collected 2-week averages of PM2.5 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 PM2.5 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.     

Wintertime PM2.5 and PM10 Source Apportionment at Sacramento,California

ABSTRACT

The chemical mass balance (CMB) model was applied to winter (November through January) 1991–1996 PM2.5 and PM10 data from the Sacramento 13th and T Streets site in order to identify the contributions from major source categories to peak 24-hr ambient PM_2.5 and PM₁₀ levels. The average monthly PM₁₀ monitoring data for the nine-year period in Sacramento County indicate that elevated concentrations are typical in the winter months. Concentrations on days of highest PM₁₀ are dominated by the PM2.5 fraction. One factor contributing to increased PM_2.5 concentrations in the winter is meteorology (cool temperatures, low wind speeds, low inversion layers, and more humid conditions) that favors the formation of secondary nitrate and sulfate aerosols. Residential wood burning also elevates fine particulate concentrations in the Sacramento area.

The results of the CMB analysis highlight three key points. First, the source apportionment results indicate that primary motor vehicle exhaust and wood smoke are significant sources of both PM_2.5 and PM₁₀ in winter. Second, nitrates, secondarily formed as a result of motor-vehicle and other sources of nitrogen oxide (NO_x), are another principal cause of the high PM_2.5 and PM₁₀ levels during the winter months. Third, fugitive dust, whether it is resuspended soil and dust or agricultural tillage, is not the major contributor to peak winter PM_2.5 and PM10 levels in the Sacramento area.     

Spatial and seasonal variation of PM10 mass concentrations in Taiwan

Hourly data of PM10 concentration collected from an air quality-monitoring network has been analyzed over Taiwan from 1994 to 1999. Fourteen sites from 72 monitoring stations were selected to evaluate the spatial and seasonal variations in the regions of north, southwest, south, east and National Park. The selected monitoring sites are located in a suburban environment, except Nantz and Linyuan that are located in industrial areas. Moreover, Yangming and Hengchuen are located in National Park. Spatial and seasonal variations of PM10 concentrations are rather large over Taiwan. Annual average in south is approximately six times higher than in National parks. In northern sites, the highest concentration occurs in March–May, which is attributed to the occurrence of dust storms in arid regions of central Asia and the transport of dust by northeasterly monsoon. A marked seasonal variation of PM10 concentrations can be observed both in southwestern and southern regions. The pattern is characterized by high concentrations in winter and low in summer. Appearance of the highest monthly PM10 concentration in winter of south may be in part due to the lowest number of monthly precipitation days and low temperature, both of which occurred in winter. The frequency of PM10 daily mean concentration for exceeded 150 μg m⁻³ is 15% during winter in south, which reflects the serious pollution problem there. Monitoring sites in National Park are representatives of remote environments, but the PM10 concentrations are still affected by the dust storms and human activities.     

Analysis of PM10, PM2.5, and PM2 5-10 concentrations in Santiago, Chile, from 1989 to 2001

Daily particle samples were collected in Santiago, Chile, at four urban locations from January 1, 1989, through December 31, 2001. Both fine PM with da < 2.5 microm (PM2.5) and coarse PM with 2.5 < da < 10 microm (PM2.5-10) were collected using dichotomous samplers. The inhalable particle fraction, PM10, was determined as the sum of fine and coarse concentrations. Wind speed, temperature and relative humidity (RH) were also measured continuously. Average concentrations of PM2.5 for the 1989-2001 period ranged from 38.5 microg/m3 to 53 microg/m3. For PM2.5-10 levels ranged from 35.8-48.2 microg/m3 and for PM10 results were 74.4-101.2 microg/m3 across the four sites. Both annual and daily PM2.5 and PM10 concentration levels exceeded the U.S. National Ambient Air Quality Standards and the European Union concentration limits. Mean PM2.5 levels during the cold season (April through September) were more than twice as high as those observed in the warm season (October through March); whereas coarse particle levels were similar in both seasons. PM concentration trends were investigated using regression models, controlling for site, weekday, month, wind speed, temperature, and RH. Results showed that PM2.5 concentrations decreased substantially, 52% over the 12-year period (1989-2000), whereas PM2.5-10 concentrations increased by approximately 50% in the first 5 years and then decreased by a similar percentage over the following 7 years. These decreases were evident even after controlling for significant climatic effects. These results suggest that the pollution reduction programs developed and implemented by the Comisión Nacional del Medio Ambiente (CONAMA) have been effective in reducing particle levels in the Santiago Metropolitan region. However, particle levels remain high and it is thus imperative that efforts to improve air quality continue.     

Statistical characterization of atmospheric PM10 and PM2.5 concentrations at a non-impacted suburban site of Istanbul, Turkey

Inhalable particulate matter (PM10) has been monitored at several stations by Istanbul Municipality. On the other hand, information about fine fraction aerosols (PM2.5) in Istanbul atmosphere was not reported. In this study, 86 daily aerosol samples were collected between July 2002 and July 2003. The PM10 annual arithmetic mean value of 47.1 microg m(-3), was lower than the Turkish air quality standard of 60 microg m(-3). On the other hand, this value was found higher than the annual European Union air quality PM(10) standard of 40 microg m(-3). Furthermore, the annual mean concentration of PM2.5 20.8 microg m(-3) was found higher than The United States EPA standard of 15 microg m(-3). The statistics and relationships of fine, coarse, and inhalable particles were studied. Cyclic behavior of the monthly average concentrations of PM10 and PM2.5 data were investigated. Several frequency distribution functions were used to fit the measured data. According to Chi-squared and Kolmogorov-Smirnov tests, the frequency distributions of PM2.5 and PM10 data were found to fit Log-logistic functions.     

Short-term temporal variation in PM2.5 mass and chemical composition during the Atlanta Supersite Experiment, 1999

Measurements in urban Atlanta of transient aerosol events in which PM2.5 mass concentrations rapidly rise and fall over a period of 3-6 hr are reported. The data are based on new measurement techniques demonstrated at the U.S. Environmental Protection Agency (EPA) Atlanta Supersite Experiment in August 1999. These independent instruments for aerosol chemical speciation of NO3-, SO4(2-), NH4+, and organic and elemental carbon (OC and EC), reconstructed the observed hourly dry PM2.5 mass to within 20% or better. Data from the experiment indicated that transient PM2.5 events were ubiquitous in Atlanta and were typically characterized by a sudden increase of EC (soot) and OC in the early morning or SO4(2-) in the late afternoon. The frequent temporal decoupling of these events provides insights into their origins, suggesting mobile sources in metro Atlanta as the main contributor to early morning PM2.5 and more regionally located point SO2 sources for afternoon PM2.5 events. The transient events may also have health implications. New data suggest that short-term PM2.5 exposures may lead to adverse health effects. Standard integrated filter-based techniques used in PM2.5 compliance monitoring networks and in most past PM2.5 epidemiologic studies collect samples over 24-hr periods and thus are unable to capture these transient events. Moreover, health-effects studies that focus on daily PM2.5 mass alone cannot evaluate the health implications of the unique and variable chemical properties of these episodes.     

A four-year size-segregated characterization study of particles PM10, PM2.5 and PM1 depending on air mass origin at Melpitz

PM₁₀ measurements were started in November 1992 at Melpitz site. The mean PM₁₀ concentration in 1993 was 38 μg m^?3 in the summer season (May until October) and about 44 μg m^?3 in the winter season (November until April). The mean PM₁₀ level decreased until 1999 and varies now in ranges from 20–34 μg m^?3 to 17–24 μg m^?3 (minimum and maximum mean values for 1999–2008) in winter and summer seasons, respectively. High volume filter samples of particles PM₁₀, PM_2.5 and PM₁ were characterized for mass, water-soluble ions, organic and elemental carbon from 2004 until 2008. The percentage of PM_2.5 in PM₁₀ varies between summer (71.6%) and winter seasons (81.9%). Mean concentrations of PM₁₀, PM_2.5 and PM₁ in Melpitz were 20, 15, and 13 μg m^?3 in 2004, 22, 18, and 13 μg m^?3 in 2005, 24, 19, and 12 μg m^?3 in 2006 and 22, 17, and 12 μg m^?3 in 2007, respectively. In the four winters the rural background concentration PM₁₀ at Melpitz exceeded the daily 50 μg m^?3 limit for Europe on 8, 8, 7 and 6 days, respectively.Findings for a simple two-sector-classification of the samples (May 2004 until April 2008) using 96-h backward trajectories for the identification of source regions are: Air masses were transported most of time (60%) from the western sector and secondly (17%) from the eastern sector. The lowest daily mean mass concentration PM₁₀ were found during western inflow in summer (17 μg m^?3) containing low amounts of sulphate (2.4 μg m^?3), nitrate (1.7 μg m^?3), ammonium (1.1 μg m^?3) and TC (3.7 μg m^?3). In opposite the highest mean mass concentration PM₁₀ was found during eastern inflow in winter (35 μg m^?3) with high amounts of sulphate (6.1 μg m^?3), nitrate (5.4 μg m^?3), ammonium (3.8 μg m^?3) and TC (9.4 μg m^?3). An estimation of secondary formed OC (SOA) shows 0.8–0.9 μg m^?3 for air masses from West and 2.1–2.2 μg m^?3 from East. The seasonal difference can be neglected.The half-hourly measurements of the particle mass concentration PM₁₀ evaluated as mean daily courses using a TEOM^® show low values (14–21 μg m^?3) in summer and winter for air masses transported from West and the highest concentrations (31–38 μg m^?3) in winter for air masses from East.The results demonstrate the influence of meteorological parameters on long-range transport, secondary particle mass formation and re-emission which modify mass concentration and composition of PM₁₀, PM_2.5 and PM₁. Melpitz site is located in the East of Germany faraway from strong local anthropogenic emissions (rural background). Therefore, this site is suitable for investigation of the influence of long-range transport of air pollution in continental air masses from the East with source regions inside and outside of the European Union.     

Synoptic evaluation of regional PM2.5 concentrations

By comparing short-term fluctuations in PM2.5 species concentrations among nearby air quality monitors and among species, it becomes possible to understand the regional and local events leading to higher concentrations. This approach was applied at thirteen sites in the Maryland area for the 2001–2006 timeframe in order to identify and explain the behavior of eighteen different analytes as well as the daily Air Quality Index.Findings included identification of local upwind events such as fireworks displays, construction and demolition, the spatial extent of sulfate, nitrate, and ammonium correlations between ground-level monitors, correlations between some crustal species to indicate similar emissions sources in urban areas, and indicators of particle adsorption as a rate-limiting step for certain species. For example, the bromine behavior suggests that bromine concentrations on particulate matter may be limited by the particle adsorption rate and thus show a dependence on the Air Quality Index measurements.     

Oxalic acid in PM2.5 particulate matter in California

Ambient air monitoring for organic acids in PM2.5 was conducted at several locations in California. During the study, it was found that oxalic acid (ethanedioc acid) was the most abundant organic acid found in the PM2.5 fraction. Samples from Azuza (in southern California), San Jose (in the San Francisco Bay area), and Fresno (in central California), a PM2.5 Super Site, were collected in 1999 and analyzed. The results for oxalic acid concentrations during this monitoring effort are presented.     

Oxalic Acid in PM2.5 Particulate Matter in California

ABSTRACT

Ambient air monitoring for organic acids in PM₂₅ was conducted at several locations in California. During the study, it was found that oxalic acid (ethanedioc acid) was the most abundant organic acid found in the PM_{2 5} fraction. Samples from Azuza (in southern California), San Jose (in the San Francisco Bay area), and Fresno (in central California), a PM_2.5 Super Site, were collected in 1999 and analyzed. The results for oxalic acid concentrations during this monitoring effort are presented.     

Airborne particle PM2.5/PM10 mass distribution and particle-bound PAH concentrations near a medical waste incinerator

This study attempts to determine the influence of air quality in a residential area near a medical waste incineration plant. Ambient air concentrations of polycyclic aromatic hydrocarbons (PAHs), PM₁₀ and PM_2.5 (PM—particulate matter) were determined by collecting air samples in areas both upwind and downwind of the plant. The differences in air pollutant levels between the study area and a reference area 11 km away from the plant were evaluated.Dichotomous samplers were used for sampling PM_2.5 and PM₁₀ from ambient air. Two hundred and twenty samples were obtained from the study area, and 100 samples were taken from a reference area. Samples were weighed by an electronic microbalance and concentrations of PM_2.5 and PM₁₀ were determined. A HPLC equipped with a fluorescence detector was employed to analyze the concentrations of 15 PAHs compounds adsorbed into PM_2.5 and PM₁₀.The experimental results indicated that the average concentrations of PM_2.5 and PM₁₀ were 30.34±17.95 and 36.81±20.45 μg m⁻³, respectively, in the study area, while the average ratio of PM_2.5/PM₁₀ was 0.82±0.01. The concentrations of PM_2.5 and PM₁₀ of the study area located downwind of the incinerator were significantly higher than the study area upwind of the incinerator (P<0.05).The concentration of PAHs in PM_2.5 in the study area was 2.2 times higher than in the reference area (P<0.05). Furthermore, the benzo(a)pyrene concentrations in PM_2.5 and PM₁₀ were 0.11±0.05 ng m⁻³ and 0.12±0.06 ng m⁻³ in the study area, respectively. The benzo(a)pyrene concentrations of PM_2.5 and PM₁₀ in the study area were 7 and 5.3 times higher than in the reference area (P<0.05), respectively.The study indicated that the air quality of PM_2.5, PM₁₀ and PAHs had significant contamination by air pollutants emitted from a medical waste incineration factory, representing a public health problem for nearby residences, despite the factory being equipped with a modern air pollution control system.     

TEOM vs. manual gravimetric methods for determination of PM2.5 aerosol mass concentrations

Comparison of 24 h mean PM2.5 aerosol loadings determined by a TEOM and by two manual gravimetric samplers (a low-volume filter sampler and a Micro Orifice Uniform Deposit Impactor) in four Australian cities, on 15 days in the winter half-year, revealed systematically lower results from the TEOM by an average of >30%. This result is consistent with reports from elsewhere suggesting that semi-volatile aerosol material is lost from the heated sample filter employed on the TEOM.     

Spatial and temporal variations in PM10 and PM2.5 source contributions and comparison to emissions during the 1995 integrated monitoring study

The ambient PM₁₀ and PM_2.5 data collected during the fall and winter portions of the 1995 Integrated Monitoring Study (IMS95) were used to conduct Chemical Mass Balance (CMB) Modeling to determine source contribution estimates. Data from the core and saturation monitoring sites provided an extensive database for evaluating the spatial and temporal variations of contributing sources. Geological sources dominated fall samples, while secondary ammonium nitrate and carbonaceous sources were the largest contributors for winter samples. Secondary ammonium nitrate concentrations were uniform across all sites during both the fall and winter. Site-to-site variability was primarily due to differences in geological contributions in the fall, and carbonaceous source contributions in the winter. During the winter, diurnal profiles of particulate matter (PM) were driven by variations in carbonaceous sources at urban sites, and by variations in secondary ammonium nitrate at rural sites. Although records of day-specific PM activities were recorded during the study, no correlation was observed between 24-h CMB results and specific activities. The ambient data collected during IMS95 was also used to evaluate the adequacy of the emissions inventory. Comparison of ambient and emissions based ratios of NMHC/NO_x, PM/NO_x, CO/NO_x, and SO_x/NO_x suggested that emissions of NMHC and CO in some locations may be underestimated, while emissions for PM and SO_x may be overestimated. Comparison of fractional primary CMB source contribution estimates to corresponding fractional emissions estimates indicated that geological sources were overemphasized in the inventory, while carbonaceous sources were underrepresented.     

PM2.5 mass and light extinction reconstruction in IMPROVE

Compliance under the Regional Haze Rule of 1999 is based on Interagency Monitoring of Protected Visual Environments (IMPROVE) protocols for reconstructing aerosol mass and light extinction from aerosol chemical concentrations measured in the IMPROVE network. The accuracy, consistency, and potential biases in these formulations were examined using IMPROVE aerosol chemistry and light extinction data from 1988-1999. Underestimation of particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) by the IMPROVE mass reconstruction formula by 12%, on average, appears to be related to the exclusion of sodium, chlorine, and other elements and to artifacts associated with the measurement of organic carbon, but not to absorption of water by sulfates and nitrates on IMPROVE Teflon filters during weighing. Light scattering measured by transmissometry is not consistent with nephelometer scattering or single-scatter albedos expected for remote locations. Light scattering was systematically overestimated by 34%, on average, with the IMPROVE particle scattering (Bsp) reconstruction formula. The use of climatologically based hygroscopic growth factors f(RH) suggested for compliance with the Haze Rule contributes significantly to this overestimation and increases the amount of light extinction attributable to sulfates for IMPROVE samples between 1993 and 1999 by 5 percentage points.     

Loss of PM2.5 Nitrate from Filter Samples in Central California

Abstract

Evaporative loss of particulate matter (with aerodynamic diameter <2.5 μm, [PM_2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from <10% during cold months to >80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM_2.5 acquired on Teflon-membrane filters, measured PM_2.5 mass was 8–16% lower than actual PM_2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM_2.5 was as much as 32–44% lower than actual PM_2.5 at three California Central Valley locations.     

Elemental characterization of PM10, PM2.5 and PM1 in the town of Genoa (Italy)

The particulate matter (PM) concentration and composition, the PM10, PM2.5, PM1 fractions, were studied in the urban area of Genoa, a coastal town in the northwest of Italy. Two instruments, the continuous monitor TEOM and the sequential sampler PARTISOL, were operated almost continuously on the same site from July 2001 to September 2004. Samples collected by PARTISOL were weighted to obtain PM concentration and then analysed by PIXE (particle induced X-ray emission) and by ED-XRF (energy dispersion X-ray fluorescence), obtaining concentrations for elements from Na to Pb. Some of the filters used in the TEOM microbalance were analysed by ED-XRF to calculate Pb concentration values averaged over 7-30 d periods.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.