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.     

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.     

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.     

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.     

Characterization of PM2.5 and PM10 in the South Coast Air Basin of southern California: Part 1--Spatial variations

In December 1994, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive program, the PM10 Technical Enhancement Program (PTEP), to characterize fine PM in the South Coast Air Basin (SCAB). A 1-year special particulate monitoring project was conducted from January 1995 to February 1996 as part of the PTEP. Under this enhanced monitoring, HNO3, NH3, and speciated PM10 and PM2.5 concentrations were measured at five stations (Anaheim, downtown Los Angeles, Diamond Bar, Fontana, and Rubidoux) in the SCAB and at one background station at San Nicolas Island. PM2.5 and PM10 mass and 43 individual species were analyzed for a full chemical speciation of the particle data. The PTEP data indicate that the most abundant chemical components of PM10 and PM2.5 in the SCAB are NH4+ (8-9% of PM10 and 14-17% of PM2.5), NO3- (23-26% of PM10 and 28-41% of PM2.5), SO4- (6-11% of PM10 and 9-18% of PM2.5), organic carbon (OC) (15-19% of PM10 and 18-26% of PM2.5), and elemental carbon (EC) (5-8% of PM10 and 8-13% of PM2.5). On an annual average basis, PM2.5 comprises 52-59% of the SCAB PM10. Annual average PM10 and PM2.5 concentrations showed strong spatial variations, low at coastal sites and high at inland sites. Annual average PM10 concentrations varied from 40.8 micrograms/m3 at Anaheim to 76.8 micrograms/m3 at Rubidoux, while annual average PM2.5 concentrations varied from 21.7 micrograms/m3 at Anaheim to 39.8 micrograms/m3 at Rubidoux. The chemical characterizations of the PM2.5 and PM10 concentrations, as well as their spatial variations, were examined; the important findings are summarized in this paper, and the temporal variations are discussed in the companion paper.     

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.     

Temporal Variations of PM2.5, PM10, and Gaseous Precursors during the 1995 Integrated Monitoring Study in Central California

ABSTRACT

The spatial and temporal distributions of particle mass and its chemical constituents are essential for understanding the source-receptor relationships as well as the chemical, physical, and meteorological processes that result in elevated particulate concentrations in California’s San Joaquin Valley (SJV). Fine particulate matter ₍PM_2.5), coarse particulate matter (PM₁₀), and aerosol precursor gases were sampled on a 3-hr time base at two urban (Bakersfield and Fresno) and two non-urban (Kern Wildlife Refuge and Chowchilla) core sites in the SJV during the winter of 1995–1996.

Day-to-day variations of PM_2.5 and PM₁₀ and their chemical constituents were influenced by the synoptic-scale meteorology and were coherent among the four core sites. Under non-rainy conditions, similar diurnal variations of PM_2.5 and coarse aerosol were found at the two urban sites, with concentrations peaking during the nighttime hours. Conversely, PM_2.5 and coarse aerosol peaked during the morning and afternoon hours at the two non-urban sites. Under rainy and foggy conditions, these diurnal patterns were absent or greatly suppressed.

In the urban areas, elevated concentrations of primary pollutants (e.g., organic and elemental carbons) during the late afternoon and nighttime hours reflected the impact from residential wood combustion and motor vehicle exhaust. During the daytime, these concentrations decreased as the mixed layer deepened. Increases of secondary nitrate and sulfate concentrations were found during the daylight hours as a result of photochemical reactions. At the non-urban sites, the same increases in secondary aerosol concentrations occurred during the daylight hours but with a discernable lag time. Concentrations of the primary pollutants also increased at the non-urban sites during the daytime. These observations are attributed to mixing aloft of primary aerosols and secondary precursor gases in urban areas followed by rapid transport aloft to non-urban areas coupled with photochemical conversion.     

Spatial and temporal characterization of PM2.5 mass concentrations in California, 1980-2007

Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 microm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r2 > 0.9; mean absolute error approximately 2 microg m(-3)) from PM with an aerodynamic diameter < or =10 microm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980-2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 microg m(-3) yr(-1) (median -0.11 microg m(-3) yr(-1)), whereas urban-site trends ranged from -0.13 to -1.29 microg m(-3) yr(-1) (median -0.59 microg m(-3) yr(-1)). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 microg m(-3) at IMPROVE sites and from 9.3 to 37.1 microg m(-3) at urban sites.     

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.     

南宁市大气颗粒物TSP、PM10、PM2.5污染水平研究

2002年在南宁市的5个典型城市功能区内,共采集了125个大气样品(按季节分别采集),初步调查了大气中颗粒物TSP、PM10、PM2.5的污染状况。结果表明,南宁市TSP、PM10、PM2.5的污染很严重,超标率分别为67．5％、82．5％、92．5％,对人体健康危害更大的PM2．5占到了PM10的63．5％左右。重污染区PM2.5的浓度超过轻污染区近一倍。     

Characterization of soluble and insoluble components in PM2.5 and PM10 fractions of airborne particulate matter in Kofu city,Japan

A systematic method combining water and diluted-acid extractions has been developed for the manifold evaluation of soluble and insoluble fractions in ambient aerosol. The pre-washed regenerated cellulose membrane filter was used as a collection medium of a low-volume air sampler. The collection time of 7–14 days was required to obtain the sample amounts enough for the systematic analysis. Simple and efficient extraction procedures using the filtration of water and 0.1 M hydrochloric acid were recommended in order to obtain the information about the dissolution behaviors of various elements in the aerosol. Soluble components in both the extracts were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and ion chromatography (IC). These extraction procedures were also preferred to prepare thin-layer specimens suitable to the succeeding X-ray fluorescence spectrometry (XRF) for insoluble components. Elemental compositions of the extraction residues were conveniently determined by the XRF calibrated with thin-layer standard specimens prepared with activated carbon. The determination of the 17 representative elements (Na, Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Pb) in these three fractions from an aerosol sample was performed rapidly within 4 h. The proposed systematic method was applied to PM_2.5 and PM₁₀ aerosol samples collected in Kofu City, Central Japan, and the enrichment behaviors of various elements and their source apportionment such as soil, anthropogenic substances and vehicle exhaust particulates could be demonstrated by the present method.     

Characterisation of PM10 and PM2.5 particulate matter in the ambient air of Milan (Italy)

24-h simultaneous samplings of PM10 and PM2.5 particulate matter (PM) have been carried out during the period December 1997–September 1998 in the central urban area of Milan. The mass concentrations of the two fractions showed significant daily variations linked to different thermodynamic conditions of the planetary boundary layer (PBL) and characterised by higher values during wintertime. The elemental composition, determined by energy dispersive X-ray fluorescence technique, was quite different in the two fractions: in the finer one the presence of elements with crustal origin is reduced while the anthropogenic elements, with a relevant environmental and health impact, appear to be enriched. The composition data allowed a quantification of two major components of the atmospheric particulate: sulphates (mainly of secondary origin) and particles with crustal origin. An important but unmeasured component is likely constituted by organic and elemental carbon compounds.The multivariate analysis of elements, gaseous pollutants and mass concentration data-sets leads to the identification of four main sources contributing to PM10 and PM2.5 composition: vehicles exhaust emissions, resuspended crustal dust, secondary sulphates and industrial emissions. The existence of a possible background component with non-local origin is also suggested.     

Air quality at Santiago,Chile: a box modeling approach II. PM2.5, coarse and PM10 particulate matter fractions

Ambient monitored data at Santiago, Chile, are analyzed using box models with the goal of assessing contributions of different economic activities to air pollution levels. The box modeling approach was applied to PM₁₀, PM_2.5 and coarse (PM₁₀–PM_2.5) particulate matter (PM) fractions; the period analyzed is 1989–1999. A linear model for each PM fraction was obtained, having as independent variables CO and SO₂ concentrations, plus a term proportional to (wind speed)⁻¹ that lumps together non-combustion emissions and secondary generation terms; wet scavenging is included as another independent variable. Model identification results show good agreement for the different parameters across monitoring stations. The washout ratios and scavenging coefficients agree with data published in the literature, being higher for the coarse PM fraction. The CO and SO₂ coefficients fitted for 1989–1995 agree with a priori estimates for the same period. Background estimates for the PM fractions are in agreement with measurement campaigns in upwind sites. Results show that transportation sources have become the dominant contributors to ambient PM levels, while stationary sources have decreased their contributions in the last years. The relative importance of mobile sources to PM_2.5 ambient concentrations has doubled in the last 10 years, whereas stationary sources have reduced their relative contributions to half the value in the early 1990s. Model estimates of regional background of PM_2.5 and PM₁₀ have decreased 50% and 22% in the last decade, respectively; coarse background has shown no significant change. The final conclusion is that there is room and need for a more intensive emission reduction strategy for Santiago, focusing on mobile sources. The approach pursued in this work is feasible for cities or regions where comprehensive, transport and chemistry models are not available yet, but estimates of air quality contributions are needed for policy purposes. The methodology requires data on ambient air quality measurements and surface meteorology.     

Source apportionment of visual impairment during the California regional PM10/PM2.5 air quality study

Gases and particulate matter predictions from the UCD/CIT air quality model were used in a visibility model to predict source contributions to visual impairment in the San Joaquin Valley (SJV), the southern portion of California's Central Valley, during December 2000 and January 2001. Within the SJV, daytime (0800–1700 PST) light extinction was dominated by scattering associated with airborne particles. Measured daytime particle scattering coefficients were compared to predicted values at approximately 40 locations across the SJV after correction for the increased temperature and decreased relative humidity produced by “smart heaters” placed upstream of nephelometers. Mean fractional bias and mean fractional error were ?0.22 and 0.65, respectively, indicating reasonable agreement between model predictions and measurements. Particulate water, nitrate, organic matter, and ammonium were the major particulate species contributing to light scattering in the SJV. Daytime light extinction in the SJV averaged between December 25, 2000 and January 7, 2001 was mainly associated with animal ammonia sources (28%), diesel engines (18%), catalyst gasoline engines (9%), other anthropogenic sources (9%), and wood smoke (7%) with initial and boundary conditions accounting for 13%. The source apportionment results from this study apply to wintertime conditions when airborne particulate matter concentrations are typically at their annual maximum. Further study would be required to quantify source contributions to light extinction in other seasons.     

Characterization of PM2.5 and PM10 in the South Coast Air Basin of southern California: Part. 2--Temporal variations

The South Coast Air Quality Management District (SCAQMD) conducted a 1-year special particulate monitoring study from January 1995 to February 1996. This monitoring data indicates that high PM10 and PM2.5 concentrations were observed in the fall (October, November, and December), with November concentrations being the highest. During the rest of the year, PM2.5 and PM10 masses gradually increased from January to September. Monthly PM10 mass varied from 20 to 120 micrograms/m3, and monthly PM2.5 mass varied from 13 to 63 micrograms/m3. The PM2.5-to-PM10 ratio varied daily and ranged between 22 and 96%. Two types of high-PM days were observed. The first type was observed under fall stagnation conditions, which lead to high secondary species concentrations. The second type was observed under high wind conditions, which lead to high primary coarse particles of crustal components. The highest 24-hr average PM10 concentration (226.3 micrograms/m3) was observed at the Fontana station, while the highest PM2.5 concentration (129.3 micrograms/m3) was observed at the Diamond Bar station.     

2015年南京市PM2.5与PM10的污染特征

分析了2015年南京市PM2.5和PM10的浓度特征和大致来源类型。PM2.5和PM10的年均浓度分别为56.6 μg·m-3和96.5 μg·m-3,污染水平较高。颗粒物浓度的季节变化特征一致：冬 > 春 > 秋 > 夏;PM2.5的日变化呈"单峰单谷"型,而PM10的呈"单峰双谷"型。颗粒物浓度在城区高于郊区;植被茂盛区域的浓度较低。对PM2.5/PM10而言,比值在冬季和梅雨期较大,分别受取暖和降水的影响;比值在春季和夏末秋初较小,分别受沙尘和秸秆焚烧的影响。PM2.5多为二次颗粒物,PM10多为一次颗粒物;固定污染源对PM2.5的间接贡献和对PM10的直接贡献较移动污染源而言更大。     

Chemical speciation of PM2.5 and PM10 in south Phoenix, AZ, USA

Phoenix, AZ, experiences high particulate matter (PM) episodes, especially in the wintertime. The spatial variation of the PM concentrations and resulting differences in exposure is of particular concern. In this study, PM2.s (PM with aerodynamic diameter <2.5 microm) and PM10 (PM with aerodynamic diameter <10 microm) samples were collected simultaneously from the east and west sides of South Phoenix and at a control site in Tempe and analyzed for trace elements and bulk elemental and organic carbon. Measurements showed that although PM2.5 concentrations had similar trends in temporal scale across all sites, concentrations of PM10 did not. The difference in PM10 concentrations and fluctuation across the three sites suggest effects of a local soil source as evidenced by high concentrations of Al, Ca, and Fe in PM10. K and anthropogenic elements (e.g., Cu, Pb, and Zn) in PM2.5 samples on January 1 were strikingly high, suggesting the influence of New Year's fireworks. Concentrations of toxic elements (e.g., Pb) in the study presented here are not different from similar studies in other U.S. cities. Application of principal component analysis indicated two broad categories of emission sources--soil and combustion--together accounting for 80 and 90% of variance, respectively, in PM2.5 and PM10. The soil and combustion components explained approximately 60 and 30% of the variance in PM10, respectively, whereas combustion sources dominated PM2.5 (>50% variance). Many elements associated with anthropogenic sources were highly enriched, with enrichment factors in PM2.5 an order of magnitude higher than in PM10 relative to surface soil composition in the study area.     

Evaluation of artificial neural networks for fine particulate pollution (PM10 and PM2.5) forecasting

Multi-layer perceptron (MLP) artificial neural network (ANN) models are compared with traditional multiple regression (MLR) models for daily maximum and average O3 and particulate matter (PM10 and PM2.5) forecasting. MLP particulate forecasting models show little if any improvement over MLR models and exhibit less skill than do O3 forecasting models. Meteorological variables (precipitation, wind, and temperature), persistence, and co-pollutant data are shown to be useful PM predictors. If MLP approaches are adopted for PM forecasting, training methods that improve extreme value prediction are recommended.     

Semi-volatile species in PM2.5: comparison of integrated and continuous samplers for PM2.5 research or monitoring

Fine particles in urban atmospheres contain substantial quantities of semi-volatile material [e.g., NH4NO3 and semi-volatile organic compounds (SVOCs)] that are lost from particles during collection on a filter. Several diffusion denuder samplers have been developed for the determination of both NO3- and organic semi-volatile fine particulate components. The combination of technology used in the BOSS diffusion denuder sampler and the Harvard particle concentrator has resulted in the Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) for the 24-hr (or less) integrated collection of PM2.5, including NH4NO3 and semi-volatile organic material. Modification of the BOSS sampler allows for the weekly determination of these same species. Combination of BOSS denuder and tapered element oscillating microbalance (TEOM) monitor technology has resulted in the real-time ambient mass sampler (RAMS) for the continuous measurement of PM2.5, including the semi-volatile components. Comparison of the results obtained with the BOSS and with each of the newly developed modifications of the BOSS indicates that the modified versions can be used for the continuous, daily, or weekly monitoring of PM2.5, including semi-volatile species, as appropriate to the design of each sampler.     

Use of the aerodynamic particle sizer to measure ambient PM10-2.5: the coarse fraction of PM10

The Aerodynamic Particle Sizer (APS 3321, TSI, Inc., Shoreview, MN) rapidly measures particle number concentration by size from 0.5 to 20 microm. This work used simple assumptions for particle shape factor and density to estimate ambient coarse mode particulate matter, PM10-2.5, from APS number concentration data. This estimate was compared with that measured with time-integrated, filter-based federal reference method (FRM) samplers in four U.S. field studies: two in Phoenix, AZ; one in Gary, IN; and one in Riverside, CA. Near one-to-one agreement and a strong linear relationship were observed between APS-estimated and FRM-measured PM10-2.5 in the first Phoenix, AZ study (slope = 0.90, R2 = 1.00); the second Phoenix, AZ study (slope = 0.99, R2 = 0.99); and the Riverside, CA study (slope = 1.00, R2 = 0.84). In the Gary, IN study, PM10-2.5 estimates made with data from the APS tended to be less than that measured with the FRM samplers (slope = 0.57), but the linear relationship between the two methods was still strong (R2 = 0.90). Particle-bound water associated with wet atmospheric conditions may account for these differences. Additional testing is required to resolve this issue.