Objectives and Design of Central California's 1995 Integrated Monitoring Study of the California Regional PM10/PM2.5 Air Quality Study

ABSTRACT

The 1995 Integrated Monitoring Study (IMS95) is part of the Phase 1 planning efforts for the California Regional PM_10/PM_2.5 Air Quality Study. Thus, the overall objectives of IMS95 are to (1) fill information gaps needed for planning an effective field program later this decade; (2) develop an improved conceptual model for pollution buildup (PM10, PM2.5, and aerosol precursors) in the San Joaquin Valley; (3) develop a uniform air quality, meteorological, and emissions database that can be used to perform initial evaluations of aerosol and fog air quality models; and (4) provide early products that can be used to help with the development of State Implementation Plans for PM_10. Consideration of the new particulate matter standards were also included in the planning and design of IMS95, although they were proposed standards when IMS95 was in the planning process.     

Comparison of particle light scattering and fine particulate matter mass in central California

Particle light scattering (Bsp) from nephelometers and fine particulate matter (PM2.5) mass determined by filter samplers are compared for summer and winter at 35 locations in and around California's San Joaquin Valley from December 2, 1999 to February 3, 2001. The relationship is described using particle mass scattering efficiency (sigmasp) derived from linear regression of Bsp on PM2.5 that can be applied to estimated PM2.5 from nephelometer data within the 24-hr filter sampling periods and between the every-6th-day sampling frequency. An average of sigmaSp = 4.9 m2/g was found for all of the sites and seasons; however, sigmasp averaged by site type and season provided better PM2.5 estimates. On average, the sigmasp was lower in summer than winter, consistent with lower relative humidities, lower fractions of hygroscopic ammonium nitrate, and higher contributions from fugitive dust. Winter average sigmasp were similar at non-source-dominated sites, ranging from 4.8 m2/g to 5.9 m2/g. The sigmasp was 2.3 m2/g at the roadside, 3.7 m2/g at a dairy farm, and 4.1 m2/g in the Kern County oilfields. Comparison of Bsp from nephelometers with and without a PM2.5 inlet at the Fresno Supersite showed that coarse particles contributed minor amounts to light scattering. This was confirmed by poorer correlations between Bsp and coarse particulate matter measured during a fall sampling period.     

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.     

Simulating PM concentration during a winter episode in a subtropical valley: Sensitivity simulations and evaluation methods

We investigated a two-week episode with high PM concentrations in California Central Valley during the Christmas–New Year of 2000–2001 using a modeling system that consists of a computationally efficient, 3-D photochemical–microphysical transport model, a mesoscale meteorological model, emission models, and an evaluation package. One hundred simulations were conducted with fine resolutions and observational constraints, to reproduce spatial and temporal features of observed PM concentrations and to understand the formation mechanism of the episode. Simulated PM concentrations consist of secondary inorganic components, mainly ammonium nitrate, and total carbon in areas with elevated concentrations in the accumulation mode, and consist of mainly dust and sea salt in the coarse mode. Simulated oxidants and nitrate were significantly elevated over the valley, and the latter showed much less amplitude than the former. Simulated PM concentrations were evaluated with observations systematically with spatially and temporally paired method, a more restrictive multivariate method (NMFROC), and a more flexible “gradient evaluation” method. The paired evaluation shows that high correlation coefficient (R = ～0.8) and low fractional error (FE = ～0.1) could be achieved at stations with elevated 24-h concentration of PM in the accumulation mode in some simulations. The NMFROC method was used to extract useful information from seemingly failed simulations. A “gradient evaluation” method is introduced here to extract additional information from simulations. We found that emission reductions of NO_x and AVOC showed similar effects on percentage basis in different areas, and both are more effective than reducing NH₃ for abating elevated concentrations of accumulation mode PM in California Central Valley during the winter episode.     

Sources of fine particles in the South Coast area,California

PM_2.5 (particulate matter less than 2.5 μm in aerodynamic diameter) speciation data collected between 2003 and 2005 at two United State Environmental Protection Agency (US EPA) Speciation Trends Network monitoring sites in the South Coast area, California were analyzed to identify major PM_2.5 sources as a part of the State Implementation Plan development. Eight and nine major PM_2.5 sources were identified in LA and Rubidoux, respectively, through PMF2 analyses. Similar to a previous study analyzing earlier data (Kim and Hopke, 2007a), secondary particles contributed the most to the PM_2.5 concentrations: 53% in LA and 59% in Rubidoux. The next highest contributors were diesel emissions (11%) in LA and Gasoline vehicle emissions (10%) in Rubidoux. Most of the source contributions were lower than those from the earlier study. However, the average source contributions from airborne soil, sea salt, and aged sea salt in LA and biomass smoke in Rubidoux increased.To validate the apportioned sources in this study, PMF2 results were compared with those obtained from EPA PMF (US EPA, 2005). Both models identified the same number of major sources and the resolved source profiles and contributions were similar at the two monitoring sites. The minor differences in the results caused by the differences in the least square algorithm and non-negativity constraints between two models did not affect the source identifications.     

Comparison of two winter air quality episodes during the California Regional Particulate Air Quality Study

The duration, strength, spatial extent, and chemical makeup of particulate matter (PM) are compared for two winter air quality episodes captured during the California Regional Particulate Air Quality Study (CRPAQS). Each episode, from the beginning of the buildup through dissolution, lasted about 3 weeks. The first episode occurred from December 14, 1999, through January 1, 2000, with peak 24-hr average fine particulate matter (PM2.5) concentrations reaching 129 microg/m3. The second episode occurred a year later, from December 18, 2000, through January 8, 2001, with peak 24-hr average PM2.5 concentrations reaching 179 microg/m3. Although similar in duration, each episode exhibited unique characteristics. One significant difference was the episode buildup rate; rapid in 1999, but slow and steady in 2000. The rapid buildup of the first episode resulted in more days with PM2.5 concentrations above the 24-hr federal standard, whereas the slow and steady increase of the second episode produced higher peaks. Spatial extent and progress also differed between the two episodes. The Northern Valley was impacted more during the December 1999 episode, and the Southern Valley during the December 2000 episode. The differences carried over into chemical composition. Ammonium nitrate dominated the PM2.5 mass during the December 1999 episode. The second episode reflected a dichotomy typical to the San Joaquin Valley, with Fresno concentrations dominated by organic and elemental carbon and the rest of the Valley concentrations dominated by ammonium nitrate. Each episode showed a regional as well as a local component. Ammonium nitrate concentrations, which result from more regional-scale secondary formation and mixing of emissions, were fairly uniform among the urban and rural sites. Carbon concentrations were always higher at urban sites than at rural sites, corresponding to the higher emissions density of primary carbon sources in urban areas.     

Particulate carbon measurements in California's San Joaquin Valley

Aerosol carbon sampling methods and biases were evaluated during the California Regional PM10/PM2.5 Air Quality Study (CRPAQS) and Fresno Supersite programs. PM2.5 sampling was conducted using Desert Research Institute (DRI) sequential filter samplers (SFS) from December 1999 through February 2001 at two urban sites (Fresno and Bakersfield), one regional transport site (Angiola), and two boundary sites (Bethel Island and Sierra Nevada Foothills) during CRPAQS in the San Joaquin Valley (SJV). Additional filter-based sampling was done in Fresno as part of the US Environmental Protection Agency (EPA) Supersites program. Organic carbon (OC) and elemental carbon (EC) concentrations were higher during winter (December-February) than summer (June-August) and this trend was most pronounced at Fresno and Bakersfield. OC and EC displayed similar diurnal trends during winter and summer at Fresno and during winter at Angiola. The diurnal pattern at Angiola reflected the transport of secondary pollutants to the site. Collocated measurements of OC and EC on undenuded quartz-fiber filters were made at Fresno with the DRI SFS and the Andersen FRM and RAAS samplers. All average differences in OC between samplers were less than their respective measurement uncertainties. Positive and negative OC biases were evaluated at Fresno using the Andersen RAAS sampler with carbon-denuded and undenuded channels with Teflon-membrane and quartz-fiber filter pairs. Differences between the denuded particle OC and that obtained by subtracting the quartz-behind-Teflon or quartz-behind-quartz OC from the undenuded quartz-fiber front filter were less than twice their measurement uncertainties in most cases. Particulate OC in the denuded channel agreed most closely with the difference between undenuded front and backup quartz-fiber OC.     

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.     

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.