Ozone Formation in California's San Joaquin Valley: A Critical Assessment of Modeling and Data Needs

ABSTRACT

Data from the 1990 San Joaquin Valley Air Quality Study/ Atmospheric Utility Signatures, Predictions, and Experiments (SJVAQS/AUSPEX) field program in California's San Joaquin Valley (SJV) suggest that both urban and rural areas would have difficulty meeting an 8-hr average O₃ standard of 80 ppb. A conceptual model of O₃ formation and accumulation in the SJV is formulated based on the chemical, meteorological, and tracer data from SJVAQS/ AUSPEX. Two major phenomena appear to lead to high O₃ concentrations in the SJV: (1) transport of O₃ and precursors from upwind areas (primarily the San Francisco Bay Area, but also the Sacramento Valley) into the SJV, affecting the northern part of the valley, and (2) emissions of precursors, mixing, transport (including long-range transport), and atmospheric reactions within the SJV responsible for regional and urban-scale (e.g., downwind of Fresno and Bakersfield) distributions of O₃. Using this conceptual model, we then conduct a critical evaluation of the meteorological model and air quality model. Areas of model improvements and data needed to understand and properly simulate O₃ formation in the SJV are highlighted.     

Transport and dispersion during wintertime particulate matter episodes in the San Joaquin Valley, California

Data analysis and modeling were performed to characterize the spatial and temporal variability of wintertime transport and dispersion processes and the impact of these processes on particulate matter (PM) concentrations in the California San Joaquin Valley (SJV). Radar wind profiler (RWP) and radio acoustic sounding system (RASS) data collected from 18 sites throughout Central California were used to estimate hourly mixing heights for a 3-month period and to create case studies of high-resolution diagnostic wind fields, which were used for trajectory and dispersion analyses. Data analyses show that PM episodes were characterized by an upper-level ridge of high pressure that generally produced light winds through the entire depth of the atmospheric boundary layer and low mixing heights compared with nonepisode days. Peak daytime mixing heights during episodes were -400 m above ground level (agl) compared with -800 m agl during nonepisodes. These episode/nonepisode differences were observed throughout the SJV. Dispersion modeling indicates that the range of influence of primary PM emitted in major population centers within the SJV ranged from -15 to 50 km. Trajectory analyses revealed that little intrabasin pollutant transport occurred among major population centers in the SJV; however, interbasin transport from the northern SJV and Sacramento regions into the San Francisco Bay Area (SFBA) was often observed. In addition, this analysis demonstrates the usefulness of integrating RWP/RASS measurements into data analyses and modeling to improve the understanding of meteorological processes that impact pollution, such as aloft transport and boundary layer evolution.     

Processes influencing secondary aerosol formation in the San Joaquin Valley during winter

Air quality data collected in the California Regional PM10/ PM(2.5) Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM(2.5)) mass concentrations in California (< or = 188 microg/m3 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO(x))-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO(x) and volatile organic compound (VOC) emissions plus background O3 levels are expected to determine NO(x) oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Wintertime vertical variations in particulate matter (PM) and precursor concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Air quality monitoring was conducted at a rural site with a tower in the middle of California's San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/ PM2.5 Air Quality Study. Measurements at the surface and n a tower at 90 m were collected in Angiola, CA, from December 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.     

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract

Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM₁₀/M_2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO₂ appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM_2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Understanding particulate matter formation in the California San Joaquin Valley: conceptual model and data needs

Quantitative information from the 1995 Integrated Monitoring Study (IMS95) is used to develop a conceptual model, which describes the chemical characteristics and the physical processes responsible for the accumulation of PM in the San Joaquin Valley of California. One significant finding of the conceptual model is the sensitivity of ammonium nitrate (46% of winter PM_2.5) and nitric acid to oxidants, which may be VOC-sensitive rather than NO_x-sensitive. Key gaps in current knowledge are identified using the conceptual model, e.g., the relative sensitivity of winter oxidants to VOC and NO_x, mechanistic details of secondary organic aerosol formation, mechanisms of dispersion under calm conditions, and the importance of dry deposition. Some recommendations are also provided for the formulation of air quality models suitable to address the accumulation of PM in the San Joaquin Valley.     

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.     

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

Air quality data collected in the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM_2.5) mass concentrations in California (≤188 μg/m³ 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO_x)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO_x and volatile organic compound (VOC) emissions plus background O₃ levels are expected to determine NO_x oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Influence of synoptic and mesoscale meteorology on ozone pollution potential for San Joaquin Valley of California

The distribution of historical ozone levels for a region is tabulated as a function of its prevailing synoptic and mesoscale influences. Meteorological patterns are determined sequentially from extended records of hourly surface wind measurements sampling relevant low-level flows. A visualization method is presented to readily indicate the likelihoods for exceedances to occur under a variety of meteorological conditions. The study domain is San Joaquin Valley (SJV) of California, which is divided into three subregions (North, Central, and South). Each day from May–October of 1996–2004 is labeled using synoptic (single-day) and mesoscale (intra-day) patterns. Emissions levels are assumed roughly constant for this period following the introduction of reformulated gasoline to California. Synoptic motions largely control the regional SJV ozone pollution potential; the same single-day patterns are identified for all three SJV subregions. Additionally, a unique mesoscale flow feature is identified in each subregion that strongly affects its ozone levels: flows through minor Coast Range gaps for N-SJV, the Fresno Eddy for C-SJV, and flows through Mojave Pass for S-SJV. The strength of each mesoscale feature is characterized using 1-h surface u or v wind components that explain local ozone pollution potentials.     

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.     

Resolving the interactions between population density and air pollution emissions controls in the San Joaquin Valley, USA

The effectiveness of emissions control programs designed to reduce concentrations of airborne particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) in California's San Joaquin Valley was studied in the year 2030 under three growth scenarios: low, medium, and high population density. Base-case inventories for each choice of population density were created using a coupled emissions modeling system that simultaneously considered interactions between land use and transportation, area source, and point source emissions. The ambient PM2.5 response to each combination of population density and emissions control was evaluated using a regional chemical transport model over a 3-week winter stagnation episode. Comparisons between scenarios were based on regional average and population-weighted PM2.5 concentrations. In the absence of any emissions control program, population-weighted concentrations of PM2.5 in the future San Joaquin Valley are lowest undergrowth scenarios that emphasize low population density. A complete ban on wood burning and a 90% reduction in emissions from food cooking operations and diesel engines must occur before medium- to high-density growth scenarios result in lower population-weighted concentrations of PM2.5. These trends partly reflect the fact that existing downtown urban cores that naturally act as anchor points for new high-density growth in the San Joaquin Valley are located close to major transportation corridors for goods movement. Adding growth buffers around transportation corridors had little impact in the current analysis, since the 8-km resolution of the chemical transport model already provided an artificial buffer around major emissions sources. Assuming that future emissions controls will greatly reduce or eliminate emissions from residential wood burning, food cooking, and diesel engines, the 2030 growth scenario using "as-planned" (medium) population density achieves the lowest population-weighted average PM2.5 concentration in the future San Joaquin Valley during a severe winter stagnation event. Implications: The San Joaquin Valley is one of the most heavily polluted air basins in the United States that are projected to experience strong population growth in the coming decades. The best plan to improve air quality in the region combines medium- or high-density population growth with rigorous emissions controls. In the absences of controls, high-density growth leads to increased population exposure to PM2.5 compared with low-density growth scenarios (urban sprawl).     

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.     

Size and composition distribution of airborne particulate matter in northern California: I--particulate mass, carbon, and water-soluble ions

The San Joaquin Valley (SJV) in California has one of the most severe particulate air quality problems in the United States during the winter season. In the current study, measurements of particulate matter (PM) smaller than 10 microm in aerodynamic diameter (PM10), fine particles (PM18), and ultrafine particles (PM0.1) made during the period December 16, 2000-February 3, 2001, at six locations near or within the SJV are discussed: Bodega Bay, Davis, Sacramento, Modesto, Bakersfield, and Sequoia National Park. Airborne PM1.8 concentrations at the most heavily polluted site (Bakersfield) increased from 20 to 172 microg/m3 during the period December 16, 2000-January 7, 2001. The majority of the fine particle mass was ammonium nitrate driven by an excess of gas-phase ammonia. Peak PM0.1 concentrations (8-12 hr average) were approximately 2.4 microg/m3 measured at night in Sacramento and Bakersfield. Ultrafine particle concentrations were distinctly diurnal, with daytime concentrations approximately 50% lower than nighttime concentrations. PMO.1 concentrations did not accumulate during the multiweek stagnation period; rather, PMO.1 mass decreased at Bakersfield as PM1.8 mass was increasing. The majority of the ultrafine particle mass was associated with carbonaceous material. The high concentrations of ultrafine particles in the SJV pose a potential serious public health threat that should be addressed.     

An extended approach to calculate the ozone relative response factors used in the attainment demonstration for the National Ambient Air Quality Standards

With the promulgation of the National Ambient Air Quality Standards (NAAQS or standard) for 8-hr ozone (O₃), the U.S. Environmental Protection Agency (EPA) issued modeling guidance that advocated the use of results from photochemical air quality models in a relative sense. In doing so, the EPA provided guidance on how to calculate relative response factors (RRFs) that can project current design value (DV) mixing ratios into the future for the purpose of determining the attainment status with respect to the O₃ standard. The RRFs recommended by the EPA represent the average response of the photochemical model over a broad range of O₃ mixing ratios above a specified cutoff threshold. However, it is known that O₃ response to emission reductions of limiting precursors (i.e., NO_x and/or VOC) is greater on days with higher O₃ mixing ratios compared to days with lower mixing ratios. In this study, we present a segmented RRF concept termed band-RRF, which takes into account the different model responses at different O₃ mixing ratios. The new band-RRF concept is demonstrated in the San Joaquin Valley (SJV) region of California for the 1-hr and 8-hr O₃ standards. The 1-hr O₃ analysis is relevant to work done in support of the SJV O₃ State Implementation Plan (SIP) submitted to the EPA in 2013. The 8-hr example for the future year of 2019 is presented for illustrative purposes only. Further work will be conducted with attainment deadline of 2032 as part of upcoming SIPs for the 0.075 parts per million (ppm) 8-hr O₃ standard. The applicability of the band-RRF concept to the particulate matter (PM_2.5) standards is also discussed.

Implications:Results of photochemical models are used in regulatory applications in a relative sense using relative response factors (RRFs), which represent the impacts of emissions reductions over a wide range of ozone (O₃) values. It is possible to extend the concept of RRFs to account for the fact that higher O₃ mixing ratios (both 1-hr and 8-hr) respond more to emissions controls of limiting precursors than do lower O₃ mixing ratios. We demonstrate this extended concept, termed band-RRF, for the 1-hr and 8-hr O₃ National Ambient Air Quality Standard (NAAQS or standard) in the San Joaquin Valley of California. This extension can also be made applicable to the 24-hr PM_2.5 and annual PM_2.5 standards.     

Resolving the interactions between population density and air pollution emissions controls in the San Joaquin Valley,USA

The effectiveness of emissions control programs designed to reduce concentrations of airborne particulate matter with an aerodynamic diameter <2.5 μm (PM_2.5) in California's San Joaquin Valley was studied in the year 2030 under three growth scenarios: low, medium, and high population density. Base-case inventories for each choice of population density were created using a coupled emissions modeling system that simultaneously considered interactions between land use and transportation, area source, and point source emissions. The ambient PM_2.5 response to each combination of population density and emissions control was evaluated using a regional chemical transport model over a 3-week winter stagnation episode. Comparisons between scenarios were based on regional average and population-weighted PM_2.5 concentrations. In the absence of any emissions control program, population-weighted concentrations of PM_2.5 in the future San Joaquin Valley are lowest under growth scenarios that emphasize low population density. A complete ban on wood burning and a 90% reduction in emissions from food cooking operations and diesel engines must occur before medium- to high-density growth scenarios result in lower population-weighted concentrations of PM_2.5. These trends partly reflect the fact that existing downtown urban cores that naturally act as anchor points for new high-density growth in the San Joaquin Valley are located close to major transportation corridors for goods movement. Adding growth buffers around transportation corridors had little impact in the current analysis, since the 8-km resolution of the chemical transport model already provided an artificial buffer around major emissions sources.

Assuming that future emissions controls will greatly reduce or eliminate emissions from residential wood burning, food cooking, and diesel engines, the 2030 growth scenario using “as-planned” (medium) population density achieves the lowest population-weighted average PM_2.5 concentration in the future San Joaquin Valley during a severe winter stagnation event.

Implications: The San Joaquin Valley is one of the most heavily polluted air basins in the United States that are projected to experience strong population growth in the coming decades. The best plan to improve air quality in the region combines medium- or high-density population growth with rigorous emissions controls. In the absences of controls, high-density growth leads to increased population exposure to PM_2.5 compared with low-density growth scenarios (urban sprawl).     

Spatial and temporal variations in San Joaquin Valley fog chemistry

Fog was sampled at four locations in California’s San Joaquin Valley (SJV) during December 1995 and January 1996 as part of the 1995 Integrated Monitoring Study (IMS95). The fog sampling campaign was conducted in two phases. During the first phase, fog was sampled at three southern SJV surface locations, two urban (Fresno and Bakersfield) and one rural (near the Kern Wildlife Refuge). Both bulk samples (representative of the entire fog drop spectrum) and size-fractionated samples were collected. During the second phase, bulk fog samples were collected at three elevations on a 430 m television transmission tower in the northern SJV, representing some of the first observations of vertical variations in fog composition. SJV fog was observed to be consistently alkaline. The median pH measured in the southern SJV was 6.49, with a range from 4.97 to 7.43. Dominant species in the fog water were ammonium (median southern SJV concentration of 1008 microequivalents/l (μN)), nitrate (483 μN), sulfate (117 μN), acetate (117 μN), formate (63 μN), and formaldehyde (46 μM). Concentrations of the inorganic ions were similar in the urban and rural fogs, although occasionally much higher spikes of S(IV) and sulfate were observed in Bakersfield fog. Acetate, formaldehyde, and total organic carbon, by contrast, were observed to be present in greater concentration in the urban fogs. Bakersfield IMS95 fog concentrations of most species were similar to those measured there in the early 1980s, although concentrations of S(IV) and sulfate were much lower in IMS95 fogs. Significant differences were found between the composition of large and small fog drops, with pH differences at times exceeding one pH unit. The chemical heterogeneity present among SJV fog drop populations is likely to result in significant enhancement of aqueous sulfate production rates over those expected from average fog properties. Significant vertical variations were also observed in fog composition. Liquid water content was observed to increase strongly with elevation, while major ion aqueous concentrations in fog drops decreased with altitude. The total amount of solute contained within the fog (per unit volume of air) was observed to increase with altitude. These observations form a unique data set to be used for model evaluation and for further analysis of aerosol processing by fogs.     

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.     

Analysis of ozone in the San Joaquin Valley of California

The dynamics of ozone in the San Joaquin Valley of central California are studied by systematic diagnostic runs of the three-dimensional SARMAP Air Quality Model. Air quality in the San Joaquin Valley is the result of a complex combination of local and transported emissions. Simulations show that relatively brisk winds at points of inflow to the Valley produce a strong dependence of ozone in the Valley on upwind conditions. Furthermore, NO_x influx from boundaries and local emissions has significantly greater impact on ozone production than ROG influx and emissions.