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.     

Ozone formation in California's San Joaquin Valley: a critical assessment of modeling and data needs

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., down-wind 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.     

Future impacts of distributed power generation on ambient ozone and particulate matter concentrations in the San Joaquin Valley of California

Distributed power generation-electricity generation that is produced by many small stationary power generators distributed throughout an urban air basin-has the potential to supply a significant portion of electricity in future years. As a result, distributed generation may lead to increased pollutant emissions within an urban air basin, which could adversely affect air quality. However, the use of combined heating and power with distributed generation may reduce the energy consumption for space heating and air conditioning, resulting in a net decrease of pollutant and greenhouse gas emissions. This work used a systematic approach based on land-use geographical information system data to determine the spatial and temporal distribution of distributed generation emissions in the San Joaquin Valley Air Basin of California and simulated the potential air quality impacts using state-of-the-art three-dimensional computer models. The evaluation of the potential market penetration of distributed generation focuses on the year 2023. In general, the air quality impacts of distributed generation were found to be small due to the restrictive 2007 California Air Resources Board air emission standards applied to all distributed generation units and due to the use of combined heating and power. Results suggest that if distributed generation units were allowed to emit at the current Best Available Control Technology standards (which are less restrictive than the 2007 California Air Resources Board standards), air quality impacts of distributed generation could compromise compliance with the federal 8-hr average ozone standard in the region.     

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.     

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.     

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.     

Variability of indicator values for ozone production sensitivity: a model study in Switzerland and San Joaquin Valley (California)

The threshold values of indicator species and ratios delineating the transition between NO_x and VOC sensitivity of ozone formation are assumed to be universal by various investigators. However, our previous studies suggested that threshold values might vary according to the locations and conditions. In this study, threshold values derived from various model simulations at two different locations (the area of Switzerland by UAM Model and San Joaquin Valley of Central California by SAQM Model) are examined using a new approach for defining NO_x and VOC sensitive regimes. Possible definitions for the distinction of NO_x and VOC sensitive ozone production regimes are given. The dependence of the threshold values for indicators and indicator ratios such as NO_y, O₃/NO_z, HCHO/NO_y, and H₂O₂/HNO₃ on the definition of NO_x and VOC sensitivity is discussed. Then the variations of threshold values under low emission conditions and in two different days are examined in both areas to check whether the models respond consistently to changes in environmental conditions. In both cases, threshold values are shifted similarly when emissions are reduced. Changes in the wind fields and aging of the photochemical oxidants seem to cause the day-to-day variation of the threshold values. O₃/NO_z and HCHO/NO_y indicators are predicted to be unsatisfactory to separate the NO_x and VOC sensitive regimes. Although NO_y and H₂O₂/HNO₃ provide a good separation of the two regimes, threshold values are affected by changes in the environmental conditions studied in this work.     

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.     

Designing and Managing the San Joaquin Valley Air Quality Study

The field measurement phase of the San Joaquin Valley Air Quality Study, which was conducted in the summer of 1990, was the largest and most sophisticated study of its kind ever conducted in this country. The San Joaquin Valley has the nation’s second worst overall air quality problem and is using the study results to conduct regional modeling to refine its control strategies. The study began in 1985 and will continue into the mid-1990s. The origins of the study, and the manner in which it is being funded and administered, reflect a unique and highly successful collaboration among several levels of government and the private sector. The temporary organizational structure formed to manage the study sets an interesting precedent for how political-level leaders can work effectively with the scientific community to conduct a long term technical study.     

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.     

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.     

Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Future Impacts of Distributed Power Generation on Ambient Ozone and Particulate Matter Concentrations in the San Joaquin Valley of California

ABSTRACT

Distributed power generation—electricity generation that is produced by many small stationary power generators distributed throughout an urban air basin—has the potential to supply a significant portion of electricity in future years. As a result, distributed generation may lead to increased pollutant emissions within an urban air basin, which could adversely affect air quality. However, the use of combined heating and power with distributed generation may reduce the energy consumption for space heating and air conditioning, resulting in a net decrease of pollutant and greenhouse gas emissions. This work used a systematic approach based on land-use geographical information system data to determine the spatial and temporal distribution of distributed generation emissions in the San Joaquin Valley Air Basin of California and simulated the potential air quality impacts using state-of-the-art three-dimensional computer models. The evaluation of the potential market penetration of distributed generation focuses on the year 2023. In general, the air quality impacts of distributed generation were found to be small due to the restrictive 2007 California Air Resources Board air emission standards applied to all distributed generation units and due to the use of combined heating and power. Results suggest that if distributed generation units were allowed to emit at the current Best Available Control Technology standards (which are less restrictive than the 2007 California Air Resources Board standards), air quality impacts of distributed generation could compromise compliance with the federal 8-hr average ozone standard in the region.

IMPLICATIONS The San Joaquin Valley is a fast growing region that demands increasing power generation to sustain the economic development, and at the same time it is one of the worst polluted areas in the United States. Hence, the region demands alternatives that minimize the air quality impacts of power generation. This paper addresses the air quality impacts of distributed generation of power, an alternative to central power generation that can potentially reduce greenhouse gas and pollutant emissions throughout the United States.     

Composition and secondary formation of fine particulate matter in the Salt Lake Valley: Winter 2009

Under the National Ambient Air Quality Standards (NAAQS), put in place as a result of the Clean Air Amendments of 1990, three regions in the state of Utah are in violation of the NAAQS for PM₁₀ and PM_2.5 (Salt Lake County, Ogden City, and Utah County). These regions are susceptible to strong inversions that can persist for days to weeks. This meteorology, coupled with the metropolitan nature of these regions, contributes to its violation of the NAAQS for PM during the winter. During January–February 2009, 1-hr averaged concentrations of PM_10-2.5, PM_2.5, NO_x, NO₂, NO, O₃, CO, and NH₃ were measured. Particulate-phase nitrate, nitrite, and sulfate and gas-phase HONO, HNO₃, and SO₂ were also measured on a 1-hr average basis. The results indicate that ammonium nitrate averages 40% of the total PM_2.5 mass in the absence of inversions and up to 69% during strong inversions. Also, the formation of ammonium nitrate is nitric acid limited. Overall, the lower boundary layer in the Salt Lake Valley appears to be oxidant and volatile organic carbon (VOC) limited with respect to ozone formation. The most effective way to reduce ammonium nitrate secondary particle formation during the inversions period is to reduce NO_x emissions. However, a decrease in NO_x will increase ozone concentrations. A better definition of the complete ozone isopleths would better inform this decision.

Implications: Monitoring of air pollution constituents in Salt Lake City, UT, during periods in which PM_2.5 concentrations exceeded the NAAQS, reveals that secondary aerosol formation for this region is NO_x limited. Therefore, NO_x emissions should be targeted in order to reduce secondary particle formation and PM_2.5. Data also indicate that the highest concentrations of sulfur dioxide are associated with winds from the north-northwest, the location of several small refineries.     

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.     

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.     

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics?+?pyrogenics) was 250.6?±?73.7 ng g^?1 dw; biogenic PAH constituted 67?±?4 % of total PAH. THC were 26?±?9 % of total biogenic PAH, THP were 36?±?7 %, and perylene was 38?±?7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60–93 % of total PAH; THC, THP and perylene were 31?±?28 %, 24?±?32 %, and 45?±?36 % of biogenic PAH. At 100–103 cm depth, THP constituted 80 % of biogenic PAH and at 120–123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river’s watershed.     

Internal acid buffering in San Joaquin Valley fog drops and its influence on aerosol processing

Although several chemical pathways exist for S(IV) oxidation in fogs and clouds, many are self-limiting: as sulfuric acid is produced and the drop pH declines, the rates of these pathways also decline. Some of the acid that is produced can be buffered by uptake of gaseous ammonia. Additional internal buffering can result from protonation of weak and strong bases present in solution. Acid titrations of high pH fog samples (median pH=6.49) collected in California's San Joaquin Valley reveal the presence of considerable internal acid buffering. In samples collected at a rural location, the observed internal buffering could be nearly accounted for based on concentrations of ammonia and bicarbonate present in solution. In samples collected in the cities of Fresno and Bakersfield, however, significant additional, unexplained buffering was present over a pH range extending from approximately four to seven. The additional buffering was found to be associated with dissolved compounds in the fogwater. It could not be accounted for by measured concentrations of low molecular weight (C₁–C₃) carboxylic acids, S(IV), phosphate, or nitrophenols. The amount of unexplained buffering in individual fog samples was found to correlate strongly with the sum of sample acetate and formate concentrations, suggesting that unmeasured organic species may be important contributors. Simulation of a Bakersfield fog episode with and without the additional, unexplained buffering revealed a significant impact on the fog chemistry. When the additional buffering was included, the simulated fog pH remained 0.3–0.7 pH units higher and the amount of sulfate present after the fog evaporated was increased by 50%. Including the additional buffering in the model simulation did not affect fogwater nitrate concentrations and was found to slightly decrease ammonium concentrations. The magnitude of the buffering effect on aqueous sulfate production is sensitive to the amount of ozone present to oxidize S(IV) in these high pH fogs.     

Economic Assessment of the Effects of Air Pollution on Agricultural Crops in the San Joaquin Valley

Physical and economic impacts of 1978 ambient levels of ozone and sulfur dioxide on 33 crops In the San Joaquin Valley are estimated. The field data regression approach Is used and evaluated for estimating yield losses. The effects of alternative air pollution measures and regression functional forms are evaluated. An economic model is employed that accounts for both farm and market responses to yield improvements from reduced air pollution. Economic damages were estimated to exceed $100 million in 1978 with the biggest losers being the producers of cotton and producers and consumers of grapes, a crop that has heretofore been Ignored in agricultural assessments of pollution damage.