Standards for Air Quality in California

Abstract

During the 1950s and 1960s, hundreds of thousands of underground storage tanks (and above-ground storage tanks) containing petroleum products and hazardous chemicals were installed. Many of these tanks either have been abandoned or have exceeded their useful lives and are leaking, thereby posing a serious threat to the nation’s surface and groundwater supplies, as well as to public health. Cleaning up releases of petroleum hydrocarbons or other organic chemicals in the subsurface environment is a real-world problem,

Biological treatment of hydrocarbon-contaminated soil is considered to be a relatively low-cost and safe technology; however, its potential for effectively treating recalcitrant wastes has not been fully explored. For millions of years, microorganisms such as bacteria, fungi, actinomycete, protozoa, and others have performed the function of recycling organic matter from which new plant life can grow.

This paper examines the biological treatment technology for cleaning up petroleum product-contaminated soils, with special emphasis on microbial enzyme systems for enhancing the rate of biodegradation of petroleum hydrocarbons. Classifications and functions of enzymes, as well as the microbes, in degrading the organic contaminants are discussed. In addition, the weathering effect on biodegradation, types of hydrocarbon degraders, advantages associated with enzyme use, methods of enzyme extraction, and future research needs for development and evaluation of enzyme-assisted bioremediation are examined.     

Airborne Survey of Major Air Basins in California

An instrumented aircraft has been used to study photochemical air pollution in the State of California. Simultaneous measurements of the most important chemical constituents (ozone, total oxidant, hydrocarbons, and nitrogen oxides, as well as several meteorological variables) were made. State-of-the-art measurement techniques and sampling procedures are discussed. Data from flights over the South Coast Air Basin, the San Francisco Bay area, the Salinas Valley, and the Pacific Ocean within 200 miles of the California coast are presented. Pollutants were found to be concentrated in distinct layers up to at least 18,000 feet. In many of these layers, the pollutant concentrations were much higher than at ground level. Furthermore, the presence of stable air very effectively inhibits the dilution of air masses for distances of 30 miles or more. Very low levels of ozone were recorded over the Pacific Ocean and measurements relating to air mass aging were made. The background ozone level for the South Coast Air Basin is estimated to be 0.03 ppm. These findings bring into question the validity of the present practice of depending solely on data from ground-based monitoring stations for predictive models.     

California Experience with Air Quality Standards

Air quality standards have existed in California for almost six years. They have become an important part of the State’s air pollution control program.

The two principal uses of the standards have been to establish the goals for controlling motor vehicle emissions and to provide a basis for evaluating air quality throughout the State. The standards have also proved to be valuable as a means of communicating on air pollution problems with legislators, administrators, the press, the public, and dischargers of pollutants.

Lack of adequate data on the effects of varying concentrations of contaminants of concern in air pollution is a serious limitation in any effort to establish air quality standards.It is important that this data be obtained.

The concept of employing air quality standards as administrative goals is not unique to the air pollution field but is part of a broad trend to utilize standards for insuring a satisfactory environment. Those engaged in the air pollution field can expect to see increasing emphasis on such standards.

Air quality standards do not provide a magic formula for eliminating air pollution; they are but one element in a comprehensive program. They have limitations and are no better than the data upon which they are based. The standards, however, can play an important role in preserving satisfactory air quality and protecting man’s health.

In using air quality standards, one should keep in mind the comments of H. W. Streeter⁵ on water quality standards—“Let us devise them, try them, revise them, and apply them, but also remember that they are but ’feeble instruments of the human will’ and like all other such tools are made to be discarded for better ones when they become worn out.“     

Day-of-Week Patterns in Toxic Air Contaminants in Southern California

Abstract

Day-of-week mean ambient concentrations were computed for six high-cancer-risk toxic air contaminants (TACs): 1,3-butadiene, benzene, acetaldehyde, formalde-hyde, carbon tetrachloride (CCl₄), and perchloroethylene. Data from six urban sites in southern California, from 1989 through 2001, were analyzed. Graphical displays were used to search for repeated patterns. Benzene and 1,3-butadiene, emitted mainly by mobile sources, exhibit distinctly lower concentrations on Sundays and slightly lower concentrations on Saturdays and Wednesdays. Acetaldehyde and formaldehyde show some trace of a weekly pattern similar to that of benzene and 1,3-butadiene, but the pattern is not strongly marked. Perchloroethylene, used primarily as a dry-cleaning solvent, is also distinctly lower on Sundays. CCl₄ does not show a dayof-week pattern.     

Penetration and Duration of Oxidant Air Pollution in the South Coast Air Basin of California

On June 18, 19, and 20, 1970, two aircraft, a rawinsonde, two pibal stations, and four ground stations provided simultaneous samples of total oxidant, temperature, and winds up to 8000 ft in an area extending from Santa Monica, Calif., east to Redlands and north across the San Bernardino Mountains. It was shown that photochemical oxidant formed in the marine layer is vented up the slopes and over the crest of the San Bernardino Mountains during the day. Layers of high oxidant concentrations were detected above the inversion base, suggesting that some pollution is vented up the slopes and subsequently advected back to the south. The diurnal changes in the temperature inversion also contribute to the high concentration found above the inversion base. These processes result in multi-layers of pollution. The study suggests that oxidant air pollution is transported up to 80 mi to forested mountains, where severe damage to conifer species has been documented.     

Differences between Weekday and Weekend Air Pollutant Levels in Southern California

Abstract

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) emissions on weekday and weekend levels of ozone (O₃; 1991–1998) and particulate NO₃ ^- (1980–1999) in southern California. Despite significantly lower O₃ precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O₃ levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O₃ levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO₃ ^- or nitric acid (HNO₃, the precursor of particulate NO₃ ^-). Averaged over sites, the mean Sunday NO_x and nonmethane hydrocarbon concentrations were 25–41% and 16–30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O₃ levels were related to whether O₃ formation was limited by the availability of NO_x. A thermodynamic equilibrium model predicts that particulate NO₃ ^- levels would decrease in response to a reduction of HNO₃, and that particulate ammonium NO₃ ^- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO₃ ^- therefore did not result from limitations on the formation of particulate NO₃ ^- from its precursor, HNO₃.     

Reductions in human benzene exposure in the California South Coast Air Basin

Benzene typically contributes a significant fraction of the human cancer risk associated with exposure to urban air pollutants. In recent years, concentrations of benzene in ambient air have declined in many urban areas due to the use of reformulated gasolines, lower vehicle emissions, and other control measures. In the California South Coast Air Basin (SoCAB) ambient benzene concentrations have been reduced by more than 70% since 1989. To estimate the resulting effect on human exposures, the Regional Human Exposure (REHEX) model was used to calculate benzene exposures in the SoCAB for the years 1989 and 1997. Benzene concentration distributions in 14 microenvironments (e.g. outdoor, home, vehicle, work) were combined with California time-activity patterns and census data to calculate exposure distributions for 11 demographic groups in the SoCAB. For 1997, the calculated average benzene exposure for nonsmoking adults in the SoCAB was 2 ppb, compared to 6 ppb for 1989. For nonsmokers, about half of the 1997 exposure was due to ambient air concentrations (including their contributions to other microenvironments), but only 4% for smokers. Passive tobacco smoke contributed about one-fourth of all exposure for adult nonsmokers. In-transit microenvironments and attached garages contributed approximately 15 and 10%, respectively. From 1989 to 1997, decreases in passive smoke exposure accounted for about one-sixth of the decrease in exposure for nonsmoking adults, with the remainder due to decreases in ambient concentrations. The reductions in exposure during this time period indicate the effectiveness of reformulated fuels, more stringent emission standards, and smoking restrictions in significantly reducing exposure to benzene.     

An update on oxidant trends in the South Coast Air Basin of California

The trends in oxidant air quality in the South Coast Air Basin of California are of great interest because of the high oxidant levels in the region. In this work, we have updated the trends for daily peak oxidant levels in the entire Basin and at two sites, Azusa and San Bernardino. Since the daily oxidant levels are highly dependent on the local meteorology, we have determined trends under fixed meteorological conditions. We previously applied this approach to data from the 1971 to 1979 period. In the present work, we found that, for the 1971–1981 period, the oxidant trends basinwide and in Azusa are downward while the trend in San Bernardino is flat. An additional finding of this study is that in recent years the basinwide daily peak oxidant concentration has been occurring in San Bernardino with increasing frequency. The overall decrease in and eastward movement of the basinwide maxima are discussed in relation to the trends in the emissions of reactive hydrocarbons and nitrogen oxides over the time period as well as the predictions of smog chamber experiments.     

Cyclic Trends in Los Angeles Fine Participates

Noontime visibilities in downtown Los Angeles, averaged over the smog season of June through November, show two cycles of general deterioration and improvement. The improvement since 1962 is confirmed by available high volume filter data and conditions in 1974/75 are at least as good as at anytime since observations were begun in 1933. The decrease in frequency of “rule 57” days suggests that the improvement of the last decade and perhaps the cyclic variation of the past 40 years has been primarily of meteorological origin.     

Nitrate Artifacts during PM25 Sampling in the South Coast Air Basin of California

ABSTRACT

In February 1993, the South Coast Air Basin (SCAB) was redesignated as a “serious” nonattainment area for PM10. To improve the understanding and characterization of fine particulate matter in the SCAB, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive PM₁₀ Technical Enhancement Program (PTEP). Using enhanced PTEP monitors (specially designed multichannel/multifilter samplers), a one-year fine particulate matter (PM) monitoring program was initiated in January 1995. As part of the special monitoring program, nitric acid, ammonia, and speciated PM₁₀ and PM_2.5 concentrations were measured at five locations in the SCAB (downtown Los Angeles, Anaheim, Diamond Bar, Fontana, and Rubidoux) and at one background station (San Nicolas Island). The PM2.5 data are the first spatially resolved speciated data collected in the SCAB on an annual basis. Within the SCAB, where nitrate is a major component of PM_2.5, nitrate losses have been documented. The spatial and temporal variations of the nitrate losses during PM_2.5 sampling and the uncertainties of the nitrate losses are discussed. Significant losses occur at a low mass range, between 10 and 50 ìg/m³. Significant gains occur at an even lower mass range of less than 30 ìg/m³. On an annual average basis, nitrate losses vary between 1.25 and 2.32 ìg/m³ and the SCAB-wide average value of nitrate loss is 1.8 ìg/m³ based on five PTEP stations in the SCAB. The maximum nitrate losses for each station vary from 6.4 ìg/m³ to 22.5 ìg/m ³. Theoretical prediction of the sampling efficiency of the nitrate during PM_2.5 sam - pling was compared with the PTEP data. In general, theoretical prediction was in good agreement with measured values.     

Compounds in Airborne Participates: Salts and Hydrocarbons

Concentrations of 10 polycyclic aromatic hydrocarbons (PAH), the aliphatlcs as a group, sulfate, nitrate, fluoride, acidity, and carbon In the airborne partlculate matter were measured at 16 sites In Cleveland, OH over a 1 year period during 1971 and 1972. Analytical methods used included gas chromatography, colorimetry, and combustion techniques. Uncertainties in the concentrations associated with the sampling procedures, and the analytical methods are evaluated. The data are discussed relative to other studies and source origins. Benzo(a)pyrene and its high concentrations downwind of coke ovens are discussed. Hydrocarbon correlation studies indicated no significant relations among compounds studied.     

Air Pollution Damage to the Forests of the Sierra Nevada Mountains of California

Numerous oxidant-injured ponderosa pine and other tree species have been detected in the lower elevation forests of the southern Sierra Nevada mountain range of California in the Sequoia National Forest, Sequoia-Kings Canyon National Parks, and on state and private lands. Affected pines were observed in a broad band following the many ridges that rise above the Central Valley floor to the 1900-2600 m elevation. Slight symptoms of ozone chlorotic mottle on ponderosa pine appeared from about 1000 m altitude, increased in severity as elevation increased and then diminished in severity above 2600 m. An apparent east to west gradient of disease was discovered; severity lessened as distance from the Central Valley increased. Atmospheric monitoring in three forested sites suggests that ozone occurs in doses sufficient to elicit symptoms of this widespread disease.     

Occurrence of Eleven Metals in Airborne Participates and in Surficial Materials

The amounts of eleven metals in urban airborne particulate matter samples collected in the United States from 1965 to 1974 (urban and nonurban) are described in two frames of reference: 1) concentration per unit volume of air; and 2) relative abundance in the collected particulate matter compared with surficial materials (subsurface soils) of the continental U. S. If it may be assumed that airborne particulates of solely natural origin would contain these metals in proportions similar to those in uncontaminated subsurface soils, then instances of metals whose proportions in actual particulate samples exceed soil sample proportions may reasonably be ascribed to the influence of human activity. Lead and, tentatively, cadmium exhibit general and significant enrichment in airborne particulate matter above their natural abundances in U. S. soils. Vanadium exhibits enrichment primarily in the northeastern U. S. The enrichment of copper has been traced to contamination from the sampler's own motor. Beryllium, chromium, cobalt, iron, manganese, nickel, and titanium appear to occur in airborne particulates in proportions comparable with those to be expected in natural aeolian dusts.     

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.     

Trends and Relationships of O3, NOx and HC in the South Coast Air Basin of California

A basin-wide air quality trend analysis for the South Coast Air Basin of California is conducted for hydrocarbons (HC), NO_x, O₃ and CO using multi-station composite daily maximum-hour average ambient concentrations for the third quarter (July, August and September) from 1968 to 1985. Emissions and air quality trends are compared for the period 1968-1984. Ambient HC and NOX trends are somewhat different from estimated emission trends of HC and NO_x, while a definite, downward trend of ambient CO is consistent with vehicular emission control measures. Basin-wide ambient HC, NO_x and O₃ appear to show downward trends for the period 1970-1985, but because of high fluctuations it is difficult to delineate trends for shorter periods. The meteorology (850 mb temperature)-adjusted O₃ shows a more consistent downward trend than does unadjusted O₃. Polynomial and multiplicative regression models for basin-wide empirical O₃-HC-NO_x relationships Indicate that the O₃ variation is explained largely by the meteorological variable (850 mb temperature) although model estimations are improved by adding HC and NO_x concentration terms.     

Evaluation of the Effects of Emission Reductions on Secondary Particulate Matter in the South Coast Air Basin of California

An Aerosol Trajectory Model (ATM) is applied to the South Coast Air Basin of California for a two-day episode in August 1982 to evaluate proposed control strategies that aim to reduce atmospheric aerosols. Model predictions Indicate that secondary organic aerosols decrease linearly with reactive hydrocarbon emissions. In addition, the model shows that If sulf ate is produced only in the gas phase by oxidation of SO₂, then reduction In SO₂ emissions yields a nearly proportional decrease In sulfate levels. Reduction in ammonia emissions, combined with reduction of NO_x emissions, gives the best results In terms of nitrate control. The order in which the emission controls are implemented Is predicted to have a major impact on the reduction of secondary atmospheric aerosols.     

Ammonia emissions from a representative in-use fleet of light and medium-duty vehicles in the California South Coast Air Basin

We used Fourier Transform Infrared Spectroscopy (FTIR) to measure tailpipe ammonia emissions from a representative fleet of 41 light and medium-duty vehicles recruited in the California South Coast Air Basin. A total of 121 chassis dynamometer emissions tests were conducted on these vehicles and the test results were examined to determine the effects of several key variables on ammonia emissions. Variables included vehicle type, driving cycle, emissions technology, ammonia precursor emissions (i.e. CO and NOx) and odometer readings/model year as a proxy for catalyst age. The mean ammonia emissions factor was 46 mg km^?1 (σ = 48 mg km^?1) for the vehicle fleet. Average emission factors for specific vehicle groups are also reported in this study. Results of this study suggest vehicles with the highest ammonia emission rates possess the following characteristics: medium-duty vehicles, older emissions technologies, mid-range odometer readings, and higher CO emissions. In addition, vehicles subjected to aggressive driving conditions are likely to be higher ammonia emitters. Since the vehicles we studied were representative of recent model year vehicles and technologies in urban airsheds, the results of our study will be useful for developing ammonia emissions inventories in Los Angeles and other urban areas where California-certified vehicles are driven. However, efforts should also be made to continue emissions testing on in-use vehicles to ensure greater confidence in the ammonia emission factors reported here.     

Visibility in California

A comprehensive study is conducted of visibility in California using prevailing visibility measurements at 67 weather stations in conjunction with data on particulate concentrations and meteorology. The weather station visibility data, when handled with special techniques that account for the nature of visibility reporting practices, prove to be of very good quality for the purposes of most of the analyses that are attempted. It is found that the most important meteorological parameters with respect to visibility are relative humidity, temperature, and special weather events (especially fog). A detailed isopleth map of visibility within California, when compared with earlier work on nationwide visibility, reveals that California experiences far more severe and complex spatial gradients in visibility than those observed anywhere else in the U.S. Two major pockets of heavy man-made visibility impact in California are the Los Angeles basin and the San Joaquin Valley. The spatial, seasonal, and diurnal patterns of visibility are found to be readily explainable in terms of corresponding patterns in emissions, air quality, and meteorology. Regression analyses relating visibility to relative humidity and aerosol concentrations produce high levels of correlation and physically reasonable regression coefficients; these analyses indicate that secondary aerosols are major contributors to visibility reduction in California. An analysis of long-term visibility trends from 1949 to 1976 reveals several interesting features in historical visibility changes for California.