Weekday versus weekend activity patterns for ozone precursor emissions in California's South Coast Air Basin

Ambient O3 concentrations in California's South Coast Air Basin (SoCAB) can be as much as 55% higher on weekends than on weekdays under comparable meteorological conditions. This is paradoxical because emissions of O3 precursors (hydrocarbons, CO, and nitrogen oxides [NOx]) are lower on weekends. Day-of-week emissions activity data were collected and analyzed to investigate the hypothesized causes of the "weekend O3 effect." Emission activity data were collected for various mobile, area, and point sources throughout the SoCAB, including on-road vehicles, lawn and garden equipment, barbecues, fireplaces, solvent use, and point sources with continuous emission monitoring data. The results of this study indicate significant differences between weekday and weekend emission activity patterns and emissions. Their combined effect results in a 12-18% decrease in reactive organic gases (ROGs) and a 35-41% decrease in NOx emissions on Saturdays and Sundays, respectively, relative to weekdays in summer 2000. These changes in emissions result in an increase of more than 30% in the ROG/NOx ratio on weekends compared with weekdays, which, along with lower NOx emissions, leads to increased O3 production on weekends.     

Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin

For at least 30 years, ozone (O3) levels on weekends in parts of California's South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O3 precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NOx) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O3 formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NOx associated with black carbon (BC) to NOx associated with carbon monoxide (CO) were approximately 1.25 +/- 0.22 during weekdays and 0.76 +/- 0.07 and 0.52 +/- 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NOx emissions from diesel exhaust can be a major factor causing lower NOx mixing ratios and higher NMHC/NOx ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NOx ratios on weekend mornings.     

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.     

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.     

Projected ozone trends and changes in the ozone-precursor relationship in the South Coast Air Basin in response to varying reductions of precursor emissions

This study examined the effects of varying future reductions in emissions of oxides of nitrogen (NO_x) and volatile organic compounds (VOC) on the location and magnitude of peak ozone levels within California’s South Coast Air Basin (SoCAB or Basin). As ozone formation is currently VOC-limited in the Basin, model simulations with 2030 baseline emissions (?61% for NO_x and ?32% for VOC from 2008) predict 10–20% higher peak ozone levels (i.e., NO_x disbenefit) in the western and central SoCAB compared with the 2008 base simulation. With additional NO_x reductions of 50% beyond the 2030 baseline emissions (?81% from 2008), the predicted ozone levels are reduced by about 15% in the eastern SoCAB but remain comparable to 2008 levels in the western and central Basin. The Basin maximum ozone site shifts westward to more populated areas of the Basin and will result potentially in greater population-weighted exposure to ozone with even a relatively small shortfall in the required NO_x reductions unless accompanied by additional VOC reductions beyond 2030 baseline levels. Once committed to a NO_x-focused control strategy, NO_x reductions exceeding 90% from 2008 levels will be necessary to attain the ozone National Ambient Air Quality Standards (NAAQS). The findings from this study and other recent work that the current VOC emission estimates are underestimated by about 50% suggest that greater future VOC reductions will be necessary to reach the projected 2030 baseline emissions. Increasing the base year VOC emissions by a factor of 1.5 result in higher 2008 baseline ozone predictions, lower relative response factors, and about 20% lower projected design values. If correct, these findings have important implications for the total and optimum mix of VOC and NO_x emission reductions that will be required to attain the ozone NAAQS in the SoCAB.

Implications: Results of this study indicate that ozone levels in the western and central SoCAB would remain the same or increase with even a relatively small shortfall in the projected NO_x reductions under planned NO_x-focused controls. This possibility, therefore, warrants a rigorous analysis of the costs and effects of varying reductions of VOC and NO_x on the formation and combined health impacts of ozone and secondary particles. Given the nonlinearity of ozone formation, such analyses should include the implications of gradually increasing global background ozone concentrations and the Basin’s topography and meteorology on the practical limits of alternative emission control strategies.     

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.     

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.     

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.     

Development of a PM2 5 Emissions Inventory for the South Coast Air Basin

ABSTRACT

With the promulgation of a national PM_2.5 ambient air quality standard, it is important that PM_2.5 emissions inventories be developed as a tool for understanding the magnitude of potential PM2.5 violations. Current PM₁₀ inventories include only emissions of primary particulate matter (1 ^ï PM), whereas, based on ambient measurements, both PM₁₀ and PM2.5 emissions inventories will need to include sources of both 1^ï PM and secondary particulate matter (2^ï PM). Furthermore, the U. S. Environmental Protection Agency’s (EPA) current edition of AP-42 includes size distribution data for 1o PM that overestimate the PM_2.5 fraction of fugitive dust sources by at least a factor of 2 based on recent studies.

This paper presents a PM_2.5 emissions inventory developed for the South Coast Air Basin (SCAB) that for the first time includes both 1^ï PM and 2^ï PM. The former is calculated by multiplying PM₁₀ emissions estimates by the PM_2.5/PM₁₀ ratios for different sources. The latter is calculated from estimated emission rates of gas-phase aerosol precursor and gas to aerosol conversion rates consistent with the measured chemical composition of ambient PM_2.5 concentrations observed in the SCAB. The major finding of this PM_2.5 emissions inventory is that the ^2ï aerosol component is more than twice the ^1ï aerosol component, which may result in widely different control strategies being required for fine PM and coarse PM.     

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.     

香港港口氮氧化物和臭氧的变化特征和周末效应

为了研究香港港口氮氧化物和臭氧（NO2、NOx和O3）的周末效应,本文收集香港港口15年的污染数据进行统计分析。首先分析污染物的日变化特征,结果发现工作日NO2和NOx浓度高于周六,周六浓度高于周日的情形。与此相反,工作日O3浓度低于周六,周六浓度低于周日。其次分析污染物年变化,结果表明近些年NO2和NOx呈降低趋势,O3呈增加趋势。还发现NO2、NOx和O3的周末效应减弱。然后使用线性回归分析光化学氧化剂（OX,O3+NO2）的局地和区域贡献,结果发现受港口作业周期性变化的影响,OX的局地贡献表现出工作日高于周六,周六高于周日的周末效应现象。最后分析了OX局地贡献的昼夜差异,结果显示白天OX局地贡献的周末效应明显强于晚上。     

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

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

Projected changes in particulate matter concentrations in the South Coast Air Basin due to basin-wide reductions in nitrogen oxides,volatile organic compounds,and ammonia emissions

An ozone abatement strategy for the South Coast Air Basin (SoCAB) has been proposed by the South Coast Air Quality Management District (SCAQMD) and the California Air Resources Board (ARB). The proposed emissions reduction strategy is focused on the reduction of nitrogen oxide (NO_x) emissions by the year 2030. Two high PM_2.5 concentration episodes with high ammonium nitrate compositions occurring during September and November 2008 were simulated with the Community Multi-scale Air Quality model (CMAQ). All simulations were made with same meteorological files provided by the SCAQMD to allow them to be more directly compared with their previous modeling studies. Although there was an overall under-prediction bias, the CMAQ simulations were within an overall normalized mean error of 50%; a range that is considered acceptable performance for PM modeling. A range of simulations of these episodes were made to evaluate sensitivity to NO_x and ammonia emissions inputs for the future year 2030. It was found that the current ozone control strategy will reduce daily average PM_2.5 concentrations. However, the targeted NO_x reductions for ozone were not found to be optimal for reducing PM_2.5 concentrations. Ammonia emission reductions reduced PM_2.5 and this might be considered as part of a PM_2.5 control strategy.

Implications: The SCAQMD and the ARB have proposed an ozone abatement strategy for the SoCAB that focuses on NO_x emission reductions. Their strategy will affect both ozone and PM_2.5. Two episodes that occurred during September and November 2008 with high PM_2.5 concentrations and high ammonium nitrate composition were selected for simulation with different levels of nitrogen oxide and ammonia emissions for the future year 2030. It was found that the ozone control strategy will reduce maximum daily average PM_2.5 concentrations but its effect on PM_2.5 concentrations is not optimal.     

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

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

Water Content of Collected Aerosols in the South Coast and Southeast Desert Air Basins

Pollution prevention/waste minimization is a win-win-win situation for government, industry, and the public, which offers more than just protection of the environment for all. Industry gains from reduced capital and operating costs, reduced liabilities, cleaner and safer working conditions, conservation of energy and material resources, and the opportunity for government and industry to work together in a cooperative manner. However, a number of regulatory barriers exist which discourage pollution prevention/waste minimization. This paper provides examples from the aluminum, chemical, petroleum, and wood treating industries of how these regulatory barriers become disincentives. To promote pollution prevention/waste minimization, Congress and the U.S. EPA need to reexamine those RCRA provisions which support a command and control strategy that creates the barriers. The barriers include the distinction between value and valueless materials, offsite storage requirements prior to reuse/recycle, the “Derived from Rule”, the “Burning for Fuel Rule”, land ban technology standards, and RD&;D restrictions. A new RCRA Pollution Prevention/Waste Minimization subtitle is proposed to eliminate or minimize these barriers.     

Heavy metal monitoring of marine algae from the Turkish Coast of the Black Sea, 1998-2000

Concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined in macroalgae samples collected from the Turkish Coast of the Black Sea. Certain algae species were chosen among the green, brown and red algae species at Sile and Sinop sampling stations from 1998 to 2000. In general, as regards the influence of the collection sites on the whole metal accumulation, Sinop is considered to be more polluted than Sile. The concentrations of the heavy metals in Cystoseira barbata algae are compared with previous studies in the same stations. The results showed that all metal levels have gradually decreased during past years. At the same time, Cd, Co, Cr, Cu, Fe, Ni and Pb levels in the present study are lower than in Bosphorus and Marmara Sea algae. However, Mn and Zn concentrations are higher than Bosphorus but lower than at Marmara. According to these findings the heavy metal pollution decreased in Turkish Coast of the Black Sea during the years investigated.     

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.     

Statistical analysis of winter ozone exceedances in the Uintah Basin,Utah, USA

Because of the confluence of several factors (persistent multiday inversions, petroleum production, and snow cover), the Uintah Basin of eastern Utah, USA, exhibits high concentrations of winter ozone. A regression analysis is presented that successfully predicts daily ozone concentration with a standard error of about 11 ppb. It also predicts with 90% accuracy whether any given day will exceed the National Ambient Air Quality Standard for ozone, 70 ppb. An analysis is introduced for calculating a “pseudo-lapse rate,” a determination of inversion intensity in the absence of sounding data. By combining the model with historical meteorological data, it is possible to make long-range predictions about ozone formation. The odds of observing no exceedance days in any given season are 38%. The odds of only three or fewer exceedance days in any given season are 46%.

Implications: This paper provides an improved understanding of the scientific underpinnings of the winter ozone phenomenon and an ability to make long-range predictions.