Ozone and other air quality-related variables affecting visibility in the southeast United States

An analysis of ozone (O3) concentrations and several other air quality-related variables was performed to elucidate their relationship with visibility at five urban and semi-urban locations in the southeast United States during the summer seasons of 1980-1996. The role and impact of O3 on aerosols was investigated to ascertain a relationship with visibility. Regional trend analysis over the 1980s reveals an increase in maximum O3 concentration coupled with a decrease in visibility. However, a similar analysis for the 1990s shows a leveling-off of both O3 and visibility; in both cases, the results were not statistically significant at the 5% level. A case study of site-specific trends at Nashville, TN, followed similar trends. To better understand the relationships between O3 concentration and visibility, the analysis was varied from yearly through daily to hourly averaged values. This increased temporal resolution showed a statistically significant inverse relationship between visibility and O3. Site-specific hourly r2 values ranged from 0.02 to 0.43. Additionally, by performing back-trajectory analysis, it was found that the visibility degraded by air mass migration over polluted areas.     

Characterizing changes in surface ozone levels in metropolitan and rural areas in the United States for 1980–2008 and 1994–2008

In this analysis, we characterize urban and rural ozone (O₃) trends across the US for the periods 1980–2008 (29 years) and 1994–2008 (15 years) using three exposure metrics, which summarize daily O₃ concentrations to reflect different ways O₃ may affect human health and vegetation. We observe that a statistically significant trend at a specific monitoring site, using one exposure metric, does not necessarily result in a similar trend using the other two metrics. The two most common trends among the monitoring sites are either a continuation of negative trending over the 29-year period or a shift from negative to no trend status, indicating a leveling off of the trending. Very few sites exhibit statistically significant increases in the exposure indices. In characterizing the statistically significant changes in the distribution of hourly average O₃, we observe subtle statistically significant changes in the lower part of the distribution (i.e., below 50 ppb) that are not necessarily captured by the trending patterns associated with the three exposure metrics. Using multisite data from 12 metropolitan cities, we find that as the frequency of higher hourly average concentrations is reduced, the lower hourly average concentrations also move upward toward the mid-level values. The change in the number of the hourly average concentrations in the lower range is consistent with decreased NO scavenging. We recommend assessing possible subtle shifts in O₃ concentrations by characterizing changes in the distribution of hourly average concentrations by month. Identifying statistically significant monthly changes in the mid- and low-level hourly average concentrations may provide important information for assessing changes in physical processes associated with global climate change, long-range transport, and the efficacy of models used for emission and risk reductions. Our results indicate that it is important to investigate the change in the trending pattern with time (e.g., moving 15-year trending) in order to assess how year-to-year variability may influence the trend calculation.     

Development and Analysis of Oxygen-Sensing Probes for In Situ Monitoring of Unsaturated Solid-State Biodegradation Processes

ABSTRACT

Oxygen (O₂) sensors have been developed for in situ measurement of O₂ in high-solids degradation processes. The O₂ sensor has been shown to withstand the corrosive environment of the biodegradation process with high humidity and temperatures exceeding 60 ^oC. Calibration tests prior to and after in situ operation showed the sensor to perform accurately and reproducibly after 71 days of in situ operation.

A linear relationship between O₂-sensor output and water vapor pressure was confirmed through calibration experiments. To compensate for the effect of water vapor pressure on O₂-sensor measurements, O₂ concentration was expressed on a dry air basis using the confirmed linear relationship. In situ O₂-sensor output expressed on a dry air basis was found to follow trends of gas samples analyzed by gas chromatography with good agreement.     

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.     

Characteristics and origins of air pollutants in Wuhan,China, based on observations and hybrid receptor models

To identify the characteristics of air pollutants and factors attributing to the formation of haze in Wuhan, this study analyzed the hourly observations of air pollutants (PM_2.5, PM₁₀, NO₂, SO₂, O₃, and CO) from March 1, 2013, to February 28, 2014, and used hybrid receptor models for a case study. The results showed that the annual average concentrations for PM_2.5, PM₁₀, NO₂, SO₂, O₃, and CO during the whole period were 89.6 μg m^?3, 134.9 μg m^?3, 54.9 μg m^?3, 32.4 μg m^?3, 62.3 μg m^?3, and 1.1 mg m^?3, respectively. The monthly variations revealed that the peak values of PM_2.5, PM₁₀, NO₂, SO₂, and CO occurred in December because of increased local emissions and severe weather conditions, while the lowest values occurred in July mainly due to larger precipitation. The maximum O₃ concentrations occurred in warm seasons from May to August, which may be partly due to the high temperature and solar radiation. Diurnal analysis showed that hourly PM_2.5, PM₁₀, NO₂, and CO concentrations had two ascending stages accompanying by the two traffic peaks. However, the O₃ concentration variations were different with the highest concentration in the afternoon. A case study utilizing hybrid receptor models showed the significant impact of regional transport on the haze formation in Wuhan and revealed that the mainly potential polluted sources were located in the north and south of Wuhan, such as Baoding and Handan in Hebei province, and Changsha in Hunan province. Implications: Wuhan city requires a 5% reduction of the annual mean of PM_2.5 concentration by the end of 2017. In order to accomplish this goal, Wuhan has adopted some measures to improve its air quality. This work has determined the main pollution sources that affect the formation of haze in Wuhan by transport. We showed that apart from the local emissions, north and south of Wuhan were the potential sources contributing to the high PM_2.5 concentrations in Wuhan, such as Baoding and Handan in Hebei province, Zhumadian and Jiaozuo in Henan province, and Changsha and Zhuzhou in Hunan province.     

Long-term trends and characteristics of visibility in two megacities in southwest China: Chengdu and Chongqing

Visibility is a good indicator of air quality because it reflects the combined influences of atmospheric pollutants and synoptic processes. Trends in visibility and relationships with various factors in Chengdu and Chongqing, two megacities in southwest China, were analyzed using daily data from National Climatic Data Center and the Air Pollution Index (API) of the Ministry of Environmental Protection of China. Average annual visibility during the period of 1973–2010 was 8.1 ± 3.9 in Chengdu and 6.2 ± 4.3 km in Chongqing. PM₁₀ dominates the reported primary pollutants in both cities, although concentrations have decreased from a high of 127.9 and 150 µg m³ before 2005 to 100.4 and 93.5 µg m^?3 in Chengdu and Chongqing, respectively. Low average visibility and extremely high levels of PM10 were observed in winter, whereas relative humidity had irregular and weak seasonal variations. Visibility in both cities has deteriorated in comparison to the 1960s and 1970s, mostly due to the elevation of optical depth caused by anthropogenic pollution.

Correlations and principal component analysis (PCA) were undertaken to determine the key factors affecting visibility. Visibility was only moderately correlated with PM₁₀. In Chengdu, visibility displayed weak correlations with various factors, whereas visibility in Chongqing was most strongly related to relative humidity due to the atmospheric particulates in the region containing more hygroscopic components. PCA results further confirmed that high relative humidity and low wind speed increased the occurrence of low visibility events under high PM₁₀ concentrations. Temperature and pressure, as indicators of weather systems, also played important roles in affecting visibility. Mathematical models of visibility prediction indicated that wind speed had the largest coefficients among all meteorological factors, and reductions in PM₁₀ concentration only led to minor improvements in visibility.

Implications: Long-term data indicates that visibility in Chengdu and Chongqing has been lower than 10 km since the 1970s, and the poor visibility primarily results from anthropogenic pollution. Although PM₁₀ concentrations have decreased consistently to around 100 μg m^?3, trends of visibility have shown no improvement but much fluctuation. Correlation and principal component analysis demonstrate that low visibility in Chengdu is influenced by high relative humidity, while in Chongqing the degrading visibility is related with high relative humidity and pressure and low wind speed under a stable weather system. The results are important to understand the widespread haze event in the two megacities of southwest China.     

An ozone climatology: relationship between meteorology and ozone in the Southeast USA

A statistical analysis of ozone (O₃) concentrations and meteorological parameters was performed to determine the relationship between meteorological changes and ambient O₃ concentrations in the Southeast United States. The correlation between average daily maximum O₃ concentration and various meteorological variables was analysed on a monthly basis from April through October during 1980-1994. The correlations were strongest during the summer months, particularly June, July, and August. Analysis of long term O₃ concentration trends indicates increasing trends during the 1980s and decreasing trends during the early 1990s.     

Characterization and Identification of Trends in Average Ambient Ozone and Fine Particulate Matter Levels through Trajectory Cluster Analysis in Eastern Canada

Abstract

In many locations in Eastern Canada, ambient levels of fine particulate matter (PM_2.5) and surface ozone (O₃) depend on airflow direction and synoptic scale meteorological conditions. In this study, a cluster analysis was performed on 10 yr (1994 –2003) of back-trajectory data for 11 locations in Eastern Canada, resulting in the identification of 10 unique back-trajectory clusters (or airflows) for each location. The airflows were then used to characterize and identify spatial and temporal trends in the daily maximum 8-hr average O₃ (dmax 8-hr O₃) and the daily average PM_2.5 levels. Results showed that airflows from the southwest passing over Michigan and Southern Ontario were associated, on average, with the highest O₃ levels at most locations in Eastern Canada.For PM_2.5, the highest levels occurred with airflows from the Eastern Ohio River Valley. At major urban locations in Ontario and Quebec, the warm season mean (May to September) dmax 8-hr O₃ and the annual mean PM_2.5 were, on average, 12 parts per billion and 7.6 μg/m³ higher, respectively, than airflows from the north. Elevated levels of O₃ and PM_2.5 also occurred under light airflows, and, on average, the levels under light airflows were higher than their nonlight counterparts. At several locations in Canada, including Toronto, Montreal, Quebec City, and Kejimkujik, the annual warm season mean dmax 8-hr O₃ experienced a statistically significant (95% confidence) increasing trend over the 10-yr period. When airflow direction was considered, a number of locations experienced statistically significant upward trends in O₃ for airflow from the north and northwest. Several locations also showed significant upward trends associated with airflow from the southwest passing over Michigan and Southwestern Ontario. Although there are no statistically significant downward trends, airflows from the southwest have shown a reduction in O₃ levels in Southwestern Ontario in more recent years.     

Precursor reductions and ground-level ozone in the Continental United States

Numerous papers analyze ground-level ozone (O₃) trends since the 1980s, but few have linked O₃ trends with observed changes in nitrogen oxide (NO_x) and volatile organic compound (VOC) emissions and ambient concentrations. This analysis of emissions and ambient measurements examines this linkage across the United States on multiple spatial scales from continental to urban. O₃ concentrations follow the general decreases in both NO_x and VOC emissions and ambient concentrations of precursors (nitrogen dioxide, NO₂; nonmethane organic compounds, NMOCs). Annual fourth-highest daily peak 8-hr average ozone and annual average or 98th percentile daily maximum hourly NO₂ concentrations show a statistically significant (p < 0.05) linear fit whose slope is less than 1:1 and intercept is in the 30 to >50 ppbv range. This empirical relationship is consistent with current understanding of O₃ photochemistry. The linear O₃–NO₂ relationships found from our multispatial scale analysis can be used to extrapolate the rate of change of O₃ with projected NO_x emission reductions, which suggests that future declines in annual fourth-highest daily average 8-hr maximum O₃ concentrations are unlikely to reach 65 ppbv or lower everywhere in the next decade. Measurements do not indicate increased annual reduction rates in (high) O₃ concentrations beyond the multidecadal precursor proportionality, since aggressive measures for NO_x and VOC reduction are in place and have not produced an accelerated O₃ reduction rate beyond that prior to the mid-2000s. Empirically estimated changes in O₃ with emissions suggest that O₃ is less sensitive to precursor reductions than is found by the CAMx (v. 6.1) photochemical model. Options for increasing the rate of O₃ change are limited by photochemical factors, including the increase in NO_x sensitivity with time (NMOC/NO_x ratio increase), increase in O₃ production efficiency at lower NO_x concentrations (higher O₃/NO_y ratio), and the presence of natural NO_x and NMOC precursors and background O₃.

Implications:?This analysis demonstrates empirical relations between O₃ and precursors based on long term trends in U.S. locations. The results indicate that ground-level O₃ concentrations have responded predictably to reductions in VOC and NO_x since the 1980s. The analysis reveals linear relations between the highest O₃ and NO₂ concentrations. Extrapolation of the historic trends to the future with expected continued precursor reductions suggest that achieving the 2014 proposed reduction in the U.S. National Ambient Air Quality Standard to a level between 65 and 70 ppbv is unlikely within the next decade. Comparison of measurements with national results from a regulatory photochemical model, CAMx, v. 6.1, suggests that model predictions are more sensitive to emissions changes than the observations would support.     

Extending the Kolmogorov–Zurbenko Filter: Application to Ozone,Particulate Matter,and Meteorological Trends

Abstract

Tropospheric ozone (O₃) and particulate matter (PM) are pollutants of great concern to air quality managers. Federal standards for these pollutants have been promulgated in recent years because of the known adverse effects of the pollutants on human health, the environment, and visibility. Local meteorological conditions exert a strong influence over day‐to‐day variations in pollutant concentrations; therefore, the meteorological signal must be removed in order for air quality planners and managers to examine underlying emissions-related trends and make better air quality management decisions for the future. Although the Kolmogorov–Zurbenko (KZ) filter has been widely used for this type of trend separation in O₃ studies in the eastern United States, this article aims to extend the method in three key ways. First, whereas the KZ filter is known as a useful tool for O₃ analysis, this study also evaluates its effectiveness when applied to PM. Second, the method was applied to Tucson, AZ, a city in the semi‐arid southwestern United States (Southwest), to evaluate the appropriateness of the method in a region with weaker synoptic weather controls on air quality than the eastern United States. Third, additional forms of output were developed and tailored to be more applicable to decision-makers’ needs through a partnership between academic researchers and air quality planners and managers. Results of the study indicate that the KZ filter is a useful method for examining emissions‐related PM trends, resulting in small, but potentially significant, differences after adjustment. For the Tucson situation with weaker synoptic controls, the KZ method identified mixing height as a more important variable than has been found in other cities.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston,Texas

In Houston, some of the highest measured 8-hr ozone (O₃) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr, or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O₃ concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O₃ changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O₃ concentrations, the AQM predicted high O₃ over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O₃, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O₃ concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O₃ concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O₃ standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O₃, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.

Implications To show the attainment of the O₃ standard, the U.S. Environmental Protection Agency (EPA) requires the use of observations and model predictions under the assumption that simulations are capable of reproducing observed phenomena. The regulatory model is unable to reproduce observed behavior measured in the observational database. If the large observed hourly changes were indicative of a separate cause of high O₃, then the model would not include that cause. Inaccurate model predictions may prompt air quality regulators to enact control strategies that are effective in the modeling system, but prove ineffective in the real world.     

Visibility and Mass Concentration in a Nonurban Environment

Considerable interest is currently directed toward atmospheric visibility and its relationship to particle size and mass concentration. Previous work has been limited to heavily polluted urban areas, and visibility studies have not included particle size characterization. An air sampling program was carried out in a nonurban, low pollution area to relate: (a) total particulate mass concentration measured with a high-volume sampler, (b) particulate mass size distribution measured with aerodynamic size selective samplers, and (c) visual range measured by the integrating nephelometer. For low suspended particulate mass concentrations, the following relationship was defined between visual range (L_v) and mass concentration (M ? μg/m³):     

Defining the Photochemical Contribution to Particulate Matter in Urban Areas Using Time-Series Analysis

Abstract

The objective of this project is to demonstrate how the ambient air measurement record can be used to define the relationship between O₃ (as a surrogate for photochemistry) and secondary particulate matter (PM) in urban air. The approach used is to develop a time-series transfer-function model describing the daily PM₁₀ (PM with less than 10 μm aerodynamic diameter) concentration as a function of lagged PM and current and lagged O₃, NO or NO₂, CO, and SO₂. Approximately 3 years of daily average PM₁₀, daily maximum 8-hr average O₃ and CO, daily 24-hr average SO₂ and NO₂, and daily 6:00 a.m.-9:00 a.m. average NO from the Aerometric Information Retrieval System (AIRS) air quality subsystem are used for this analysis. Urban areas modeled are Chicago, IL; Los Angeles, CA; Phoenix, AZ; Philadelphia, PA; Sacramento, CA; and Detroit, MI. Time-series analysis identified significant autocorrelation in the O₃, PM₁₀, NO, NO₂,CO, and SO₂ series. Cross correlations between PM₁₀ (dependent variable) and gaseous pollutants (independent variables) show that all of the gases are significantly correlated with PM₁₀ and that O₃ is also significantly correlated lagged up to two previous days. Once a transfer-function model of current PM₁₀ is defined for an urban location, the effect of an O₃-control strategy on PM concentrations is estimated by calculating daily PM₁₀ concentrations with reduced O₃ concentrations. Forecasted summertime PM₁₀ reductions resulting from a 5 percent decrease in ambient O₃ range from 1.2 μg/m³ (3.03%) in Chicago to 3.9 μg/m³ (7.65%) in Phoenix.     

Plume analysis from field evaluations of a portable air quality monitoring system

ABSTRACT

Near-road measurements in Rochester, NY with a Portable Air Quality Monitoring System indicate a significant plume control of PM_2.5 black carbon (BC) concentrations. This study evaluates the performance of two portable air quality enclosures deployed at collocated research sites to determine their accuracy and usefulness in field deployments, and specifically in pollution plume analysis. One system deployed collocated sensors for measurement of particulate matter mass concentration (Thermo pDR 1500 against Tapered Element Oscillating Microbalance (TEOM) measurement) and the second system deployed sensors for measurement of black carbon (Magee AE33 aethalometer and Brechtel Tricolor Absorption Photometer) in ambient and near-road locations in Rochester, New York, respectively. While the optical PM_2.5 sensors tended to be biased in their determination of concentration by ~15%, they followed changes and trends in concentration very well. The black carbon sensors in the portable systems agreed very well with each other and with the collocated sensor. As a case study to determine the contribution from statistically significant short-lived excursions of pollutant concentration, Morlet wavelet analysis was performed on data from the portable system sensors. Black carbon was found to be strongly influenced by plume behavior with significant plume excursions representing just over 12% of all data points and contributing on average 1 µg/m³ of black carbon above ambient concentrations.

Implications: This paper first evaluates two air pollutant monitoring enclosures with wide applicability including near-road detection of pollutants. Then, we present a novel method to designate isolate statistically significant excursions in air pollution concentration which can be used to determine the impact of pollutant plumes as observed in PM and black carbon behavior near road.     

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.     

Air Quality Modeling in the South Coast Air Basin of California: What Do the Numbers Really Mean?

Abstract

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O₃) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O₃ concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O₃ concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O₃ concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O₃ concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O₃ predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O₃ concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

Development of a Speciated,Hourly, and Gridded Air Pollutants Emission Modeling System—A Case Study on the Precursors of Photochemical Smog in the Seoul Metropolitan Area,Korea

ABSTRACT

A speciated, hourly, and gridded air pollutants emission modeling system (SHEMS) was developed and applied in predicting hourly nitrogen dioxide (NO₂) and ozone (O₃) levels in the Seoul Metropolitan Area (SMA). The primary goal of the SHEMS was to produce a systemized emission inventory for air pollutants including ozone precursors for modeling air quality in urban areas.

The SHEMS is principally composed of three parts: (1) a pre-processor to process emission factors, activity levels, and spatial and temporal information using a geographical information system; (2) an emission model for each source type; and (3) a post-processor to produce report and input data for air quality models through database modeling. The source categories in SHEMS are point, area, mobile, natural, and other sources such as fugitive emissions. The emission database produced by SHEMS contains 22 inventoried compounds: sulfur dioxide, NO₂, carbon monoxide, and 19 speciated volatile organic compounds. To validate SHEMS, the emission data were tested with the Urban Airshed Model to predict NO₂ and O₃ concentrations in the SMA during selected episode days in 1994. The results turned out to be reliable in describing temporal variation and spatial distribution of those pollutants.     

Indoor Fine Particles: The Role of Terpene Emissions from Consumer Products

Abstract

Consumer products can emit significant quantities of terpenes, which can react with ozone (O₃). Resulting byproducts include compounds with low vapor pressures that contribute to the growth of secondary organic aerosols (SOAs). The focus of this study was to evaluate the potential for SOA growth, in the presence of O₃, following the use of a lime-scented liquid air freshener, a pine-scented solid air freshener, a lemon-scented general-purpose cleaner, a wood floor cleaner, and a perfume. Two chamber experiments were performed for each of these five terpene-containing agents, one at an elevated O₃ concentration and the other at a lower O₃ concentration. Particle number and mass concentrations increased and O₃ concentrations decreased during each experiment. Experiments with terpene-based air fresheners produced the highest increases in particle number and mass concentrations. The results of this study clearly demonstrate that homogeneous reactions between O₃ and terpenes from various consumer products can lead to increases in fine particle mass concentrations when these products are used indoors. Particle increases can occur during periods of elevated outdoor O₃ concentrations or indoor O₃ generation, coupled with elevated terpene releases. Human exposure to fine particles can be reduced by minimizing indoor terpene concentrations or O₃ concentrations.     

An historical experiment: Los Angeles smog evolution observed by blimp

Observations of smog over the Los Angeles Basin (LAB) links high oxidant mixing ratios with poor visibility, sometimes <5 km. By the 1970s, investigators recognized that most of the aerosol affecting visibility was from gaseous oxidation products, sulfate, nitrate, and organic carbon. This led to the 1972–1973 Aerosol Characterization Experiment (ACHEX), which included observations at the ground and from aircraft. Part of ACHEX was the measurement of smog by blimp in a Lagrangian-like format. The experiment on September 6, 1973, demonstrated that a blimp could travel with the wind across the LAB, observing ozone (O₃) and precursors, and particles of different size ranges. These included condensation nuclei (CN) concentrations dominated by particles of ≤ 0.1 µm diameter and light scattering coefficient (b_sc) representing mainly particles of 0.1–2.0 µm diameter. The results indicated a pollutant variation similar to that measured at a fixed site. Ozone was produced in an air mass, reaching a maximum of ~400 ppb in the presence of nitrogen oxides (NO_x) and nonmethane hydrocarbons (NMHCs), then declined. Although the photochemistry was developing, b_sc grew with O₃ mixing ratio to a quasi-steady state at ~9–10 × 10^?4 m^?1, decreasing in value much later with decease in O₃. The light scattering coefficient was found to be positively associated with the O₃ mixing ratio, whereas CN concentrations were negatively proportional to O₃ mixing ratio. The blimp experiment was supported with aircraft vertical profiles and ground-level observations from a mobile laboratory. The blimp flight obtained combined gas and particle changes aloft that could not be obtained by ground or fixed-wing aircraft measurements alone. The experiment was partially successful in achieving a true Lagrangian characterization of smog chemistry in a constrained or defined “open” air mass.

Implications: The Los Angeles experiment demonstrated the use of a blimp as a platform for measurement of air pollution traveling with an air mass across an urban area. The method added unique data showing the relationship between photochemical smog chemistry and aerosol dynamics in smog. The method offers an alternative to reliance on smog chamber and modeling observations to designing air quality management strategies for reactive pollutants.