Demonstrating attainment in Atlanta using urban airshed model simulations: impact of boundary conditions and alternative forms of the NAAQS

Urban Airshed Model-Version IV (UAM-IV) simulations on 7–8 July, 1988 for the Atlanta, Georgia, nonattainment area are used to investigate how recent changes in the National Ambient Air Quality Standard (NAAQS) and changes in boundary concentrations may affect attempts to comply with the standard through local emissions reductions. According to model results, the recently promulgated 8 h NAAQS at a level of 0.08 ppmv will require larger emission reductions to comply with the standard than those that are necessary to comply with the previous 1 h/0.12 ppmv NAAQS. Regardless of the form of the NAAQS or the magnitude of the concentrations of O₃ and its precursors at the model domain boundary, UAM-IV simulations for Atlanta predict that NO_x (NO+NO₂) emission reductions are more effective than volatile organic compound reductions in mitigating O₃ pollution. Moreover, the simulations indicate that NO_x emission reductions greater than 60–75% would be required to demonstrate attainment under either form of the standard, even if boundary concentrations of O₃ and its precursors were substantially reduced. Further research is necessary to determine if this weak response to emission controls is truly representative of the real atmosphere, or is a result of the meteorological conditions specific to this episode, or is an artifact of the UAM-IV model or its inputs.     

Characterization of summertime coarse particulate matter in the Desert Southwest—Arizona,USA

A year-long study was conducted in Pinal County, AZ, to characterize coarse (2.5 – 10 μm aerodynamic diameter, AD) and fine (< 2.5 μm AD) particulate matter (PMc and PMf, respectively) to further understand spatial and temporal variations in ambient PM concentrations and composition in rural, arid environments. Measurements of PMc and PMf mass, ions, elements, and carbon concentrations at one-in-six day resolution were obtained at three sites within the region. Results from the summer of 2009 and specifically the local monsoon period are presented.

The summer monsoon season (July – September) and associated rain and/or high wind events, has historically had the largest number of PM₁₀ NAAQS exceedances within a year. Rain events served to clean the atmosphere, decreasing PMc concentrations resulting in a more uniform spatial gradient among the sites. The monsoon period also is characterized by high wind events, increasing PMc mass concentrations, possibly due to increased local wind-driven soil erosion or transport. Two PM₁₀ NAAQS exceedances at the urban monitoring site were explained by high wind events and can likely be excluded from PM₁₀ compliance calculations as exceptional events. At the more rural Cowtown site, PM₁₀ NAAQS exceedances were more frequent, likely due to the impact from local dust sources.

PM mass concentrations at the Cowtown site were typically higher than at the Pinal County Housing and Casa Grande sites. Crustal material was equal to 52-63% of the PMc mass concentration on average. High concentrations of phosphate and organic carbon found at the rural Cowtown were associated with local cattle feeding operations. A relatively high correlation between PMc and PMf (R²?=?0.63) indicated that the lower tail of the coarse particle fraction often impacts the fine particle fraction, increasing the PMf concentrations. Therefore, reductions in PMc sources will likely also reduce PMf concentrations, which also are near the value of the 24-hr PM_2.5 NAAQS.

Implications: In the desert southwest, summer monsoons are often associated with above average PM₁₀ (<10 μm AD) mass concentrations. Competing influences of monsoon rain and wind events showed that rain suppresses ambient concentrations while high wind increase them. In this region, the PMc fraction dominates PM₁₀ and crustal sources contribute 52-63% to local PMc mass concentrations on average. Cattle feedlot emissions are also an important source and a unique chemical signature was identified for this source. Observations suggest monsoon wind events alone cannot explain PM₁₀ NAAQS exceedances, thus requiring these values to remain in compliance calculations rather than being removed as exceptional wind events.     

Effects of Nighttime Chemistry upon the Transport of Ozone and Ozone Precursors

It has been recognized for several years that ozone in rural areas can exceed the National Ambient Air Quality Standard (NAAQS) for photochemical oxidant whirh was 0.08 ppm for one hour, not to be exceeded more than once per year. During the summer of 1973, the NAAQS was exceeded from 15 to 37% of the time at four rural monitoring sites in Maryland, Pennsylvania, Ohio, and West Virginia.¹ This is a greater violation rate than is found in many urban areas. Dimitriades and Altshuller² have enumerated four possible sources for this rural ozone: (a) transport from urban areas, (b) local photochemical generation from urban ozone precursors, (c) local photochemical generation from precursors of rural origin which may be man-made or natural, and (d) injection of stratospheric ozone into the rural area. This paper considers the chemistry pertinent to the first two of these possible sources of rural ozone, namely the long distance (overnight) transport of ozone and ozone precursors.     

Ozone Transport

Elevated concentrations of ozone, often above the national ambient air quality standard for photochemical oxidants, have been measured in both urban and rural areas of Connecticut. One such episode took place on June 10, 1974. Ozone levels, after stabilizing at values slightly above the standard (i.e., 80 to 110 ppb; Connecticut generated ozone concentrations), rose sharply late in the afternoon reaching concentrations as high as 310 ppb (almost 4 times the standard) in Hartford. The trajectory of the air mass, which arrived in Hartford at the time of maximum O₃ occurence, had its origin in the metropolitan New York area during the early morning rush hour on the episode day. This illustrates that the advective transport of O₃ and O₃ precursors into Connecticut from New York are probably responsible for a significant portion (approximately two-thirds) of the elevated O₃ concentrations measured throughout Connecticut on days when winds are from the south-southwest direction. The fact that peak O₃ levels occur late in the afternoon, several hours after maximum sunlight intensity, reinforces the conclusion that excessive O₃ concentrations developed as O₃ and ozone precursors were generated in the vicinity of New York City and then drifted inland into Connecticut on the afternoon sea breeze.

It appears to be unrealistic to develop a hydrocarbon control strategy for Connecticut in order to meet the photochemical oxidant ambient air quality standard when O₃ and/or ozone precursors ad-vectively transported into the State cause oxidant levels to exceed the standard. The complete cessation of all anthropogenic hydrocarbon emissions in Connecticut would not necessarily assure that the standard would be attained here. The implication is that a regional (i.e., the eastern part of the United States) hydrocarbon control strategy is needed to reduce adequately ozone formation and transport so as to allow Connecticut to meet the current oxidant standard.     

An Operational Assessment of the Application of the Relative Reduction Factors in the Demonstration of Attainment of the 8-Hr Ozone National Ambient Air Quality Standard

Abstract

The U.S. Environmental Protection Agency in 1997 revised the 1-hr ozone (O₃) National Ambient Air Quality Standard (NAAQS) to one based on an 8-hr average, resulting in potential nonattainment status for substantial portions of the eastern United States. The regulatory process provides for the development of a state implementation plan that includes a demonstration that the projected future O₃ concentrations will be at or below the NAAQS based on photochemical modeling and analytical techniques.

In this study, four photochemical modeling systems, based on two photochemical models, Community Model for Air Quality and the Comprehensive Air Quality Model with extensions, and two emissions processing models, Sparse Matrix Optimization Kernel for Emissions and Emissions Modeling System, were applied to the eastern United States, with emphasis on the northeastern Ozone Transport Region in terms of their response to oxides of nitrogen and volatile organic carbon-focused controls on the estimated design values. With the 8-hr O₃ NAAQS set as a bright-line test, it was found that a given area could be termed as being in or out of attainment of the NAAQS depending upon the modeling system. This suggests the need to provide an estimate of model-to-model uncertainty in the relative reduction factor (RRF) for a better understanding of the uncertainty in projecting the status of an area's attainment. Results indicate that the model-to-model differences considered in this study introduce an uncertainty of the future estimated design value of ～3–5 ppb.     

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

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

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

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.     

Long range transport of fine particle windblown soils and coal fired power station emissions into Hanoi between 2001 to 2008

Fine particulate matter (PM_2.5), source fingerprints and their contributions have been measured and reported previously at Hanoi, Vietnam, from 25 April 2001 to 31 December 2008. In this study back trajectories are used to identify long range transport into Hanoi for two of these sources, namely, windblown dust (Soil) from 12 major deserts in China and emissions from 33 coal fired power plants (Coal) in Vietnam and China. There were 28 days of extreme Soil events with concentrations greater than 6 μg m^?3 and 25 days of extreme Coal with concentrations greater than 30 μg m^?3 from a total of 748 sampling days during the study period. Through the use of back trajectories it was found that long range transport of soil from the Taklamakan and Gobi desert regions (more than 3000 km to the north west) accounted for 76% of the extreme events for Soil. The three local Vietnamese power stations contributed to 15% of the extreme Coal events, while four Chinese power stations between 300 km and 1700 km to the north-east of Hanoi contributed 50% of the total extreme Coal events measured at the Hanoi sampling site.     

Investigation of the influence of transport from oil and natural gas regions on elevated ozone levels in the northern Colorado front range

The Northern Colorado Front Range (NCFR) has been in exceedance of the ozone National Ambient Air Quality Standard (NAAQS) since 2004, which has led to much debate over the sources of ozone precursors to the region, as this area is home to both the Denver, CO, metropolitan area and the Denver–Julesburg Basin, which has experienced rapid growth of oil and natural gas (O&NG) operations and associated emissions. Several recent studies have reported elevated levels of atmospheric volatile organic compounds (VOCs) as a result of O&NG emissions and the potential for significant ozone production from these emissions, despite implementation of stricter O&NG VOC emissions regulations in 2008. Approximately 88% of 1-hr elevated ozone events (>75 ppbv) occur during June–August, indicating that elevated ozone levels are driven by regional photochemistry. Analyses of surface ozone and wind observations from two sites, namely, South Boulder and the Boulder Atmospheric Observatory, both near Boulder, CO, show a preponderance of elevated ozone events associated with east-to-west airflow from regions with O&NG operations in the N-ESE, and a relatively minor contribution of transport from the Denver Metropolitan area to the SE-S. Transport from upwind areas associated with abundant O&NG operations accounts for on the order of 65% (mean for both sites) of 1-hr averaged elevated ozone levels, while the Denver urban corridor accounts for 9%. These correlations contribute to mounting evidence that air transport from areas with O&NG operation has a significant impact on ozone and air quality in the NCFR.

Implications: This article builds on several previous pieces of research that implied significant contributions from oil and natural gas emissions on ozone production in the Northern Colorado Front Range. By correlating increased ozone events with transport analyses we show that there is a high abundance of transport events with elevated ozone originating from the Denver–Julesburg oil and natural gas basin. These findings will help air quality regulators to better assess contributing sources to ozone production and in directing policies to curb ozone pollution in this region.     

Characteristics of the major chemical constituents of PM2.5 and smog events in Seoul,Korea in 2003 and 2004

One hundred ninety-five chemically speciated samples were collected from March 2003 to February 2005 in the Seoul Metropolitan area to investigate the characteristics of the major components in PM_2.5 and to characterize the chemical variations between smog and non-smog events. The annual average PM_2.5 concentration was 43 μg m⁻³ that is almost three times higher than the US NAAQS annual PM_2.5 standard of 15 μg m⁻³. During this sampling period, smog and yellow sand events were observed on 27 and 10 days, respectively. The PM_2.5 concentrations and its constituents during smog events were about two–three times higher than those during non-smog and yellow sand events. In particular, the mass fractions of secondary aerosols such as sulfate, nitrate, and ammonium during the smog events were higher than those of the other constituents. The mean concentration and mass fraction of secondary organic carbon (SOC) were highest during the winter smog events. Sulfate, nitrate and SOC that can have long residence times were important species during the smog events suggesting that regional scale sources rather than local sources were important. Five-day backward air trajectory analysis showed that the air parcels during smog events passed through the major industrial areas in China more often than those during non-smog events.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.     

African dust contributions to mean ambient PM10 mass-levels across the Mediterranean Basin

Data on mass-levels of PM₁₀ measured at regional background sites across the Mediterranean Basin, available from Airbase (European Environmental Agency) and from a few aerosol research sites, are compiled. PM₁₀ levels increase from north to south and west to east of the Basin. These variations are roughly coincident with the PM₁₀ African mineral dust load. However, when subtracting the African dust from mean PM₁₀ levels using a consistent methodology, the PM₁₀ background levels are still 5–10 μg m^?3 higher in the Eastern Basin (EMB) when compared with those in the Western (WMB), mainly due to the higher anthropogenic and sea spray loads.As regards for the seasonal trends, these are largely driven by the occurrence of African dust events, resulting in a spring-early summer maximum over the EMB, and a clear summer maximum in the WMB, although in this later region the recirculations of aged air masses play an important role. Furthermore, a marked seasonal trend is still evident when subtracting the African dust load. This is characterised by a high summer maximum (driven by low precipitation, high insolation) and a winter minimum (intense synoptic winds).Important inter-annual variations in the dust contribution are detected, more evident in the southern sites. These differences are generally associated with the occurrence of extreme dust events. Generally, the years with higher dust contributions over the EMB correspond with lower contributions over the WMB, and vice versa.The characterization of individual particles, collected in both basins during African dust events, by scanning electron microscopy reveals only slight differences between them. This fact probably reflects the high degree of mixture of mineral dust from different sources before the transport towards the receptor sites.     

Ground-level ozone in the Pearl River Delta region: Analysis of data from a recently established regional air quality monitoring network

The ambient air quality monitoring data of 2006 and 2007 from a recently established Pearl River Delta (PRD) regional air quality monitoring network are analyzed to investigate the characteristics of ground-level ozone in the region. Four sites covering urban, suburban, rural and coastal areas are selected as representatives for detailed analysis in this paper. The results show that there are distinct seasonal and diurnal cycles in ground-level ozone across the PRD region. Low ozone concentrations are generally observed in summer, while high O₃ levels are typically found in autumn. The O₃ diurnal variations in the urban areas are larger than those at the rural sites. The O₃ concentrations showed no statistically significant difference between weekend and weekdays in contrast to the findings in many other urban areas in the world. The average ozone concentrations are lower in urban areas compared to the sites outside urban centers. Back trajectories are used to show the major air-mass transport patterns and to examine the changes in ozone from the respective upwind sites to a site in the center of the PRD (Wanqingsha). The results show higher average ozone concentrations at the upwind sites in the continental and coastal air masses, but higher 1 h-max O₃ concentrations (by 8–16 ppbv) at the center PRD site under each of air-mass category, suggesting that the ozone pollution in the PRD region exhibits both regional and super-regional characteristics.     

Use of Plants for Air Pollution Monitoring

Leaf injury data from acute and chronic exposure studies of Dare soybean were regressed against the logarithms of exposure time and O₃ and SO₂ concentrations to develop a new two-pollutant leaf injury model (which explains 88% of the variance) and to calculate the parameters of best fit for this new model and a previously developed one-pollutant model. Using the calculated parameters, the percentage of leaf surface Injured over a growing season by O₃, SO₂, or both simultaneously was estimated for an ambient air sampling site located 2 miles from a coal burning power plant. For this site, the one- and two-pollutant models predicted that SO₂ effects would be negligible If SO₂ concentrations never exceeded the National Ambient Air Quality Standard (NAAQS) of 0.50 ppm, averaged over 3 h. However, calculations suggest that O₃ may injure up to 24% of Dare soybean leaf surface over a growing season even though the O₃ NAAQS of 0.12 ppm, averaged over 1 h, is never exceeded. Because the 3 h SO₂ standard is exceeded at very few places, the O₃ model is usually sufficient to estimate Dare soybean leaf Injury. Leaf injury is estimated by taking the logarithm of the summation of each daytime hour’s exponentiated O₃ concentration (c) measured at an ambient air sampling site over a growing season. This is expressed as: z = -0.0828 + 0.4876 in (Σco₃ ^2.618), where z is the Gaussian transform of percent leaf injury. The methods developed in this paper, using Dare soybean data as an example, may apply to other plants.     

Recent spatial gradients and time trends in Dhaka,Bangladesh, air pollution and their human health implications

Dhaka, the capital of Bangladesh, is among the most polluted cities in the world. This research evaluates seasonal patterns, day-of-week patterns, spatial gradients, and trends in PM_2.5 (<2.5 µm in aerodynamic diameter), PM₁₀ (<10 µm in aerodynamic diameter), and gaseous pollutants concentrations (SO₂, NO₂, CO, and O₃) monitored in Dhaka from 2013 to 2017. It expands on past work by considering multiple monitoring sites and air pollutants. Except for ozone, the average concentrations of these pollutants showed strong seasonal variation, with maximum during winter and minimum during monsoon, with the pollution concentration of PM_2.5 and PM₁₀ being roughly five- to sixfold higher during winter versus monsoon. Our comparisons of the pollutant concentrations with Bangladesh NAAQS and U.S. NAAQS limits analysis indicate particulate matter (PM_2.5 and PM₁₀) as the air pollutants of greatest concern, as they frequently exceeded the Bangladesh NAAQS and U.S. NAAQS, especially during nonmonsoon time. In contrast, gaseous pollutants reported far fewer exceedances throughout the study period. During the study period, the highest number of exceedances of NAAQS limits in Dhaka City (Darus-Salam site) were found for PM_2.5 (72% of total study days), followed by PM₁₀ (40% of total study days), O₃ (1.7% of total study days), SO₂ (0.38% of total study days), and CO (0.25% of total study days). The trend analyses results showed statistically significant positive slopes over time for SO₂ (5.6 ppb yr^?1, 95% confidence interval [CI]: 0.7, 10.5) and CO (0.32 ppm yr^?1, 95% CI: 0.01, 0.56), which suggest increase in brick kilns operation and high-sulfur diesel use. Though statistically nonsignificant annual decreasing slopes for PM_2.5 (?4.6 µg/m³ yr^?1, 95% CI: ?12.7, 3.6) and PM₁₀ (?2.7 µg/m³ yr^?1, 95% CI: ?7.9, 2.5) were observed during this study period, the PM_2.5 concentration is still too high (~ 82.0 µg/m³) and can cause severe impact on human health.

Implications: This study revealed key insights into air quality challenges across Dhaka, Bangladesh, indicating particulate matter (PM) as Dhaka’s most serious air pollutant threat to human health. The results of these analyses indicate that there is a need for immediate further investigations, and action based on those investigations, including the conduct local epidemiological PM exposure-human health effects studies for this city, in order to determine the most public health effective interventions.     

The Chemical and Meteorological Conditions Associated with High and Low Ozone Concentrations in Southeastern Michigan and Nearby Areas of Ontario

This analysis represents the first characterization of the photochemistry and transport of ozone in the Detroit metropolitan area and provides a basis for comparing data for Detroit to that for other cities. The characterization is based on a comprehensive set of meteorological and chemical measurements obtained at a site in the urban core of Detroit during the summer of 1981, together with measurements of O₃, nitrogen oxides (NO _X ), and nonmethane organic compounds (NMOC) from rural, suburban, and urban areas in southeastern Michigan and adjacent areas of Ontario.

For the quartile (23 days) with highest ozone maxima (97-180 ppb), the maxima occurred 10-70 km north-northeast of the city on days that were warm and hazy with light southsouthwest winds. On such days there was a marked accumulation of ozone precursors (NMOC and NO_X) in the early morning, as well as a rapid chemical removal of NO _X (NO _X half-life of ～5 h) from morning to midday. The timing of the daily ozone increase across the study region suggests that local photochemical generation in a moving plume was responsible for more than half of the ozone measured downwind. However, there was also evidence that ozone transported into Detroit as part of the regional background was a significant part of the O₃ maxima on high ozone days. The average contributions of photochemistry and transport for the 23 days with the highest ozone maxima were estimated to be 57 ppb and 47 ppb, respectively.     

A Re-Examination of Ambient Air Ozone Monitor Interferences

Abstract

Attaining the National Ambient Air Quality Standard (NAAQS) for ozone (O₃) could cost billions of dollars nationwide. Attainment of the NAAQS is judged on O₃ measurements made by the Federal Reference Method (FRM), ethylene chemiluminescence, or a Federal Equivalent Method (FEM), predominantly ultraviolet (UV) absorption. Starting in the 1980s, FRM monitors were replaced by FEMs so that today virtually all monitoring in the United States uses the UV methodology. This report summarizes a laboratory and collocated ambient air monitoring study of interferences in O₃ monitors. Potential interferences examined in the laboratory included water vapor, mercury, o-nitrophenol, naphthalene, p-tolualdehyde, and mixed reaction products from smog chamber simulations of urban atmospheric photochemistry. UV absorption O₃ monitors modi?ed for humidity equilibration were also collocated with UV FEM O₃ monitors at six sites in Houston, TX, during the 2007 summer O₃ season. The results suggest that humidity and interfering species can positively bias (overestimate) O₃ measured by FEM monitors used to determine compliance with the O₃ standards. The results also suggest that humidity equilibration can mitigate this bias.     

Measurement and modeling of O3 variability in Shanghai,China: Application of the WRF-Chem model

Since 2005, Shanghai Meteorological Bureau (SMB) has established an observational network for measuring VOC, NO_x, O₃ and aerosols in the Shanghai region. In this study, a rapid O₃ changes from Aug/02/2007 to Aug/11/2007 was observed in the region. During this 10 day period, the noontime O₃ maximum decreased from 100 to 130 ppbv to about 20–30 ppbv. In order to analyze the processes in controlling this rapid change of O₃ during this short period, a newly developed regional chemical/dynamical model (WRF-Chem) is applied to study O₃ variability in the Shanghai region. The model performances are evaluated by comparing the model calculation to the measurement. The result shows that the calculated magnitudes and diurnal variations of O₃ are close to the measured results in city sites, but are underestimated at a rural petroleum industrial site, suggesting that the emissions from petroleum factories around this rural site are significantly underestimated and need to be improved. The calculated rapid changes of O₃ concentrations, O₃ precursors, and aerosols are consistent with the measured results, suggesting that the model is suitable to study the causes of this rapid O₃ change. The model analysis indicates that weather conditions play important roles in controlling the surface O₃ in the Shanghai region. During summer, there is a persistent sub-tropical high pressure system (SUBH) in southeast of Shanghai over Pacific Ocean. During the earlier time of the period (Aug/02–Aug/05), the SUBH system was weak, resulting in weak surface winds. With the calm winds, a noticeable noontime sea-breeze produced an inflow from ocean to land, generating a cycling pattern of wind directions. As a result, the high O₃ concentrations were trapped in the Shanghai region, with a maximum concentration of 100–130 ppbv. By contrast, during the later time of the period (Aug/06–Aug/11), the SUBH was enhanced, resulting in strong surface winds. The high O₃ concentrations formed in the city were rapidly transported to the downwind region of the city, resulting in low O₃ concentrations in the Shanghai region. This study illustrates that the WRF-Chem model is a useful tool for studying the high variability of O₃ concentrations in Shanghai, which has important implication for the prediction of high O₃ concentration events in the city.     

Seasonal trends,meteorological impacts,and associated health risks with atmospheric concentrations of gaseous pollutants at an Indian coastal city

This study presents surface ozone (O₃) and carbon monoxide (CO) measurements conducted at Bhubaneswar from December 2010 to November 2012 and attempts for the very first time a health risk assessment of the atmospheric trace gases. Seasonal variation in average 24 h O₃ and CO shows a distinct winter (December to February) maxima of 38.98?±?9.32 and 604.51?±?145.91 ppbv, respectively. O₃ and CO characteristics and their distribution were studied in the form of seasonal/diurnal variations, air flow patterns, inversion conditions, and meteorological parameters. The observed winter high is likely due to higher regional emissions, the presence of a shallower boundary layer, and long-range transport of pollutants from the Indo-Gangetic Plain (IGP). Large differences between daytime and nighttime O₃ values during winter compared to other seasons suggest that photochemistry is much more active on this site during winter. O₃ and CO observations are classified in continental and marine air masses, and continental influence is estimated to increase O₃ and CO by up to 20 and 120 ppbv, respectively. Correlation studies between O₃ and CO in various seasons indicated the role of CO as one of the O₃ precursors. Health risk estimates predict 48 cases of total premature mortality in adults due to ambient tropospheric O₃ during the study period. Comparatively low CO concentrations at the site do not lead to any health effects even during winter. This study highlights the possible health risks associated with O₃ and CO pollution in Bhubaneswar, but these results are derived from point measurements and should be complemented either with regional scale observations or chemical transport models for use in design of mitigation policies.     

Beryllium-7 Measurements in the Houston and Phoenix Urban Areas: An Estimation of Upper Atmospheric Ozone Contributions

Abstract

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O₃) and aerosols in the troposphere. Beryllium-7 (⁷Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. ⁷Be has a 53.29-day half-life (478 keV γ) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O₃ from aloft can be transported into rural and urban regions during stratospheric–tropospheric folding events leading to increased background levels of O₃ at the surface. ⁷Be can be used as a tracer of upper atmospheric air parcels and the O₃ associated with them. Aerosol samples with a 2.5-µm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August– September of 2000, and at Waddell, AZ, near Phoenix, in June–July of 2001. A comparison of ⁷Be levels with 12-hr O₃ averages and maxima shows little correlation. Comparison of nighttime and daytime O₃ levels indicate that during the day, when mixing is anticipated to be higher, the correlation of ⁷Be with O₃ in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O₃ by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O₃ variance can be explained by the correlation with ⁷Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for ⁷Be correlations with either O₃ 24-hr averages or O₃ 12-hr maxima and is also in the range of the low O₃ levels (25 ppb) observed at Deer Park during a tropical storm event where the O₃ is attributable primarily to background air masses. That is, maximum background O₃ level contributions from stratospheric sources aloft are estimated to be in the range of 15–30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.