Comparison of Nonmethane Organic Compound Concentration Data Collected by Two Methods in Atlanta

Title I of the Clean Air Act Amendments of 1990 calls for “enhanced monitoring” of ozone, which is planned to include measurements of atmospheric non-methane organic compounds (NMOCs). NMOC concentration data gathered by two methods in Atlanta, Georgia during July and August 1990 are compared in order to assess the reliability of such measurements in an operational setting. During that period, automated gas chromatography (GO) systems (Field systems) were used to collect NMOC continuously as one-hour averages. In addition, canister samples of ambient air were collected on an intermittent schedule for quality control purposes and analyzed by laboratory GC (the Lab system). Data from the six-site network included concentrations of nitrogen oxides (NOX), carbon monoxide (CO), ozone, total NMOC (TNMOC), and 47 identified NMOCs. Regression analysis indicates that the average TNMOC concentration from the Lab system is about 50 percent higher than that from the Field system, and that the bulk of the difference is due to unidentified NMOCs recorded by the Lab system. Also, there are substantial uncertainties in predicting a single Field TNMOC concentration from a measured Lab concentration. Considering individual identified NMOCs, agreement between the systems is poor for many olefins that occur at low concentrations but may be photochemically important. Regressions of TNMOC against CO and NOX lead to the conclusion that the larger unidentified component being reported by the Lab system is not closely related to local combustion or automotive sources.     

An exploratory look at hydrocarbon data from the Photochemical Assessment Monitoring Stations network

This paper describes some characteristics of speciated nonmethane organic compound (NMOC) data collected in 1994 at five Photochemical Assessment Monitoring Stations (PAMS) and archived in the U.S. Environmental Protection Agency's Aerometric Information Retrieval System (AIRS). Topics include data completeness, distribution of individual NMOCs in concentration categories relative to minimum detectable levels, percentage of total NMOC associated with the sum of the 55 PAMS target compounds, and use of scatterplots to diagnose chromatographic misidentification of compounds. This is an early examination of a database that is expanding rapidly, and the insights presented here may be useful to both the producers and future users of the data for establishing consistency and quality control.     

Inhalable Particulate Levels in Northern Idaho from the Initial Eruptions of Mount St. Helens

ABSTRACT

This paper describes some characteristics of speciated nonmethane organic compound (NMOC) data collected in 1994 at five Photochemical Assessment Monitoring Stations (PAMS) and archived in the U.S. Environmental Protection Agency’s Aerometric Information Retrieval System (AIRS). Topics include data completeness, distribution of individual NMOCs in concentration categories relative to minimum detectable levels, percentage of total NMOC associated with the sum of the 55 PAMS target compounds, and use of scatterplots to diagnose chromatographic misidentification of compounds. This is an early examination of a database that is expanding rapidly, and the insights presented here may be useful to both the producers and future users of the data for establishing consistency and quality control.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

Weekday/Weekend differences in ambient air pollutant concentrations in atlanta and the southeastern United States

The authors quantified changes between mean weekday and weekend ambient concentrations of ozone (O3) precursors (volatile organic compounds [VOC], carbon monoxide [CO], nitric oxide, and oxides of nitrogen [NOx]) in Atlanta and surrounding areas to observe how weekend precursor emission levels influenced ambient O3 levels. The authors analyzed CO, nitric oxide (NO), and NO, measurements from 1998 to 2002 and speciated VOC from 1996 to 2003. They observed a strong weekend effect in the Atlanta region, with median daytime (6:00 a.m. to 3:00 p.m. Eastern Standard Time) decreases of 62%, 57%, and 31%, respectively, in the ambient levels of NO, NOx, and CO from Wednesdays to Sundays, during the ozone season (March to October). They also observed significant decreases in ambient VOC levels between Wednesdays and Sundays, with decreases of 28% for the sum of aromatic compounds and 19% for the sum of Photochemical Assessment Monitoring Stations target compounds. Despite large reductions in O3 precursor levels on weekends, day-of-week differences in O3 mixing ratios in and near Atlanta were much smaller. Averaging overall O3-season days, the 1-hr and 8-hr mean peak daily O3 maxima on Sundays were 4.5% and 2.3% lower, respectively, than their mean levels on Wednesdays (median of 14 site differences), with no sites showing statistically significant Wednesday-to-Sunday differences. When restricted to high-O3 days (highest 3 peak O3 days per day of week per site per year), the 1-hr and 8-hr Sunday O3 mixing ratios were 11% and 10% lower, respectively, than their mean peak levels on Wednesdays (median of 14 site differences), with 6 of 14 sites showing statistically significant Wednesday-to-Sunday differences. The analyses of weekday/weekend differences in O3 precursor concentrations show that different emission reductions than normally take place each weekend will be required to achieve major reductions in ambient ozone levels in the Atlanta area.     

Meteorologically adjusted trends of daily maximum ozone concentrations in Taipei,Taiwan

The meteorological conditions exert large impacts on ozone concentrations, and may mask the long-term trends in ozone concentrations resulting from precursor emissions. Estimation of long-term trends of ozone concentrations due to the changes in precursor emissions is important for corresponding control strategy. Multiple linear regression (method I), multilayer perceptron (MLP) neural network (method II) and Komogorov-Zurbenko (KZ) filter method plus MLP methodology (method III), are used to estimate the meteorologically adjusted long-term trends of daily maximum ozone concentrations by removing the masking effects of meteorological conditions in this study. The daily maximum ozone concentrations and relative meteorological variables were extracted from six air-monitoring stations in Taipei area from 1994 to 2001. The data collected during 1994–2000 period were used as modeling set and utilized to estimate the meteorologically adjusted trends, and the data of 2001 were used as the validation data. The meteorologically adjusted trends of ozone for these three methods were calculated and compared. The results show that both MLP and KZ filter +MLP models are more suitable than multiple linear regression for estimating the long-term trends of ozone in Taipei, Taiwan. The long-term linear trends of meteorologically adjusted ozone concentrations due to the precursor emissions show an increase trend at all stations, and the percent changes per year range from 1.0% to 2.25% during the modeling period in Taipei area.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta,Georgia

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C₂–C₁₀ non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*k_OH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C₇–C₁₀ alkanes and 3% C₂-C₆ alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ～50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.     

Impact of biogenic terpene emissions from <Emphasis Type="Italic">Brassica napus</Emphasis> on tropospheric ozone over saxony (Germany)

INTRODUCTION: The role of biogenic emissions in tropospheric ozone production is currently under discussion and major aspects are not well understood yet. This study aims towards the estimation of the influence of biogenic emissions on tropospheric ozone concentrations over Saxony in general and of biogenic emissions from brassica napus in special. MODELLING TOOLS: The studies are performed by utilizing a coupled numerical modelling system consisting of the meteorological model METRAS and the chemistry transport model MUSCAT. For the chemical part, the Euro-RADM algorithm is used. EMISSIONS: Anthropogenic and biogenic emissions are taken into account. The anthropogenic emissions are introduced by an emission inventory. Biogenic emissions, VOC and NO, are calculated within the chemical transport model MUSCAT at each time step and in each grid cell depending on land use type and on the temperature. The emissions of hydrocarbons from forest areas as well as biogenic NO especially from agricultural grounds are considered. Also terpene emissions from brassica napus fields are estimated. SIMULATION SETUP AND METEOROLOGICAL CONDITIONS: The simulations were performed over an area with an extension of 160 x 140 km2 which covers the main parts of Saxony and neighboring areas of Brandenburg, Sachsen-Anhalt and Thuringia. Summer smog with high ozone concentrations can be expected during high pressure conditions on hot summer days. Typical meteorological conditions for such cases were introduced in an conceptual way. RESULTS: It is estimated that biogenic emissions change tropospheric ozone concentrations in a noticeable way (up to 15% to 20%) and, therefore, should not be neglected in studies about tropospheric ozone. Emissions from brassica napus do have a moderate potential to enhance tropospheric ozone concentrations, but emissions are still under consideration and, therefore, results vary to a high degree. CONCLUSIONS: Summing up, the effect of brassica napus terpene emissions on ozone concentrations is noticeable, but not too pronounced. The results give a preliminary estimate on what the effect due to brassica napus emissions could be until better parameterizations can be derived from measurements.     

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.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Predictive mapping of air pollution involving sparse spatial observations

A limited number of sample points greatly reduces the availability of appropriate spatial interpolation methods. This is a common problem when one attempts to accurately predict air pollution levels across a metropolitan area. Using ground-level ozone concentrations in the Tucson, Arizona, region as an example, this paper discusses the above problem and its solution, which involves the use of linear regression. A large range of temporal variability is used to compensate for sparse spatial observations (i.e. few ozone monitors). Gridded estimates of emissions of ozone precursor chemicals, which are developed, stored, and manipulated within a geographic information system, are the core predictor variables in multiple linear regression models. Cross-validation of the pooled models reveals an overall R2 of 0.90 and approximately 7% error. Composite ozone maps predict that the highest ozone concentrations occur in a monitor-less area on the eastern edge of Tucson. The maps also reveal the need for ozone monitors in industrialized areas and in rural, forested areas.     

Differences between Weekday and Weekend Air Pollutant Levels in Atlanta; Baltimore; Chicago; Dallas–Fort Worth; Denver; Houston; New York; Phoenix; Washington,DC; and Surrounding Areas

Abstract

We evaluated day-of-week differences in mean concentrations of ozone (O₃) precursors (nitric oxide [NO], nitrogen oxides [NO_x], carbon moNO_xide [CO], and volatile organic compounds [VOCs]) at monitoring sites in 23 states comprising seven geographic focus areas over the period 1998– 2003. Data for VOC measurements were available for six metropolitan areas in five regions. We used Wednesdays to represent weekdays and Sundays to represent weekends; we also analyzed Saturdays. At many sites, NO, NO_x, and CO mean concentrations decreased at all individual hours from 6:00 a.m. to 3:00 p.m. on Sundays compared with corresponding Wednesday means. Statistically significant (p < 0.01) weekend decreases in ambient concentrations were observed for 92% of NO_x sites, 89% of CO sites, and 23% of VOC sites. Nine-hour (6:00 a.m. to 3:00 p.m.) mean concentrations of NO, NO_x, CO, and VOCs declined by 65, 49, 28, and 19%, respectively, from Wednesdays to Sundays (median site responses). Despite the large reductions in ambient NO_x and moderate reductions in ambient CO and VOC concentrations on weekends, ozone and particulate matter (PM) nitrate did not exhibit large changes from week-days to weekends. The median differences between Wednesday and Sunday mean ozone concentrations at all monitoring sites ranged from 3% higher on Sundays for peak 8-hr concentrations determined from all monitoring days to 3.8% lower on Sundays for peak 1-hr concentrations on extreme-ozone days. Eighty-three percent of the sites did not show statistically significant differences between Wednesday and weekend mean concentrations of peak ozone. Statistically significant weekend ozone decreases occurred at 6% of the sites and significant increases occurred at 11% of the sites. Average PM nitrate concentrations were 2.6% lower on Sundays than on Wednesdays. Statistically significant Sunday PM nitrate decreases occurred at one site and significant increases occurred at seven sites.     

The impact of the congestion charging scheme on ambient air pollution concentrations in London

On 17th February 2003, a congestion charging scheme (CCS), operating Monday–Friday, 07:00–18:00, was introduced in central London along with a programme of traffic management measures. We investigated the potential impact of the introduction of the CCS on measured pollutant concentrations (oxides of nitrogen (NO_X, NO and NO₂), particles with a median diameter less than 10 microns (PM₁₀), carbon monoxide (CO) and ozone (O₃)) measured at roadside and background monitoring sites across Greater London. Temporal changes in pollution concentrations within the congestion charging zone were compared to changes, over the same time period, at monitors unlikely to be affected by the CCS (the control zone) and in the boundary zone between the two. Similar analyses were done for CCS hours during weekends (when the CCS was not operating).Based on the single roadside monitor with the CCS Zone, it was not possible to identify any relative changes in pollution concentrations associated with the introduction of the scheme. However, using background monitors, there was good evidence for a decrease in NO and increases in NO₂ and O₃ relative to the control zone. There was little change in background concentrations of NO_X. There was also evidence of relative reductions in PM₁₀ and CO. Similar changes were observed during the same hours in weekends when the scheme was not operating.The causal attribution of these changes to the CCS per se is not appropriate since the scheme was introduced concurrently with other traffic and emissions interventions which might have had a more concentrated effect in central London. This study provides important pointers for study design and data requirements for the evaluation of similar schemes in terms of air quality. It also shows that results may be unexpected and that the overall effect on toxicity may not be entirely favourable.     

Summertime measurements of benzene and toluene in Athens using a differential optical absorption spectroscopy system

In this paper, measurements of benzene, toluene, p,m-xylene, ozone (O3), nitrogen dioxide (NO2), and sulfur dioxide (SO2) made using the differential optical absorption spectroscopy (DOAS) technique during a 4-month period of summer 2000 (June-September) in Athens, Greece, are presented. An assessment of benzene mean value concentrations during this 4-month period exceeded 10 microg/m3, which is 2 times greater than the average yearly limit proposed by European authorities. Toluene measurements present mean values of approximately 33 microg/m3. Benzene and especially toluene measurements are highly correlated with NO2 and anticorrelated with O3. High values of benzene, NO2, and toluene are also correlated with winds from the southeast section, an area of industrial activity where emissions of volatile organic compounds (VOCs) have been recorded in previous studies. O3 is correlated with winds from the south-southwest section affected by the sea breeze circulation. Diurnal variations of O3, NO2, and SO2 concentrations are compatible with measurements from the stations of the Ministry of Environment's network. Outliers are combined with weak winds from the south-southwest. As far as p,m-xylene measurements are concerned, there is a poor correlation between gas chromatography (GC) and DOAS Opsis measurements, also observed in previous relevant campaigns and eventually a criticism in the use of the DOAS Opsis model for the measurement of p,m-xylene.     

Careers in Air Pollution Control Plant Pathology

ABSTRACT

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas [LPG], and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C₅ and C₆ saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C₂-C₄ saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): analysis of short-term and episodic variations in PM2.5 concentrations using hourly air monitoring data

One-hour average ambient concentrations of particulate matter (PM) with an aerodynamic diameter < 2.5 microm (PM2.5) were determined in Steubenville, OH, between June 2000 and May 2002 with a tapered element oscillating microbalance (TEOM). Hourly average gaseous copollutant [carbon monoxide (CO), sulfur dioxide (SO2), nitrogen oxide (NOx), and ozone (O3)] concentrations and meteorological conditions also were measured. Although 75% of the 14,682 hourly PM2.5 concentrations measured during this period were < or = 17 microg/m3, concentrations > 65 microg/m3 were observed 76 times. On average, PM2.5 concentrations at Steubenville exhibited a diurnal pattern of higher early morning concentrations and lower afternoon concentrations, similar to the diurnal profiles of CO and NO(x). This pattern was highly variable; however, PM2.5 concentrations > 65 microg/m3 were never observed during the mid-afternoon between 1:00 p.m. and 5:00 p.m. EST. Twenty-two episodes centered on one or more of these elevated concentrations were identified. Five episodes occurred during the months June through August; the maximum PM2.5 concentration during these episodes was 76.6 microg/m3. Episodes occurring during climatologically cooler months often featured higher peak concentrations (five had maximum concentrations between 95.0 and 139.6 microg/m3), and many exhibited strong covariation between PM2.5 and CO, NO(x), or SO2. Case studies suggested that nocturnal surface-based temperature inversions were influential in driving high nighttime concentrations of these species during several cool season episodes, which typically had dramatically lower afternoon concentrations. These findings provide insights that may be useful in the development of PM2.5 reduction strategies for Steubenville, and suggest that studies assessing possible health effects of PM2.5 should carefully consider exposure issues related to the intraday timing of PM2.5 episodes, as well as the potential for toxicological interactions among PM2.5, and primary gaseous pollutants.     

Modeling the effects of VOC/NOx emissions on ozone synthesis in the cascadia airshed of the Pacific Northwest

A modeling system consisting of MM5, Calmet, and Calgrid was used to investigate the sensitivity of anthropogenic volatile organic compound (VOC) and oxides of nitrogen (NOx) reductions on ozone formation within the Cascadia airshed of the Pacific Northwest. An ozone episode that occurred on July 11-14, 1996, was evaluated. During this event, high ozone levels were recorded at monitors downwind of Seattle, WA, and Portland, OR, with one monitor exceeding the 1 hr/120 ppb National Ambient Air Quality Standard (at 148 ppb), and six monitors above the proposed 8 hr/80 ppb standard (at 82-130 ppb). For this particular case, significant emissions reductions, between 25 and 75%, would be required to decrease peak ozone concentrations to desired levels. Reductions in VOC emissions alone, or a combination of reduced VOC and NOx emissions, were generally found to be most effective; reducing NOx emissions alone resulted in increased ozone in the Seattle area. When only VOC emissions were curtailed, ozone reductions occurred in the immediate vicinity of densely populated areas, while NOx reductions resulted in more widespread ozone reductions.     

Evaluation of ozone-nitrogen oxides-volatile organic compound sensitivity of Cincinnati, Ohio

Ambient concentrations of ozone (O3), nitrogen oxides (NOx), total reactive nitrogen (NOy), nitric acid (HNO3), and hydrogen peroxide (H2O2) were measured during September 2003 at an urban site of Cincinnati, OH. The aim of this study was two-fold: to investigate whether O3 formation in this population exposure-type site is NOx, sensitive or volatile organic compound (VOC) sensitive and to test the practicality of using two combined observational-based methods to identify the sensitivity of O3 formation in midlevel polluted locations. The evaluation of the indicator species: NOy, O3/NOy, O3/HNO3, H2O2/ HNO3, and O3/(estimated NOx reaction products), as well as the combined hypothesis testing analysis of the weekend/weekday (WE/WD) differences of 1-hr and 8-hr average maximum O3 and of the 6:00 a.m.-9:00 a.m. average nitric oxide and NOx concentrations, show evidence that Cincinnati is likely VOC sensitive. Average WE 1-hr and 8-hr maximum O3, as well as duration of WE O3 accumulation, were not lower than the corresponding WD levels in spite of the observed significant reduction in NO, emissions on WE, a typical situation in VOC-sensitive locations. The possibility that the seasonal transition from summer to autumn could have influenced the results was also investigated through an exploratory analysis of the afternoon O3 maximum/NOx measured and of the WE/WD differences of peak O3 and morning average NO and NO, concentrations observed at this site from June through September 2003. The results suggest that a VOC-sensitive chemistry regime dominated along the summer season. The findings of this study suggest that additional reductions in regional NO, emissions in Cincinnati, a potential nonattainment area under the 8-hr O3 standard, may cause an increase in local O3. Future strategies to reduce O3 in Southwest Ohio should be further evaluated carefully. The combination of observational-based methods might provide a consistent complementary approach in the identification of the NO,-VOC sensitive characteristics of mid-to-moderate polluted urban areas.     

A comparison of PAMS and air toxics measurements

One of the requirements of the 1990 Clean Air Act Amendments (CAA) is that 1-h ozone nonattainment areas that are classified severe or higher category are required to operate a network of photochemical assessment monitors (PAMS) to provide hourly measurements of volatile organic compounds (VOCs) comprising of Carbon number <12 (C2–C12), along with carbonyl measurements at 3-h intervals during the summer ozone season. Often collocated with PAMS are 24-h-integrated canister and cartridge-based measurements of selected air toxic compounds, thereby providing an opportunity for inter-comparison and validation of both sets of data. In this study, we report such a comparison and estimates of trend for benzene, m-, p- and o-xylene, toluene, ethylbenzene, 1,2,4-trimethylbenzene, formaldehyde and acetaldehyde at Bronx, NY. The analysis shows that hourly PAMS and 24-h-integrated air toxics are in good agreement with each other exhibiting similar trends and that the PAMS with the higher temporal resolution offers information on excursions of the toxic compounds that would be quite useful in assessment of acute health effects. These findings were also found to be applicable to other locations such as South De Kalb, GA; Gary, IN and Lynn, MA.     

Summer-time distribution of air pollutants in Sequoia National Park, California

Concentrations of air pollutants were monitored during the May November 1999 period on a network of forested sites in Sequoia National Park, California. Measurements were conducted with: (1) active monitors for nitric oxide (NO), nitrogen dioxide (NO2) and ozone (O3); (2) honeycomb denuder/filter pack systems for nitric acid vapor (HNO3), nitrous acid vapor (HNO2), ammonia (NH3), sulfur dioxide (SO2), particulate nitrate (NO3-), ammonium (NH4+), and sulfate (SO4(2-)); and (3) passive samplers for O3, HNO3 and NO2. Elevated concentrations of O3 (seasonal means 41-71 ppb), HNO3 (seasonal means 0.4-2.9 microg/m3), NH3 (seasonal means 1.6-4.5 microg/m3), NO3 (1.1-2.0 microg/m3) and NH4+ (1.0-1.9 microg/m3) were determined. Concentrations of other pollutants were low. With increasing elevation and distance from the pollution source area of O3, NH3 and HNO3 concentrations decreased. Ammonia and NH4+ were dominant N pollutants indicating strong influence of agricultural emissions on forests and other ecosystems of the Sequoia National Park.