Nonmethane Organic Compound to Nitrogen Oxide Ratios and Organic Composition in Cities and Rural Areas

The observed ranges in nonmethane organic compound (NMOC) concentrations, NMOC composition and nitrogen oxides (NO_X) concentrations have been evaluated for urban and nonurban areas at ground level and aloft of the contiguous United States. The ranges in NMOC to NO_X ratios also are considered. The NMOC composition consistently shifts towards less reactive compounds, especially the alkanes, in air parcels over nonurban areas compared to the NMOC composition near ground level within urban areas. The values for the NMOC to NO_X ratios, 1.2 to 4.2, in air aloft over nonurban areas are lower than in air at ground level urban sites, ≥8, and much lower than in air at ground level nonurban sites, ≥20.

The layers of air aloft over a number of nonurban areas of the United States tend to accumulate NO_X emissions from the tall stacks of large fossil fuel power plants located at nonurban sites. During the night into the morning hours, the air aloft is isolated from any fresh NMOC emissions predominately coming from near surface sources. Conversely, during this extended period of restricted vertical mixing, air near the surface accumulates NMOC emissions while this air is isolated from the major NO_X sources emitting aloft. These differences in the distribution of NMOC and NO_X sources appear to account for the much larger NMOC to NO_X ratios reported near ground level compared to aloft over nonurban areas.

Two types of experimental results are consistent with these conclusions: (1) observed increases in surface rural NO_X concentrations during the morning hours during which the mixing depth increases to reach the altitude at which NO_X from the stacks of fossil fuel power plants is being transported downwind; (2) high correlations of total nitrate at rural locations with Se, which is a tracer for coal-fired power plant NO_X emissions.

The implications of these conclusions from the standpoint of air quality strategies are suggested by use of appropriate scenarios applied to both urban and regional scale photochemical air quality models. The predictions from urban model scenarios with NMOC to NO_X ratios up to 20 are that NO_X control will result in the need for the control of more NMOC emissions than necessary in the absence of NO_X control, in order to meet the O₃ standard. On a regional scale, control of NO_X emissions from fossil fuel power plants has little overall effect regionally but does result on a more local scale in both small decreases and increases in O₃ concentrations compared to the baseline scenario without NO_X control. The regional modeling results obtained to date suggest that NO_X control may be effective in reducing O₃ concentrations only for a very limited set of conditions in rural areas.     

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.     

An examination of the 6:00 a.m.-9:00 a.m. measurements of ozone precursors in the New York City metropolitan area

In recent years, ambient measurements of hourly ozone precursor concentrations, namely speciated and total nonmethane organic compounds (NMOCs), have become available through the Photochemical Assessment Monitoring Stations (PAMS) program. Prior to this, NMOCs were measured in the central business district using a canister to obtain the 3-hr integrated sample for the 6:00 a.m.-9:00 a.m. period. Such sampling had been carried out annually for nearly a decade at three locations in the New York City metropolitan area. The intent of these measurements, along with measurements of the other ozone precursor, NO(x), was to provide an understanding of ozone formation and the emissions loading and mix in the urban area. The analysis of NMOC and NO(x) measurements shows a downward trend in the case of NMOC. In addition, we compared the canister-based NMOC concentrations with data obtained from the PAMS program for the 6:00 a.m.-9:00 a.m. period. Analysis of the NMOC concentrations reveals poor spatial correlation between the various monitors, reflecting the effect of localized emissions. This suggests that NMOC measurements made at a single location cannot be viewed as representative of the entire region. On the other hand, correlations were found to be higher among the NO(x) monitors, indicating the commonality of emission     

Statistical Assumptions Matter in Data Analysis for Texas Ozone Nonattainment Sites

Strategies for control of ozone aim at regulation of its chemical precursors, non-methane organic compounds (NMOC) and nitrogen oxides (NOx). It is therefore important to analyze how these precursors vary temporally and geographically. This study finds significant and important differences among four Texas ozone nonattainment sites, Dallas, Ft. Worth, El Paso, and Houston, for 1984, 1985, and 1986 for NMOC, NOx, and their ratio NNR. These differences were detected through nonparametric analysis of variance and Student-New-man-Keuls’s test for multiple comparisons on rank-transformed data. A noteworthy feature of the data analysis is its attention to the assumptions underlying the statistical methods. Classical models based on normal or lognormal theory had to be abandoned for lack of realism. It is demonstrated how alternative models may be applied to yield appropriate, rather than inappropriate, conclusions.     

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.     

Rural and Urban Ozone Relationships In New York State

High ozone concentrations, often in excess of the national ambient air quality standard for photochemical oxidants, have been measured simultaneously in urban and rural areas of New York State. Average daily rural ozone concentrations were found to correlate well with daily maximum urban ozone concentrations suggesting a common source. Estimations of the quantity of ozone advectively transported into New York State are more than an order of magnitude greater than estimations of the potential photochemical generation of ozone from hydrocarbon emissions within New York State. It is suggested thai the high rural ozone levels are not primarily due to the transport of ozone and ozone precursors from olher urban areas, but are rather due to natural phenomena such as photochemical generation from naturally occurring precursors or transport of ozone from the stratosphere to the troposphere. The effectiveness of a hydrocarbon control strategy for New York State to meet the ambient air quality standard for photochemical oxidants when background levels themselves may be above the standard is questioned.     

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.     

Comparative analysis of chemical reaction mechanisms for photochemical smog—II. Sensitivity of EKMA to chemical mechanism and input parameters

The six chemical reaction mechanisms for photochemical smog described in Pan I (Leone and Seinfeld, 1985, Atmospheric Environment 19,437–464) were used to study the effect of input parameters on volatile organic compound (VOC) control requirements needed to meet the National Ambient Air Quality Standard for ozone. The parameters studied were initial VOC composition, dilution rate, post 8-a.m. emissions, base case (present day) O₃ levels, entrainment from aloft of VOC and ozone and initial VOC/NO_x ratio. The Empirical Kinetic Modeling Approach (EKMA) was used to generate ozone isopleths for each chemical mechanism. The VOC control needed to reduce the maximum ozone concentration from some present day value to 0.12 ppm, assuming no NO_x control and a specified initial VOC/NO_x ratio, was calculated using the six chemical reaction mechanisms. The initial VOC/NO_x ratio was found to have the largest effect of all the parameters studied on VOC control requirements. Choice of chemical mechanism, ozone and VOC entrainmem from aloft, base-case ozone and the composition of the initial VOC mixture also had a large effect on predicted control requirements. To reduce the degree of uncertainty in control predictions using EKMA it is necessary to establish as accurately as possible the composition of urban air in early morning. Also, because of the substantial effect the choice of chemical mechanism has on the predicted control requirements using EKMA, it is important that future work continues to be directed toward evaluating candidate chemical mechanisms with respect to their ability to simulate atmospheric smog chemistry.     

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.     

A Study of Ozone Levels in a Maritime and Land Environment

During the summer of 1976, a comparison was made between ozone measurements for a coastal industrial concentration area (Norfolk/Virginia Beach, Virginia) and an offshore station (Chesapeake Light Station, 15 miles out to sea). The anticipated dominance of high offshore ozone readings with offshore flow was not observed. A surprising number of high O₃ concentrations were observed at both the offshore and land sites with northeasterly and easterly winds. This suggests that the phenomenon of long range transport of contaminants from highly urbanized centers in the northeast to the mid-Atlantic states via an offshore sea route must be given careful consideration. The body of information presented in this paper points out the need for a clearer understanding of the complex urban/rural O₃ problem coupled with transport effects before costly control strategies are to be implemented.     

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.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 2. Ozone trends and sensitivity to NMOC emissions in Atlanta,Georgia

Non-methane organic carbon (NMOC) measurements made in Atlanta, Georgia from 1999–2007 are used with nitrogen oxide (NO_x or NO_y) and ozone (O₃) data to investigate relationships between O₃ precursors and peak 8-hour O₃ concentrations in the city. Data from a WNW-to-ENE transect of sites illustrate that the mean urban peak 8-hour O₃ excess constitutes about 20% of the peak 8-hour O₃ measured at the area-wide maximum O₃ site when air-mass movement is from the northwest quadrant; local influence is potentially greater on days with more stagnation or recirculation. The peak 8-hour O₃ concentrations in Atlanta increase as (1) surface temperature (T), ambient NMOC and NO_y concentrations, and previous-day peak O₃ concentrations increase, and as (2) relative humidity, surface wind speeds, and ratios of NMOC-to-NO_y decrease. An observation-based statistical model is introduced to relate area-wide peak 8-hour O₃ concentrations to ambient NMOC and NO_y concentrations, while accounting for the non-linear dependences of peak 8-hour O₃ concentrations on meteorological factors. On the majority of days when the area-wide peak 8-hour O₃ exceeds 75 ppbv, meteorologically-adjusted peak 8-hour O₃ concentrations increase as ambient NMOC concentrations increase (NMOC sensitive) and ambient NO_y concentrations decrease. This result contrasts with regional conditions in which O₃ formation appears to be NO_x-sensitive in character. The results offer observationally-based information of relevance to O₃ management strategies in the Atlanta area, potentially contributing to “weight-of-evidence” assessments.     

Hydrocarbon Production and Photochemical Ozone Formation in Forest Burn Plumes

The purpose of this paper is to describe ozone production in forest slash burn plumes. Plumes from controlled fires in the state of Washington were monitored using an instrumented aircraft. Ozone, oxides of nitrogen, condensation nuclei, and visual range (nephelometer) were measured continuously on board the plane. Airborne grab samples were collected for detailed hydrocarbon analysis.

The slash burn plumes were found to contain significant quantities of ozone. A buildup of 40–50 ppb above the ambient background ozone concentrations was not unusual. Hydrocarbon analyses revealed the presence of many photochemically reactive olefins in the plume. Hydrocarbon/NO _x ratios were favorable for photochemical oxidant production.     

Ozone pollution and ozone biomonitoring in European cities. Part I: Ozone concentrations and cumulative exposure indices at urban and suburban sites

In the frame of a European research project on air quality in urban agglomerations, data on ozone concentrations from 23 automated urban and suburban monitoring stations in 11 cities from seven countries were analysed and evaluated. Daily and summer mean and maximum concentrations were computed based on hourly mean values, and cumulative ozone exposure indices (Accumulated exposure Over a Threshold of 40 ppb (AOT40), AOT20) were calculated. The diurnal profiles showed a characteristic pattern in most city centres, with minimum values in the early morning hours, a strong rise during the morning, peak concentrations in the afternoon, and a decline during the night. The widest amplitudes between minimum and maximum values were found in central and southern European cities such as Düsseldorf, Verona, Klagenfurt, Lyon or Barcelona. In the northern European cities of Edinburgh and Copenhagen, by contrast, maximum values were lower and diurnal variation was much smaller. Based on ozone concentrations as well as on cumulative exposure indices, a clear north–south gradient in ozone pollution, with increasing levels from northern and northwestern sites to central and southern European sites, was observed. Only the Spanish cities did not fit this pattern; there, ozone levels were again lower than in central European cities, probably due to the direct influence of strong car traffic emissions. In general, ozone concentrations and cumulative exposure were significantly higher at suburban sites than at urban and traffic-exposed sites. When applying the newly established European Union (EU) Directive on ozone pollution in ambient air, it was demonstrated that the target value for the protection of human health was regularly surpassed at urban as well as suburban sites, particularly in cities in Austria, France, northern Italy and southern Germany. European target values and long-term objectives for the protection of vegetation expressed as AOT40 were also exceeded at many monitoring sites.     

Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

Statistical Analysis of Trends in Urban Ozone Air Quality

The purpose of this paper is to demonstrate the use of some statistical methods for examining trends in ambient ozone air quality downwind of major urban areas. To this end, daily maximum 1 -hr ozone concentrations measured over New Jersey, metropolitan New York City and Connecticut for the period 1980 to 1989 were assembled and analyzed. This paper discusses the application of the bootstrap method, extreme value statistics and a nonparametric test for evaluating trends in urban ozone air quality. The results indicate that although there is an improvement in ozone air quality downwind of New York City, there has been little change in ozone levels upwind of New York City during this ten-year period.     

Ozone removal by HVAC filters

Residential and commercial HVAC filters that have been loaded with particles during operation in the field can remove ozone from intake or recirculated air. However, knowledge of the relative importance of HVAC filters as a removal mechanism for ozone in residential and commercial buildings is incomplete. We measured the ozone removal efficiencies of clean (unused) fiberglass, clean synthetic filters, and field-loaded residential and commercial filters in a controlled laboratory setting. For most filters, the ozone removal efficiency declined rapidly but converged to a non-zero (steady-state) value. This steady-state ozone removal efficiency varied from 0% to 9% for clean filters. The mean steady-state ozone removal efficiencies for loaded residential and commercial filters were 10% and 41%, respectively. Repeated exposure of filters to ozone following a 24-h period of no exposure led to a regeneration of ozone removal efficiency. Based on a theoretical scaling analysis of mechanisms that are involved in the ozone removal process, we speculate that the steady-state ozone removal efficiency is limited by reactant diffusion out of particles, and that regeneration is due to internal diffusion of reactive species to sites available to ozone for reaction. Finally, by applying our results to a screening model for typical residential and commercial buildings, HVAC filters were estimated to contribute 22% and 95%, respectively, of total ozone removal in HVAC systems.     

Wintertime vertical variations in particulate matter (PM) and precursor concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Air quality monitoring was conducted at a rural site with a tower in the middle of California's San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/ PM2.5 Air Quality Study. Measurements at the surface and n a tower at 90 m were collected in Angiola, CA, from December 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Ozone concentrations at a high altitude station in the Central Massif (Spain)

In order to contribute to current knowledge of ozone concentrations and transport across the Central Massif, a monitoring station was installed at 1780 m on the upper Spanish plateau about 55 km from the city of Madrid. Ozone concentrations and standard meteorological variables were measured in June and July 2002. A smoothed ozone hourly cycle was obtained with mean values of 120 and 110 microgm(-3) during day-time and night-time, respectively. The highest ozone concentrations were recorded in the SE-S-SW wind sectors, proving the influence of transport from the Madrid urban plume to the upper plateau. This assumption was also supported by the satisfactory correlation between ozone peaks obtained at the monitoring site and those recorded in a representative station on the foothill located on the lower plateau during episodic situations. To assess the contribution of long-range transport, backward air mass trajectories were computed each day of measurements at 820 hPa. The lowest ozone mean was linked to Atlantic Ocean air masses, and the highest to air masses from Central Europe.