Effects of uncertainty in the reaction of the hydroxyl radical with nitrogen dioxide on model-simulated ozone control strategies

We evaluated the effect of a 20% reduction in the rate constant of the reaction of the hydroxyl radical with nitrogen dioxide to produce nitric acid (OH+NO₂→HNO₃) on model predictions of ozone mixing ratios ([O₃]) and the effectiveness of reductions in emissions of volatile organic compounds (VOC) and nitrogen oxides (NO_x) for reducing [O₃]. By comparing a model simulation with the new rate constant to a base case scenario, we found that the [O₃] increase was between 2 and 6% for typical rural conditions and between 6 and 16% for typical urban conditions. The increases in [O₃] were less than proportional to the reduction in the OH+NO₂ rate constant because of negative feedbacks in the photochemical mechanism. Next, we used two different approaches to evaluate how the new OH+NO₂ rate constant changed the effectiveness of reductions in emissions of VOC and NO_x: first, we evaluated the effect on [O₃] sensitivity to small changes in emissions of VOC (d[O₃]/dE_VOC) and NO_x (d[O₃]/dE_NOx); and secondly, we used the empirical kinetic modeling approach to evaluate the effect on the level of emissions reduction necessary to reduce [O₃] to a specified level. Both methods showed that reducing the OH+NO₂ rate constant caused control strategies for VOC to become less effective relative to NO_x control strategies. We found, however, that d[O₃]/dE_VOC and d[O₃]/dE_NOx did not quantitatively predict the magnitude of the change in the control strategy because the [O₃] response was nonlinear with respect to the size of the emissions reduction. We conclude that model sensitivity analyses calculated using small emissions changes do not accurately characterize the effect of uncertainty in model inputs (in this case, the OH+NO₂ rate constant) on O₃ attainment strategies. Instead, the effects of changes in model inputs should be studied using large changes in precursor emissions to approximate realistic attainment scenarios.     

Reduced ozone by air filtration consistently improved grain yield in wheat

This study considered effects of reduced [O₃] on wheat yield. Open-top chamber charcoal filtered air treatments were compared with non-filtered treatments for field-grown wheat. 30 experiments meeting requirements were found, representing nine countries in North America, Europe and Asia. 26 experiments reported improved yield and 4 experiments reduced yield by filtration, a significant positive effect. Average yield improvement was 9%. Average daytime [O₃] was reduced by filtration from 35 to 13 nmol mol⁻¹. Filtration efficiency was 63% for O₃ and 56% for SO₂. For NO_x it was observed that NO₂ was reduced and NO increased by filtration. Thus, filters convert NO₂ to NO. Most experiments reported low or very low [SO₂] and [NO_x]. Thus, O₃ can be concluded to be the main phytotoxic component in the experiments. Elevated [NO₂] was observed in one experiment. The conclusion is that current [O₃] over large parts of the world adversely affect wheat yield.     

Comparison of the SCAQS Tunnel Study with Other On Road Vehicle Emission Data

The Van Nuys Tunnel experiment conducted in 1987 by Ingalls et al. (see A&WMA Paper 89-137.3), to verify automotive emission inventories as part of the Southern California Air Quality Study (SCAQS), gave higher CO and HC emission-rate values than expected on the basis of automotive-emission models—by factors of approximately 3 and 4, respectively. The CO/NO_X and HC/NO_X emission-rate ratios moreover were higher than expected—by similar factors (NO_X emission rates were about as expected). The purpose of the present paper is to review the literature on dynamometer and on-road (in tunnels and along roadways) testing of in-use vehicles, and on urban-air CO/HC/NO_X concentration ratios, to see whether the Van Nuys Tunnel results are reasonable in terms of previous experience. The conclusions are that (1) on-road CO and HC emissions higher than expected have been reported before, (2) on-road CO and HC emissions consistent with the Van Nuys Tunnel results have been reported before, and (3) on-road CO/NO_X and HC/NO_X emission-rate ratios higher than expected have been reported before. The Van Nuys Tunnel NO_X results actually are lower than in other on-road experiments, and the CO/NO_X and HC/NO_X ratios consequently are higher. The higher-than-predicted CO/NO_X and HC/NO_X ratios at Van Nuys and other on-road sites suggest richer operation on-road than predicted or than observed in the inuse- vehicle dynamometer tests which serve as the model inputs. Support for these suggestions and conclusions is found in comparison of urban-air and emission-inventory HC/NO_X ratios.     

Estimation of night-time N2O5 concentrations from ambient NO2 and NO3 radical concentrations and the role of N2O5 in night-time chemistry

Dinitrogen pentoxide (N₂O₅), which is present in equilibrium with NO₃ radicals and NO₂, has been recognized for some time as an intermediate in the NO_x chemistry of night-time atmospheres. However, until the advent of long pathlength spectroscopic techniques for the measurement of atmospheric NO₃ radical concentrations, no reliable method for estimating N₂O₅ concentrations has been available. We have calculated maximum night-time N₂O₅ concentrations from the available experimentally determined concentrations of the NO₃ radical and NO₂ in the U.S. and Germany, and find that N₂O₅ concentrations as high as ~ 15 ppb can occur. We have also estimated removal rates for N₂O₅ and for NO₃ radicals during these nights. From data obtained under conditions devoid of point sources of NO_x, upper limit estimates of the homogeneous rate constant for the reaction of N₂O₅ with water vapor are obtained, leading to the conclusion that the homogeneous gas phase rate constant for this reaction is ⩽ 1 × 10⁻²¹ cm³ molecule⁻¹ s⁻¹ at 298 K, consistent with recent environmental chamber data.     

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX?=?O₃?+?NO₂), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO₂ and OX cycles. The variation of OX concentrations with NO _x is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO _x was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO₂]/[OX] and [NO₂]/[NO _x ] vs. [NO _x ] were analysed to find the fraction of OX in the form of NO₂, and the possible source of the local NO _x -dependent contribution, respectively. The progressive increase of the ratio [NO₂]/[OX] with [NO _x ] observed shows a greater proportion of OX in the form of NO₂ as the level of NO _x increases. The higher measured values in the ratio [NO₂]/[NO _x ] should not be attributed to NO _x emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO₂ photolysis, J _NO2?=?0.18–0.64 min^?1, a key atmospheric reaction that influence O₃ production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.     

Product Guide/1970

Abstract

In Mexico City, the use and composition of fuels determine that carbon monoxide (CO) comes mostly from mobile sources, and sulfur dioxide (SO₂) from fixed and mobile sources. By simultaneously measuring hydrocarbons (HC), CO, and SO₂ in the atmosphere of Mexico City, the relative amounts coming from different sources can be estimated. Assuming that some HC are emitted proportionally to CO emissions, we can establish that [HC]₁= m1? [CO], where the proportionality constant ml corresponds to the ratio of emissions factor for HC and CO in mobile sources. Similarly for fuels containing sulfur, it can be assumed that [HC]₂ = m2 ? [SO₂]. In this way, the total HC are [HC]_total=[HC]₀+ ml ? [CO]+ m2 ? [SO₂], where [HC]₀ corresponds mainly to other sources like solvent evaporation, gas consumption, and natural emissions. In this way, it can be estimated that in Mexico City 75% of average HC comes from mobile sources, 5% from sulfur-related sources, and 19% from natural sources and solvent evaporation. Compared with the HC/CO ratio measured in the exhaust pipe of vehicles, we estimated that 70% of HC emitted from mobile sources are evaporative losses, and only 30% come through the exhaust system.     

Measurement of surface ozone and its precursors in an urban area in South Brazil

Weekly and seasonal variations of surface ozone and their precursors – nitrogen oxides, carbon monoxide-associated with meteorological parameters (wind direction, temperature, solar radiation) – are reported. Measurements were performed continuously during 2006 at two sampling stations located in the metropolitan area of Porto Alegre, Brazil. Results have shown that O₃ concentrations remained almost constant between weekdays. Levels of NO_x precursors decreased especially on Sundays, due to lighter traffic. The seasonal variation has shown a maximum O₃ concentration during summer and spring while NO_x and NO₂ have maxima at the colder months. The daily cycle of highest ozone concentrations reveals a lower nightly level and an inverse relation between O₃ and NO_x, evidencing the photochemical formation of O₃. There are seasonal variation and source heterogeneity.     

Effect of Hydrocarbon and NO x on Photochemical Smog Formation under Simulated Transport Conditions

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. Concern has been expressed over the appropriate hydrocarbon and NO _x control strategy to be used in minimizing the effects of ozone and NO₂ on urban population centers and their downwind environs. O₃ and NO₂ formation were studied in smog chamber irradiations as a function of the initial NO _x concentration at three hydrocarbon concentrations. By carrying out the irradiations for a period of time equivalent to one solar day in a continuously diluting system, smog formation in a chemically reacting pollutant system under transport was simulated. The results of this experimental simulation suggest that hydrocarbon reduction reduces O₃ in urban as well as downwind areas while NO _x reduction increases O₃ in the urban area and has little effect on O₃ in downwind areas. Both hydrocarbon and NO _x reduction will reduce atmospheric NO₂ levels, with the effect of NO _x reduction generally being more pronounced.     

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 local and regional atmospheric oxidants at Athens (Greece)

In the present study, the investigation of the levels of the local and regional oxidants concentration at Athens, Greece, is attempted by analyzing the observations obtained at an urban and a rural station, during 2001–2011 and 2007–2011, respectively. A progressive increase of the daytime and nighttime average of [NO₂]/[O_x] versus [NO_x] is observed showing a larger proportion of O_x in the form of NO₂ when the level of NO_x increases. Similar results are observed when studying the variation of mean values of [NO₂]/[NO_x] versus [NO_x]. The results obtained when compared with those that have earlier detected elsewhere, revealed similarities and discrepancies that are discussed in detail. The parameterized curves that are presented for the first time in this paper may be used by the air quality planners to track the trends in other cities also, and to understand what is or was driving them.     

Assessment of the Ozone-Nitrogen Oxide-Volatile Organic Compound Sensitivity of Mexico City through an Indicator-Based Approach: Measurements and Numerical Simulations Comparison

Abstract

The ozone (O₃) sensitivity to nitrogen oxides (NO_x, or nitric oxide [NO] + nitrogen dioxide [NO₂]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O₃/NO_y (where NO_y represents the sum of NO + NO₂ + nitric acid [HNO₃] + peroxyacetyl nitrate [PAN] + others), NO_y, and the semiempirically derived O₃/NO_{z surrogate} (where NO_{z surrogate} is the derived surrogate NO_z, and NO_z represents NO_x reaction products, or NO_y – NO_x) with results of numerical predictions reproducing the transition regimes between NO_x and VOC sensitivities. Ambient air concentrations of O₃, NO_x, and NO_y were measured from April 14 to 25, 2004 in one downwind receptor site of photo-chemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O₃/NO_y, O₃/NO_{z surrogate}, and NO_y in MCMA suggest that O₃ in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NO_x ratios, have concluded that O₃ in Mexico City is NO_x-sensitive. Simulated MCMA-derived sensitive transition values for O₃/NO_y, hydrogen peroxide (H₂O₂)/HNO₃, and NO_y were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O₃/NO_z and O₃/HNO₃ was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O₃ concentrations and 6:00- to 9:00-a.m. NO_x and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NO_x emissions in MCMA might cause an increase in presently high O₃ levels.     

Rate constant for the reaction of ozone with diethyl sulfide

The rate constant for the reaction of diethyl sulfide (DES; C₂H₅SC₂H₅) with ozone was determined for the first time, which was (2.77±0.27)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ under a room temperature of (289±1) K. Experiments were conducted under supposedly pseudo-first-order decay conditions, keeping [DES]₀>50[O₃]₀, but having different combinations of [DES]₀ and [O₃]₀. Cyclohexane was added into the reactor to eliminate the effect of OH radicals. The wall decay of ozone and the role of cyclohexane were also discussed in the present work.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

Toxicity of various anions associated with methoxyethyl methyl imidazolium-based ionic liquids on Clostridium sp

We investigated the effects on the growth of the anaerobic bacterium, Clostridium sp., of the ionic liquid, 1-methoxyethyl-3-methyl imidazolium [MOEMIM]⁺, derived from imidazolium cation and paired with one of a variety of counter-ions, viz., tetrafluoroborate [BF₄]^-, hexafluorophosphate [PF₆]^-_, trifluoroacetate [CF₃COO]^-, bis(trifluoromethane)sulfonamide [Tf₂N]^-, methane sulfonate [OMS], and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄]. These anions, in association with [MOEMIM]⁺ lowered the growth rate of the bacterium, showing the following trend: [Tf₂N]^- ≧ [PF₆]^- > [BF₄]^- > [CF₃COO]^- > [OMS]⁻. Anions incorporating fluorine were more toxic than those without it, and their toxicity rose with an increase in the number of fluorine atoms. Also, [MOEMIM]⁺[BF₄]^- was less toxic than [BMIM]⁺[BF₄]^-, probably due to the presence of a methoxyethyl functional group integrated in the cation side chain.     

The Clean Air Act Amendments and Motor Vehicle Inspection/Maintenance

Seventeen days of detailed measurements of NO, NO₂, O₃, HNO₃ and the frequency of NO₂ photolysis—j(NO₂)—were carried out in Claremont, CA, in September 1980. Under conditions when the rate of change of NO concentration is small, there must be a balance between formation and loss processes. In the classical photostationary state this balance is between NO₂ photolysis: NO₂ + hv → NO + O and reaction with ozone: NO + O₃ → NO₂ + O₂. The results show that the latter reaction with ozone is inadequate to balance the formation step; a significant contribution is required from another NO oxidation process, possibly peroxy radical oxidation. If so, the inferred concentration of peroxy radicals shows a diurnal variation, peaking around solar noon.     

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton’s reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H₂O₂ dosing rate, initial concentration of Fe²⁺, and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H₂O₂. Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H₂O₂ 40% lower than that used in the Fenton process to remove 90% of COD.     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

Trends and Relationships of O3, NOx and HC in the South Coast Air Basin of California

A basin-wide air quality trend analysis for the South Coast Air Basin of California is conducted for hydrocarbons (HC), NO_x, O₃ and CO using multi-station composite daily maximum-hour average ambient concentrations for the third quarter (July, August and September) from 1968 to 1985. Emissions and air quality trends are compared for the period 1968-1984. Ambient HC and NOX trends are somewhat different from estimated emission trends of HC and NO_x, while a definite, downward trend of ambient CO is consistent with vehicular emission control measures. Basin-wide ambient HC, NO_x and O₃ appear to show downward trends for the period 1970-1985, but because of high fluctuations it is difficult to delineate trends for shorter periods. The meteorology (850 mb temperature)-adjusted O₃ shows a more consistent downward trend than does unadjusted O₃. Polynomial and multiplicative regression models for basin-wide empirical O₃-HC-NO_x relationships Indicate that the O₃ variation is explained largely by the meteorological variable (850 mb temperature) although model estimations are improved by adding HC and NO_x concentration terms.