Ground level ozone concentrations and its association with NOx and meteorological parameters in Kathmandu valley, Nepal

This paper summarizes the results of a yearlong continuous measurements of gaseous pollutants, NO, NO₂, NO_x and O₃ in the ambient air at Kathmandu valley. Measured concentration of the pollutants in study area is a function of time. NO, NO₂ and O₃ peak occurred in succession in presence of sunlight. At the time of maximum O₃ concentration most of the NO_x are utilized. The diurnal cycle of ground level ozone concentrations, revealed mid-day peak with lower nocturnal concentrations and inverse relationship exists between O₃ and NO_x, which are evidences of photochemical O₃ formation. The observed ground level ozone during monsoon is slight lower than the pre-monsoon value. Further, lack of rainfall and higher temperature, solar radiation in the pre-monsoon have given rise to the gradual build up of ozone and it is lowest during winter. Ground level ozone concentrations measured during bandha (general strike) and weekend are 19% and 13% higher than those measured during weekdays. The most effective ozone abatement strategy for Kathmandu Valley may be control of NO_x emissions.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.     

Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies

Both similarities and differences in summertime atmospheric photochemical oxidation appear in the comparison of four field studies: TEXAQS2000 (Houston, 2000), NYC2001 (New York City, 2001), MCMA2003 (Mexico City, 2003), and TRAMP2006 (Houston, 2006). The compared photochemical indicators are OH and HO₂ abundances, OH reactivity (the inverse of the OH lifetime), HO_x budget, OH chain length (ratio of OH cycling to OH loss), calculated ozone production, and ozone sensitivity. In terms of photochemical activity, Houston is much more like Mexico City than New York City. These relationships result from the ratio of volatile organic compounds (VOCs) to nitrogen oxides (NO_x), which are comparable in Houston and Mexico City, but much lower in New York City. Compared to New York City, Houston and Mexico City also have higher levels of OH and HO₂, longer OH chain lengths, a smaller contribution of reactions with NO_x to the OH reactivity, and NO_x-sensitivity for ozone production during the day. In all four studies, the photolysis of nitrous acid (HONO) and formaldehyde (HCHO) are significant, if not dominant, HO_x sources. A problematic result in all four studies is the greater OH production than OH loss during morning rush hour, even though OH production and loss are expected to always be in balance because of the short OH lifetime. The cause of this discrepancy is not understood, but may be related to the under-predicted HO₂ in high NO_x conditions, which could have implications for ozone production. Three photochemical indicators show particularly high photochemical activity in Houston during the TRAMP2006 study: the long portion of the day for which ozone production was NO_x-sensitive, the calculated ozone production rate that was second only to Mexico City's, and the OH chain length that was twice that of any other location. These results on photochemical activity provide additional support for regulatory actions to reduce reactive VOCs in Houston in order to reduce ozone and other pollutants.     

Production of boundary layer ozone from tropical American Savannah biomass burning emissions

Boundary layer ozone and carbon monoxide were measured at a savannah site in the Orinoco river basin, during the dry and wet seasons. CO and O₃ concentrations recorded around noontime show a good linear correlation, suggesting that the higher ozone levels observed during the dry season are photochemically produced during the oxidation of reactive hydrocarbons in the presence of NO_x both emitted by biomass burning. The rate of photochemical ozone production in the boundary layer ozone by biomass burning calculated from the production ratio ΔO₃/ΔCO (0.17±0.01 v : v) and the amount of CO produced by fires (0.26–1.3 mole m⁻² dry season⁻¹), ranges from 0.6 to 2.6 ppbv h⁻¹ for 8 h of daylight. This O₃ production rate is in fairly good agreement with the value derived from RO₂ radical measurements made in the Venezuelan savannah during the dry season. The net boundary layer production of O₃ from all tropical America savannah fires is estimated to range between 0.28 and 0.36 Tmol O₃ per year, which is about 3 times higher than the O₃ produced from pollution sources in the eastern United States during the summer. An extrapolation to all of the world's savannah would indicate a net boundary layer ozone production of about 1.2 Tmol yr⁻¹. This is discussed in the context of the overall global budget of tropospheric ozone.     

Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions

The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NO_x. Photochemical ozone production rates responded differently to 30% NO_x and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NO_x and VOCs also produced changes in OH. The responses in OH to 30% reductions in NO_x and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NO_x reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NO_x and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NO_x and VOC reductions under consideration.

Implications: The purpose of this paper is to compare predicted ozone responses to NO_x and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their application in the air quality models used for policymaking.     

In situ measurements of NO,NO2, NOy,and O3 in Dinghushan (112°E, 23°N), China during autumn 2008

Measurements of O₃, NO, NO₂, and NO_y mixing ratios were carried out at a station-Dinghushan in Guangdong province of China from Oct. 18th, 2008 to Nov. 7th, 2008. This research shows that under conditions of a strong subtropical high (temperature high, relative humidity low), on Oct. 29th, 2008 the Dinghushan station observed severe photochemical pollution. The Maximum hour average concentration of O₃ reached 128 ppbv, and the serious photochemical pollution is caused by superposition of local photochemical reaction and regional transport. The observation that NO_x ozone production efficiency (OPE) values for high O₃ pollution on Oct. 29–30th, 2008 were 10.5 and 15, which were more than the values of the city source region and lower than that of the surrounding clean areas. It means the sensitivity of O₃ generated was transitioning from VOCs limited condition to NOx-limited regime. By applying a Smog Production Model, the results show that the extent of reaction values less than 0.6 were occurred on 17 days during campaign, and 13 days for the extents of reactions more than 0.6. However, there were no data with values over 0.8, which indicates that the observation station represent a VOCs sensitive system during campaign. Analysis of the extents of reactions and wind data show that the pollution is mostly subject to a southeasterly airflow influence.     

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.     

Sensitivity Studies of the Effects of Model Formulation on the Evaluation of Control Strategies for Photochemical Air Pollution Formation in the United Kingdom

In the OZIPP (ozone isopleth plotting package, developed by United States Environmental Protection Agency) a number of model specific assumptions with respect to chemical and physical processes are made. These assumptions are introduced into an alternative model developed at AERE Harwell, United Kingdom, in which a detailed chemistry and mixture of organic emissions is included. The impact on the AERE Harwell model results of the assumptions made in OZIPP of omitting ground removal of ozone (O₃) and peroxyacetylnitrate (PAN) and of employing an incomplete PAN chemistry and adopting a reaction rate coefficient of the key reaction NO + HO₂ → NO₂ + OH which is a factor 10 lower than the accepted value, are discussed. The composition of the organic emissions is an important model parameter, and it is shown how grouping of nonmethane hydrocarbon (NMHC) emissions into a small group of NMHC thought to be representative, often implies that O₃ and other pollutants are overestimated. The O₃ isopleth diagram for London constructed using the AERE Harwell model gives a somewhat different picture from that obtained with OZIPP. OZIPP in general predicts that NO_x control or combined hydrocarbon(HC) and NO_x control is efficient with respect to O₃ reduction whilst the AERE Harwell model predicts that HC control alone usually is more efficient than combined HC and NO_x control. Furthermore NO_x control alone may often increase the O₃ burden downwind in the AERE Harwell model.     

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.     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).     

Characterizations of chemical oxidants in Mexico City: A regional chemical dynamical model (WRF-Chem) study

The formation of chemical oxidants, particularly ozone, in Mexico City were studied using a newly developed regional chemical/dynamical model (WRF-Chem). The magnitude and timing of simulated diurnal cycles of ozone (O₃), carbon monoxide (CO) and nitrogen oxides (NO_x)_, and the maximum and minimum O₃ concentrations are generally consistent with surface measurements. Our analysis shows that the strong diurnal cycle in O₃ is mainly attributable to photochemical variations, while diurnal cycles of CO and NO_x mainly result from variations of emissions and boundary layer height. In a sensitivity study, oxidation reactions of aromatic hydrocarbons (HCs) and alkenes yield highest peak O₃ production rates (20 and 18 ppbv h⁻¹, respectively). Alkene oxidations, which are generally faster, dominate in early morning. By late morning, alkene concentrations drop, and oxidations of aromatics dominate, with lesser contributions from alkanes and CO. The sensitivity of O₃ concentrations to NO_x and HC emissions was assessed. Our results show that daytime O₃ production is HC-limited in the Mexico City metropolitan area, so that increases in HC emissions increase O₃ chemical production, while increases in NO_x emissions decrease O₃ concentrations. However, increases in both NO_x and HC emissions yield even greater O₃ increases than increases in HCs alone. Uncertainties in HC emissions estimates give large uncertainties in calculated daytime O₃, while NO_x emissions uncertainties are less influential. However, NO_x emissions are important in controlling O₃ at night.     

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.     

OH and HO2 measurements in a forested region of north-western Greece

Boundary layer concentrations of hydroxyl (OH) and hydroperoxyl (HO₂) radicals were measured at 1180 m elevation in a mountainous, forested region of north-western Greece during the AEROsols formation from BIogenic organic Carbon (AEROBIC) field campaign held in July–August 1997. In situ measurements of OH radicals were made by laser-induced fluorescence (LIF) at low pressure, exciting in the (0, 0) band of the A–X system at 308 nm. HO₂ radicals were monitored by chemical titration to OH upon the addition of NO, with subsequent detection by LIF. The instrument was calibrated regularly during the field campaign, and demonstrated a sensitivity towards OH and HO₂ of 5.2×10⁵ and 2.4×10⁶ molecule cm⁻³, respectively, for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Diurnal cycles of OH and HO₂ were measured on 10 days within a small clearing of a forest of Greek Fir (Abies Borisi-Regis). In total 4165 OH data points and 1501 HO₂ data points were collected at 30 s intervals. Noon-time OH and HO₂ concentrations were between 4–12×10⁶ and 0.4–9×10⁸ molecule cm⁻³, respectively. The performance of the instrument is evaluated, and the data are interpreted in terms of correlations with controlling variables. A significant correlation (r²=0.66) is observed between the OH concentration and the rate of photolysis of ozone, J(O¹D). However, OH persisted into the early evening when J(O¹D) had fallen to very low values, consistent with the modelling study presented in the following paper (Carslaw et al., 2001, OH and HO₂ radical chemistry in a forest region of north-western Greece. Atmospheric Environment 35, 4725–4737) that predicts a significant radical source from the ozonolysis of biogenic alkenes. Normalisation of the OH concentrations for variations in J(O¹D) revealed a bell-shaped dependence of OH upon NO_x (NO+NO₂), which peaked at [NO_x] ∼1.75 ppbv. The diurnal variation of HO₂ was found to be less correlated with J(O¹D) compared to OH.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Understanding the Effectiveness of Precursor Reductions in Lowering 8-Hr Ozone Concentrations—Part II. The Eastern United States

Abstract

Analyses of ozone (O₃) measurements in conjunction with photochemical modeling were used to assess the feasibility of attaining the federal 8-hr O₃ standard in the eastern United States. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NO_x) emission reductions were effective in lowering modeled peak 1-hr O₃ concentrations. VOC emissions reductions alone had only a modest impact on modeled peak 8-hr O₃ concentrations. Anthropogenic NO_x emissions reductions of 46–86% of 1996 base case values were needed to reach the level of the 8-hr standard in some areas. As NO_x emissions are reduced, O₃ production efficiency increases, which accounts for the less than proportional response of calculated 8-hr O₃ levels. Such increases in O₃ production efficiency also were noted in previous modeling work for central California. O₃ production in some urban core areas, such as New York City and Chicago, IL, was found to be VOC-limited. In these areas, moderate NO_x emissions reductions may be accompanied by increases in peak 8-hr O₃ levels. The findings help to explain differences in historical trends in 1- and 8-hr O₃ levels and have serious implications for the feasibility of attaining the 8-hr O₃ standard in several areas of the eastern United States.     

Seasonal dependence of the oxidation capacity of the city of Santiago de Chile

The oxidation capacity of the highly polluted urban area of Santiago de Chile has been evaluated during a winter measurement campaign from May 25 to June 07, 2005, with the results compared and contrasted with those previously evaluated during a summer campaign from March 8 to 20, 2005. The OH radical budget was evaluated in both campaigns employing a simple quasi-photostationary state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O₃, NO, NO₂, j(O¹D), j(NO₂), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used for the analysis of the radical budgets and concentrations of OH, HO₂ and RO₂. Besides the above parameters, the MCM model has been constrained by the measured CO and other volatile organic compounds (VOCs) including alkanes and aromatics. Total production and destruction rates of OH and HO₂ in winter are about two times lower than that during summer. Simulated OH levels by both PSS and MCM models are similar during the daytime for both winter and summer indicating that the primary OH sources and sinks included in the simple PSS model are predominant. On a 24 h basis, HONO photolysis was shown to be the most important primary OH radical source comprising 81% and 52% of the OH initiation rate during winter and summer, respectively followed by alkene ozonolysis (12.5% and 29%), photolysis of HCHO (6.1% and 15%), and photolysis of O₃ (<1% and 4%), respectively. During both winter and summer, there was a balance between the OH secondary production (HO₂ + NO) and destruction (OH + VOCs) showing that initiation sources of RO₂ and HO₂ are no net OH initiation sources. This result was found to be fulfilled also for all other studies investigated. Seasonal impacts on the radical budgets are also discussed.     

Measurement of total OH reactivity by laser-induced pump and probe technique—comprehensive observations in the urban atmosphere of Tokyo

Total OH reactivity was observed by use of the laser-induced pump and probe technique, and the urban air quality in Tokyo was diagnosed comprehensively. The concentrations of NO_x, CO, O₃, non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (OVOCs) were observed simultaneously. The observations were conducted in July and August 2003, and in January, February, May, and November 2004. Generally, the observed OH reactivity was higher than the calculated values derived using the observed concentrations of the trace species. The differences between the observed and calculated values in summer, spring, and autumn were approximately 30%. However, the difference in winter was smaller than those in the other seasons. In addition, while the differences observed in summer, spring, and autumn correlated with the total reactivity of the OVOCs (Σ_i k_OVOCi[OVOC_i](s⁻¹), k_i is rate constant of its compounds with OH), the correlations were not confirmed in the case of winter because atmospheric oxidation was less active and OVOCs levels were low in winter. These results suggest that the secondary products of the photochemical reactions in the atmosphere would be a missing sink for the OH loss process in the urban area.     

Climatic forcing of nitrogen oxides through changes in tropospheric ozone and methane; global 3D model studies

A three-dimensional global chemical tracer model and a radiation transfer model have been used to study the role of NO_x emissions for radiative forcing of climate. Through production of tropospheric O₃, NO_x emissions lead to positive radiative forcing and warming. But by affecting the concentration of OH radicals, NO_x also reduces the levels of CH₄, thereby giving negative forcing and cooling. The lifetime of NO_x varies from hours to days, giving large spatial variations in the levels of NO_x. We have selected geographical regions representing different chemical and physical conditions, and chemical and radiative effects of reducing NO_x emissions by 20% in each region are studied. Due to nonlinearities in the O₃ chemistry as well as differences in convective activity, there are large geographical differences in the effect of NO_x on O₃ as well as variations in the annual profile of the changes. The effect of NO_x emissions on methane is also found to depend on the localisation of the emissions. The calculated ozone and methane forcing are of similar magnitude but of opposite sign. The methane effect acts on a global scale with a delay of approximately a decade, while the ozone effect is of regional character and occurs during weeks.