Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

The Role of In Situ Photochemistry in the Control of Ozone during Spring at the Jungfraujoch (3,580 m asl) – Comparison of Model Results with Measurements

A photochemical box model has been used to model themeasured diurnal ozone cycle in spring at Jungfraujochin the Swiss Alps. The comparison of the modelleddiurnal ozone cycle with the mean measured diurnalozone cycle in spring, over the period 1988–1996,shows a good agreement both with regard to the shapeand amplitude. Ozone concentrations increase duringthe daytime and reach a maximum at about 16:00–17:00(GMT) in both the modelled and the mean observed ozonecycle, indicative of net ozone production during thedaytime at Jungfraujoch in spring. The agreement isbetter when the modelled ozone cycle is compared withthe mean measured diurnal cycle (1988–1996) filteredfor north-westerly winds >5 m/s (representative ofregional background conditions at Jungfraujoch). Inaddition to ozone, the modelled diurnal cycle of[HO₂] + [CH₃O₂] also shows rather goodagreement with the mean diurnal cycle of the peroxyradicals measured during FREETEX '96, a FREETropopsheric Experiment at Jungfraujoch in April/May1996. Furthermore, this mean diurnal cycle of the sumof the peroxy radicals measured during FREETEX '96 isused to calculate, using steady-state expressions, therespective diurnal cycle of the OH radical. Thecomparison of the OH diurnal cycle, calculated fromthe peroxy radical measurements during FREETEX '96,with the modelled one, reveals also good agreement.The net ozone production rate during the day-time is0.27 ppbv h^-1 from the model, and 0.13 ppbvh^-1 from the observations during FREETEX '96. Theobservations and model results both suggest that thediurnal ozone variation in spring at Jungfraujoch isprimarily of photochemical origin. Furthermore, theobserved and modelled positive net ozone productionrates imply that tropospheric in situphotochemistry contributes significantly to theobserved high spring ozone values in the observedbroad spring-summer ozone maximum at Jungfraujoch.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.     

DOAS observations of formaldehyde and its impact on the HO<Subscript>x</Subscript> balance in the tropical Atlantic marine boundary layer

Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO₂ production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HO_x (HO₂+OH) balance of the remote marine boundary layer.     

Modelled and measured concentrations of peroxy radicals and nitrate radical in the U.S. Gulf Coast region during TexAQS 2006

Measurements of total peroxy radicals (HO₂?+?RO₂) and nitrate radical (NO₃) were made on the NOAA research vessel R/V?Brown along the U.S. Gulf Coast during the TexAQS 2006 field campaign. The measurements were modelled using a constrained box-model based upon the Master Chemical Mechanism (MCM). The agreement between modelled and measured HO₂?+?RO₂ was typically within ??40% and, in the unpolluted regions, within 30%. The analysis of the model results suggests that the MCM might underestimate the concentrations of some acyl peroxy radicals and other small peroxy radicals. The model underestimated the measurements of NO₃ by 60?C70%, possibly because of rapid heterogeneous uptake of N₂O₅. The MCM model results were used to estimate the composition of the peroxy radical pool and to quantify the role of DMS, isoprene and alkenes in the formation of RO₂ in the different regions. The measurements of HO₂?+?RO₂ and NO₃ were also used to calculate the gas-phase budget of NO₃ and quantify the importance of organic peroxy radicals as NO₃ sinks. RO₂ accounted, on average, for 12?C28% of the total gas-phase NO₃ losses in the unpolluted regions and for 1?C2% of the total gas-phase NO₃ losses in the polluted regions.     

A method for the selective measurement of HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript> radical concentrations using a Nafion-PERCA system

An instrument is developed for the measurement of peroxy radical using chemical amplification coupled with NO₂-luminol chemiluminescence detection. The chain length of 147 ± 10 (1σ) is determined by an HO₂ source that uses the photolysis of water vapor under 184.9 nm in air. A Nafion system equipped with a Nafion tube of ~2.2 mm external diameter and 350 mm length is employed in the PERCA instrument (Nafion-PERCA system). When flowing an air sample containing HO₂ through the Nafion system, it is found that - 94.6 % of HO₂ is removed. In contrast, only 17.8 % of RO₂ radicals (a mixtures of CH₃O₂ and CH₃C(O)O₂ with a ratio of 1.1:0.9) are removed. The results indicate the Nafion system has a good selective removing performance of HO₂ radical during the PERCA measurement. Therefore, the method could be applied to ambient and laboratory measurements of absolute concentrations of RO₂ as well as the sum of HO₂ and RO₂.     

Free Radicals and Fast Photochemistry during BERLIOZ

The free radicals OH, HO₂, RO₂, and NO₃ are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date.We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation –Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals.In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses.In addition considerable night-time peroxy radical production related to VOC reactions with NO₃ and O₃ could be quantified.     

Radical variability determined from LIMS and SAMS satellite data

Using satellite data, the variability of a large number of stratospheric trace constituents can be estimated. These constituents need not themselves be measured by the satellite; their concentrations can be derived using photochemical steady-state relationships. The global coverage provided by the satellite over a long time period means that, for example, monthly zonal mean profiles can be derived. This has been done for H, OH, HO₂, H₂O₂, Cl, ClO, HCl, HOCl, ClONO₂, NO and O. The standard deviation of these quantities is a measure of their variability. We argue that comparing theoretical variability estimates with measurements is a better test of a photochemical theory than simply the comparison of single modelled and observed profiles.     

On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

A Three-Dimensional Simulation of HO x Concentrations Over East Asia During TRACE-P

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is used to simulate three-dimensional concentration distributions of hydroxyl (OH) and hydroperoxyl (HO₂) radicals over the western Pacific Ocean during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign. Modeled values of OH and HO₂ and their closely related chemical species and photolysis rates are compared with observational data collected onboard the DC-8 aircraft. Comparison shows that the model reasonably reproduced these observed values over a broad range of conditions with an overall tendency to overestimate the measured OH and HO₂ by a factor of 1.56 and 1.24, respectively. A case study of OH, HO₂ and their closely related chemical species and photolysis rates along the DC-8 flights 11 and 12 conducted on 17–18 March 2001 shows that the model reproduces the temporal and spatial variations reasonable well, and produces more reliable OH and HO₂ concentrations in the polluted environment than in the clean marine boundary layer.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 3. Comparison of Modelled C2–C5 Hydrocarbons with Surface Measurements

In part 3 of this series of papers on a new 3-D global troposphericchemical transport model, using an Integrated Modelling System (IMS), anevaluation of the model performance in simulating global distributions andseasonal variations for volatile organic compounds (VOCs) in the atmosphere,is presented. Comparisons of model OH concentrations with previous modelstudies show consistent modelled OH levels from the subtropics tomidlatitudes, while more discrepancies occur over the tropical lowlatitudes, with IMS predicting the highest levels of OH. The close agreementbetween modelled OH concentrations over midlatitudes, where high surfaceNO_xand VOC concentrations are also found, is indicative of the strongphotochemical coupling between NO_x, VOCs and O₃ overthese latitudes. IMSOH concentrations in the Northern Hemisphere (NH) midlatitudes during summerare generally lower than available measurements, implying that models ingeneral are underestimating OH levels at this location and time of year.Substantial differences between model OH concentrations over low latitudesclearly highlight areas of uncertainty between models. IMS OH concentrationsare the highest in general of the models compared, one possible reason isthat biogenic emissions of species such as isoprene and monoterpenes arehighest in IMS, leading to higher O₃ levels and hence higher OH.Generally, the IMS VOC concentrations show a similar seasonality to themeasurements at most locations. In general though, IMS tends to underestimatethe NH wintertime VOC maximum and overestimate the NH summertime VOCminimum. Such an overestimate in summer could be due to IMSunderestimating OH levels, or an overestimation of VOC emissions or possiblya problem with model transport, all of these possibilities are explored.Except for n-pentane, the model underprediction of a VOC maximum during theNH winter month strongly suggests a missing emission mechanism in the modelor an underestimate of an existing one. It is very likely that there is alack of time varying emission sources in the model to account for theseasonal change in emission behaviour such as increasing energy usage (e.g.,electricity and gas), road transportation, engine performance, and otheranthropogenic factors which show strong seasonal characteristics. Theanomalous overprediction of wintertime n-pentane compared with its closesummertime prediction with the measurements suggest that emissions in thiscase may be too high.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

Vertical Distribution Characteristics of PM<Subscript>2.5</Subscript> Observed by a Mobile Vehicle Lidar in Tianjin,China in 2016

We present mobile vehicle lidar observations in Tianjin, China during the spring, summer, and winter of 2016. Mobile observations were carried out along the city border road of Tianjin to obtain the vertical distribution characteristics of PM_2.5. Hygroscopic growth was not considered since relative humidity was less than 60% during the observation experiments. PM_2.5 profile was obtained with the linear regression equation between the particle extinction coefficient and PM_2.5 mass concentration. In spring, the vertical distribution of PM_2.5 exhibited a hierarchical structure. In addition to a layer of particles that gathered near the ground, a portion of particles floated at 0.6–2.5-km height. In summer and winter, the fine particles basically gathered below 1 km near the ground. In spring and summer, the concentration of fine particles in the south was higher than that in the north because of the influence of south wind. In winter, the distribution of fine particles was opposite to that measured during spring and summer. High concentrations of PM_2.5 were observed in the rural areas of North Tianjin with a maximum of 350 μg m^–3 on 13 December 2016. It is shown that industrial and ship emissions in spring and summer and coal combustion in winter were the major sources of fine particles that polluted Tianjin. The results provide insights into the mechanisms of haze formation and the effects of meteorological conditions during haze–fog pollution episodes in the Tianjin area.     

HO x production due to radon decay in air

The HO _x (OH and HO₂) production rate in indoor air caused by radon decay was measured by the chemical amplification technique. The average HO _x production rate was found to be (4.31±0.07)×10⁵ HO _x per Rn decay per second (Bq) within the range of relative humidity from 3.4 to 55.0 percent at 22 °C. This work providedG(HO _x )-value, 7.86±0.13 #/100 eV in air by directly measuring [HO _x ] from radiolysis of water vapor. It is also found that there is no obvious relationship between the HO _x production rate and the relative humidity in this range. Therefore, this work provides both the basic data for the evaluation of radioactive pollution in indoor air as well as a potentially useful way to produce HO _x concentrations in air.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 2. Model Chemistry and Comparison of Modelled CH4, CO, and O3 with Surface Measurements

In part two of this series of papers on the IMS model, we present the chemistry reaction mechanism usedand compare modelled CH₄, CO, and O₃ witha dataset of annual surface measurements. The modelled monthly and 24-hour mean tropospheric OH concentrationsrange between 5–22 × 10⁵ moleculescm^–3, indicating an annualaveraged OH concentration of about 10 × 10⁵ moleculescm^–3. This valueis close to the estimated 9.7 ± 0.6 × 10⁵ moleculescm^–3 calculated fromthe reaction of CH₃CCl₃ with OH radicals.Comparison with CH₄ generally shows good agreementbetween model and measurements, except for the site at Barrow where modelledwetland emission in the summer could be a factor 3 too high.For CO, the pronounced seasonality shown in the measurements is generally reproduced by the model; however, the modelled concentrations are lower thanthe measurements. This discrepancy may due to lower the CO emission,especially from biomass burning,used in the model compared with other studies.For O₃, good agreement between the model and measurements is seenat locations which are away from industrial regions. The maximum discrepancies between modelled results and measurementsat tropical and remote marine sites is about 5–10 ppbv,while the discrepancies canexceed 30 ppbv in the industrial regions.Comparisons in rural areas at European and American continental sites arehighly influenced by the local photochemicalproduction, which is difficult to model with a coarse global CTM.The very large variations of O₃ at these locations vary from about15–25 ppbv in Januaryto 55–65 ppbv in July–August. The observed annual O₃amplitude isabout 40 ppbv compared with about 20 ppbv in the model. An overall comparison of modelled O₃ with measurements shows thatthe O₃seasonal surface cycle is generally governed bythe relative importance of two key mechanisms that drivea springtime ozone maximum and asummertime ozone maximum.     

Cloud chemistry effects on tropospheric photooxidants in polluted atmosphere — Model results

The mathematical model presented in this paper describes in detail the gas-phase chemistry (22 reactions), gas-phase/liquid-phase equilibrium (18 equilibria) and liquid-phase chemistry (57 reactions and equilibria) in a stratiform cloud system. The model is used to analyze the influence of the liquid phase on the photooxidant formation and destruction for different gaseous SO₂ concentrations with and without consideration of organic aqueous phase chemistry. It has been shown that for [SO₂]>1 ppb the cloud is quantitatively a sink for H₂O₂, OH, HO₂ and O₃. The ozon destruction via O₃+O₂ ^-, which is most important in remote areas, is in polluted areas only significant at summer days. The role of organic components in cloud water consists in the transformation OH HO₂ where HO₂ is further transformed into H₂O₂.     

OH in the tropical upper troposphere and its relationships to solar radiation and reactive nitrogen

In situ measurements of [OH], [HO₂] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O₃] and [H₂O] ([O₃]?[H₂O]), or its sink [NO_y]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O₃], [NO], and [NO_y]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HO_x] ([OH] + [HO₂]) correlated reasonably well with [O₃]?[H₂O]/[NO_y], suggesting that [O₃]?[H₂O] and [NO_y] are the significant source and sink, respectively, of [HO_x].     

Seasonal characteristics of tropical marine boundary layer air measured at the Cape Verde Atmospheric Observatory

Observations of the tropical atmosphere are fundamental to the understanding of global changes in air quality, atmospheric oxidation capacity and climate, yet the tropics are under-populated with long-term measurements. The first three years (October 2006–September 2009) of meteorological, trace gas and particulate data from the global WMO/Global Atmospheric Watch (GAW) Cape Verde Atmospheric Observatory Humberto Duarte Fonseca (CVAO; 16° 51′ N, 24° 52′ W) are presented, along with a characterisation of the origin and pathways of air masses arriving at the station using the NAME dispersion model and simulations of dust deposition using the COSMO-MUSCAT dust model. The observations show a strong influence from Saharan dust in winter with a maximum in super-micron aerosol and particulate iron and aluminium. The dust model results match the magnitude and daily variations of dust events, but in the region of the CVAO underestimate the measured aerosol optical thickness (AOT) because of contributions from other aerosol. The NAME model also captured the dust events, giving confidence in its ability to correctly identify air mass origins and pathways in this region. Dissolution experiments on collected dust samples showed a strong correlation between soluble Fe and Al and measured solubilities were lower at high atmospheric dust concentrations. Fine mode aerosol at the CVAO contains a significant fraction of non-sea salt components including dicarboxylic acids, methanesulfonic acid and aliphatic amines, all believed to be of oceanic origin. A marine influence is also apparent in the year-round presence of iodine and bromine monoxide (IO and BrO), with IO suggested to be confined mainly to the surface few hundred metres but BrO well mixed in the boundary layer. Enhanced CO₂ and CH₄ and depleted oxygen concentrations are markers for air-sea exchange over the nearby northwest African coastal upwelling area. Long-range transport results in generally higher levels of O₃ and anthropogenic non-methane hydrocarbons (NMHC) in air originating from North America. Ozone/CO ratios were highest (up to 0.42) in relatively fresh European air masses. In air heavily influenced by Saharan dust the O₃/CO ratio was as low as 0.13, possibly indicating O₃ uptake to dust. Nitrogen oxides (NO_x and NO_y) show generally higher concentrations in winter when air mass origins are predominantly from Africa. High photochemical activity at the site is shown by maximum spring/summer concentrations of OH and HO₂ of 9?×?10⁶ molecule cm^?3 and 6?×?10⁸ molecule cm^?3, respectively. After the primary photolysis source, the most important controls on the HO_x budget in this region are IO and BrO chemistry, the abundance of HCHO, and uptake of HO_x to aerosol.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.