Measurements of surface ozone at semi-arid site Anantapur (14.62°N, 77.65°E, 331 m asl) in India

In the present study, an attempt has been made to examine the governing photochemical processes of surface ozone (O₃) formation in rural site. For this purpose, measurements of surface ozone and selected meteorological parameters have been made at Anantapur (14.62°N, 77.65°E, 331 m asl), a semi-arid zone in India from January 2002 to December 2003. The annual average diurnal variation of O₃ shows maximum concentration 46 ppbv at noon and minimum 25 ppbv in the morning with 1σ standard deviation. The average seasonal variation of ozone mixing ratios are observed to be maximum (about 60 ppbv) during summer and minimum (about 22 ppbv) in the monsoon period. The monthly daytime and nighttime average surface ozone concentration shows a maximum (55 ± 7 ppbv; 37 ± 7.3 ppbv) in March and minimum (28 ± 3.4 ppbv; 22 ± 2.3 ppbv) in August during the study period. The monthly average high (low) O₃ 48.9 ± 7.7 ppbv (26.2 ± 3.5 ppbv) observed at noon in March (August) is due to the possible increase in precursor gas concentration by anthropogenic activity and the influence of meteorological parameters. The rate of increase of surface ozone is high (1.52 ppbv/h) in March and lower (0.40 ppbv/h) in July. The average rate of increase of O₃ from midnight to midday is 1 ppbv/h. Surface temperature is highest (43–44°C) during March and April months leading to higher photochemical production. On the other hand, relative humidity, which is higher during the rainy season, shows negative correlation with temperature and ozone mixing ratio. It can be seen that among the two parameters are measured, correlation of surface ozone with wind speed is better (R ²=0.84) in compare with relative humidity (R ²=0.66).     

Synoptic patterns in relation to ozone concentrations in west-central Taiwan

Summary Recent studies have shown that regional orography and synoptic patterns greatly affect ozone concentrations. The orography of certain locations is unfavorable for pollutant dispersion, and specific synoptic patterns in these locations lead to serious air pollution episodes. Frequent ozone episodes (defined as hourly ozone ≥ 120 ppbv) in west-central Taiwan during recent years have generated much concern. High ozone days (defined as hourly ozone ≥ 80 ppbv) are also occurring more frequently. High ozone days occur mainly during autumn, but there has been no clear linear relationship demonstrated between any single meteorological variable and pollutant concentration. In this study, statistical data from 1997–1999 has shown that high ozone levels occur with two types of synoptic patterns. The first type consists of a continental anticyclone emanating from mainland China which is swept towards Taiwan. The second is a tropical low pressure system moving northwards closer to Taiwan. West-central Taiwan is located in the lee of the Central Ranges (altitude of 2500 ∼ 3500 m). These synoptic patterns are unfavorable for pollutant dispersion and cause high ozone days. Received October 14, 2000/Revised January 5, 2001     

Evaluation of surface ozone measurements during 2000–2005 at a rural area in the upper Spanish plateau

This paper presents the main experimental results of surface ozone concentrations measured at a rural area in Northern Spain from February 2000 to December 2005. Daily and seasonal variation of ozone has been analysed. The peak concentration levels are obtained in the afternoon, mean value around 88 μg m⁻³, with extreme average values of 59 μg m⁻³ in January and 113 μg m⁻³ in July. Small differences are found in the mean and median of the ozone levels from April to August, when spring and summer maxima are observed. Despite the great inter-annual ozone variability obtained, most air quality indicators showed a positive trend. Further analysis of the monthly mean ozone concentrations of the main percentiles have also been performed using a harmonic model. The upward trend was 6.2 ± 1.7 μg m⁻³ for the 98th percentile. To interpret the main features of the annual cycle and describe the ozone peaks, the influence of meteorological factors is studied. In summer, ozone production is governed by local processes, air temperature being the major controlling factor. However, the origin of the spring maximum is not so well identified.     

Ozone in ambient air at a tropical megacity, Delhi: characteristics, trends and cumulative ozone exposure indices

Seven year data of hourly surface ozone concentration is analyzed to study diurnal cycle, trends, excess of ozone levels above threshold value and cumulative ozone exposure indices at a tropical megacity, Delhi. The ozone levels clearly exhibit a diurnal cycle, similar to what has been found in other urban places. A sharp increase in the ozone levels during forenoon and a sharp decrease in the early afternoon can be observed. The average rate of increase in ozone concentration between 09 and 12 h has been observed to be 7.1 ppb h⁻¹. We find that the daily maximum and daytime 8-h (10–17 h) ozone levels are increasing at a rate of about 1.7 (± 0.7) and 1.3 (± 0.56) ppb y⁻¹, respectively. The directives on ozone pollution in ambient air provided by United Nations Economic Commission for Europe and World Health Organization for vegetation (AOT40) and human health protection were used to assess the air quality. The present surface ozone levels in the city are high enough to exceed “Critical Levels” which are considered to be safe for human health, vegetation and forest. The human health threshold was exceeded for up to ~45 days per year. The AOT40 (Accumulated exposure Over a Threshold of 40 ppb) threshold was exceeded significantly during winter (D-J-F) and pre-monsoon (M-A-M) (Rabi crop growing season) season in India. Translating AOT40 exceedances during pre-monsoon into relative yield loss we estimate yield loss of 22.7%, 22.5%, 16.3% and 5.5% for wheat, cotton, soybean and rice, respectively.     

Volatile organic compounds at a rural site in western Senegal

The objectives of this study were to identify species and levels of volatile organic compounds (VOCs), and determine their oxidation capacity in the rural atmosphere of western Senegal. A field study was conducted to obtain air samples during September 14 and September 15, 2006 for analyses of VOCs. Methanol, acetone, and acetaldehyde were the most abundant detected chemical species and their maximum mixing ratios reached 6 parts per billion on a volume basis (ppbv). Local emission sources such as firewood and charcoal burning strongly influenced VOC concentrations. The VOC concentrations exhibited little temporal variations due to the low reactivity with hydroxyl radicals, with reactivity values ranging from 0.001 to 2.6 s⁻¹. The conditions in this rural site were rather clean. Low ambient NO _x levels limited ozone production. Nitrogen oxide (NO _x ) levels reached values less than 2 ppbv and maximum VOC/NO _x ratios reached 60 ppbvC/ppbv, with an overall average of 2.4 ± 4.5 ppbvC/ppbv. This indicates that the rural western Senegal region is NO _x limited in terms of oxidant formation potential. Therefore, during the study period photochemical ozone production became limited due to low ambient NO _x levels. The estimated ozone formation reactivity for VOCs was low and ranged between −5.5 mol of ozone/mol of benzaldehyde to 0.6 mol/mol of anthropogenic dienes.     

Downward transport and modification of tropospheric ozone through moist convection

This study estimated the largely unstudied downward transport and modification of tropospheric ozone associated with tropical moist convection using a coupled meteorology-chemistry model. High-resolution cloud resolving model simulations were conducted for deep moist convection events over West Africa during August 2006 to estimate vertical transport of ozone due to convection. Model simulations realistically reproduced the characteristics of deep convection as revealed by the estimated spatial distribution of temperature, moisture, cloud reflectivity, and vertical profiles of temperature and moisture. Also, results indicated that vertical transport reduced ozone by 50% (50 parts per billion by volume, ppbv) in the upper atmosphere (12–15 km) and enhanced ozone by 39% (10 ppbv) in the lower atmosphere (<2 km). Field observations confirmed model results and indicated that surface ozone levels abruptly increased by 10–30 ppbv in the area impacted by convection due to transport by downdrafts from the upper troposphere. Once in the lower troposphere, the lifetime of ozone decreased due to enhanced dry deposition and chemical sinks. Ozone removal via dry deposition increased by 100% compared to non-convective conditions. The redistribution of tropospheric ozone substantially changed hydroxyl radical formation in the continental tropical boundary layer. Therefore, an important conclusion of this study is that the redistribution of tropospheric ozone, due to deep convection in non-polluted tropical regions, can simultaneously reduce the atmospheric loading of ozone and substantially impact the oxidation capacity of the lower atmosphere via the enhanced formation of hydroxyl radicals.     

High resolution simulation of recent Arctic and Antarctic stratospheric chemical ozone loss compared to observations

Simulations of polar ozone losses were performed using the three-dimensional high-resolution (1^∘ × 1^∘) chemical transport model MIMOSA-CHIM. Three Arctic winters 1999–2000, 2001–2002, 2002–2003 and three Antarctic winters 2001, 2002, and 2003 were considered for the study. The cumulative ozone loss in the Arctic winter 2002–2003 reached around 35% at 475 K inside the vortex, as compared to more than 60% in 1999–2000. During 1999–2000, denitrification induces a maximum of about 23% extra ozone loss at 475 K as compared to 17% in 2002–2003. Unlike these two colder Arctic winters, the 2001–2002 Arctic was warmer and did not experience much ozone loss. Sensitivity tests showed that the chosen resolution of 1^∘ × 1^∘ provides a better evaluation of ozone loss at the edge of the polar vortex in high solar zenith angle conditions. The simulation results for ozone, ClO, HNO₃, N₂O, and NO _y for winters 1999–2000 and 2002–2003 were compared with measurements on board ER-2 and Geophysica aircraft respectively. Sensitivity tests showed that increasing heating rates calculated by the model by 50% and doubling the PSC (Polar Stratospheric Clouds) particle density (from 5 × 10⁻³ to 10⁻² cm⁻³) refines the agreement with in situ ozone, N₂O and NO _y levels. In this configuration, simulated ClO levels are increased and are in better agreement with observations in January but are overestimated by about 20% in March. The use of the Burkholder et al. (1990) Cl₂O₂ absorption cross-sections slightly increases further ClO levels especially in high solar zenith angle conditions. Comparisons of the modelled ozone values with ozonesonde measurement in the Antarctic winter 2003 and with Polar Ozone and Aerosol Measurement III (POAM III) measurements in the Antarctic winters 2001 and 2002, shows that the simulations underestimate the ozone loss rate at the end of the ozone destruction period. A slightly better agreement is obtained with the use of Burkholder et al. (1990) Cl₂O₂ absorption cross-sections.     

An ozone depletion event in the sub-arctic surface layer over Hudson Bay,Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrO _x remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO₂ ratio.     

A 10-year study of background surface ozone concentrations on the island of Gozo in the Central Mediterranean

A 10-year study of surface ozone mixing ratios in the Central Mediterranean was conducted based on continuous ozone measurements from 1997 to 2006 by a background regional Global Atmospheric Watch (GAW) station on the island of Gozo. The mean annual maximum mixing ratio is of the order of 66 ppbv in April–May with a broad secondary maximum of 64 ppbv in July–September. No long-term increase or decrease in the background level of surface ozone could be observed over the last 10 years. This is contrary to observations made in the Eastern Mediterranean, where a slow decrease in the background ozone mixing ratio was observed over the past 7 years. Despite the very high average annual ozone mixing ratio exceeding 50 ppbv—in fact, the highest average background ozone mixing ratio ever measured in Europe—, the diurnal O _{3 max}/O _{3 min} index of <1.40 indicates that the island of Gozo is a good site for measuring background surface ozone. However, frequent photosmog events from June to September during the past 10 years with ozone mixing ratios exceeding 90 ppbv indicate that the Central Mediterranean is prone to long-range transport of air pollutants from Europe by northerly winds. This was particularly evident during the so-called “August heatwave” of the year 2003 when the overall ozone mixing ratio was 4.6 ppbv higher than the average of all other 9 months of August since 1997. Air mass back-trajectory analysis of the August 2003 photosmog episodes on Gozo confirmed that ozone pollution originated from the European continent. Regression analysis was used to analyse the 10-year data set in order to model the behaviour of the ozone mixing ratio in terms of the meteorological parameters of wind speed, relative humidity, global radiation, temperature, month of year, wind sector, atmospheric pressure, and time of day (predictors). Most of these predictors were found to significantly affect the ozone mixing ratios. From March to November, the monthly average of the AOT40 threshold value for the protection of crops and vegetation against ozone was constantly exceeded on Gozo during the past 10 years.     

Kinetic Study of the Reactions of Ozone with Polycyclic Aromatic Hydrocarbons Adsorbed on Atmospheric Model Particles

In this experimental study, rate constants were measured for the reactions of ozone with 13 polycyclic aromatic hydrocarbons (PAHs) adsorbed on different types of particles. Graphite and silica were chosen to model, respectively, carbonaceous and mineral atmospheric particles. The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate PAH concentrations versus time. Second order rate constants were calculated considering the ozone gaseous concentration. At room temperature, rate constants varied, in the case of graphite particles, between (1.5 ± 0.5) × 10⁻¹⁷ and (1.3 ± 0.7) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for chrysene and dibenzo[a,l]pyrene, respectively, and, in the case of silica particles, between (1.5 ± 0.3) × 10⁻¹⁷ and (1.4 ± 0.3) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for fluoranthene and benzo[a]pyrene, respectively. Different granulometric parameters (particle size, pore size) and different PAH concentrations were tested in the case of silica particles. Heterogeneous reactions of ozone with particulate PAHs are shown to be more rapid than those occurring in the gas-phase, and may be competitive with atmospheric photodegradation.     

An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m³ during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.     

Modelling of near-surface ozone over South Asia

Hourly, three-dimensional, fields of tropospheric ozone have been produced for 12 consecutive months on a domain covering South Asia, using the regional Eulerian off-line chemistry transport model MATCH. The results were compared with background observations to investigate diurnal and seasonal variations of near-surface ozone in the region. MATCH reproduced the seasonality of near-surface ozone at most locations in the area. However, the current, and previous, studies indicate that the model consequently overestimate night-time concentrations, while it occasionally underestimates the day-time, near-surface, ozone concentrations. The lowest monthly-mean concentrations of near-surface ozone are typically experienced in June–September, coincident with the rainy season in most areas. The seasonality is not identical across the domain; some locations have a completely different trend. Large areas in Northern India and Nepal show a secondary minimum during the cold winter season (December–January). High concentrations of near-surface ozone are found over the oceans, close to the Indian subcontinent, due to the less efficient dry deposition to water surfaces; over parts of Tibet due to influence of free tropospheric air and little deposition to snow covered surfaces; and along the Gangetic valley due to the large emissions of precursors in this region. Monthly-mean ozone concentrations in the densely populated northern India range from 30–45 ppb(v). The model results were also used to produce maps of AOT40. The results point towards similar levels of AOT40 in India as in Europe: large areas of India show 3-month AOT40 values above 3 ppm(v) hours.

The atmospheric sulfur cycle in ECHAM-4 and its impact on the shortwave radiation

 The atmospheric general circulation model ECHAM-4 is coupled to a chemistry model to calculate sulfate mass distribution and the radiative forcing due to sulfate aerosol particles. The model simulates the main components of the hydrological cycle and, hence, it allows an explicit treatment of cloud transformation processes and precipitation scavenging. Two experiments are performed, one with pre-industrial and one with present-day sulfur emissions. In the pre-industrial emission scenario SO₂ is oxidized faster to sulfate and the in-cloud oxidation via the reaction with ozone is more important than in the present-day scenario. The atmospheric sulfate mass due to anthropogenic emissions is estimated as 0.38 Tg sulfur. The radiative forcing due to anthropogenic sulfate aerosols is calculated diagnostically. The backscattering of shortwave radiation (direct effect) as well as the impact of sulfate aerosols on the cloud albedo (indirect effect) is estimated. The model predicts a direct forcing of −0.35 W m^-2 and an indirect forcing of −0.76 W m^-2. Over the continents of the Northern Hemisphere the direct forcing amounts to −0.64 W m^-2. The geographical distribution of the direct and indirect effect is very different. Whereas the direct forcing is strongest over highly polluted continental regions, the indirect forcing over sea exceeds that over land. It is shown that forcing estimates based on monthly averages rather than on instantaneous sulfate pattern overestimate the indirect effect but have little effect on the direct forcing. Received: 16 October 1996/Accepted: 24 October 1996     

Variability of ozone in the marine boundary layer of the equatorial Pacific Ocean

This study examines the processes controlling the diurnal variability of ozone (O₃) in the marine boundary layer of the Kwajalein Atoll, Republic of the Marshall Islands (latitude 8° 43′ N, longitude 167° 44′ E), during July to September 1999. At the study site, situated in the equatorial Pacific Ocean, O₃ mixing ratios remained low, with an overall average of 9–10 parts per billion on a volume basis (ppbv) and a standard deviation of 2.5 ppbv. In the absence of convective storms, daily O₃ mixing ratios decreased after sunrise and reached minimum during the afternoon in response to photochemical reactions. The peak-to-peak amplitude of O₃ diurnal variation was approximately 1–3 ppbv. During the daytime, O₃ photolysis, hydroperoxyl radicals, hydroxyl radicals, and bromine atoms contributed to the destruction of O₃, which explained the observed minimum O₃ levels observed in the afternoon. The entrainment of O₃-richer air from the free troposphere to the local marine boundary layer provided a recovery mechanism of surface O₃ mixing ratio with a transport rate of 0.04 to 0.2 ppbv per hour during nighttime. In the presence of convection, downward transport of O₃-richer tropospheric air increased surface O₃ mixing ratios by 3–12 ppbv. The magnitude of O₃ increase due to moist convection was lower than that observed over the continent (as high as 20–30 ppbv). Differences were ascribed to the higher O₃ levels in the continental troposphere and weaker convection over the ocean. Present results suggest that moist convection plays a role in surface-level O₃ dynamics in the tropical marine boundary layer.     

Dynamics,stratospheric ozone,and climate change

Abstract

Dynamics affects the distribution and abundance of stratospheric ozone directly through transport of ozone itself and indirectly through its effect on ozone chemistry via temperature and transport of other chemical species. Dynamical processes must be considered in order to understand past ozone changes, especially in the northern hemisphere where there appears to be significant low‐frequency variability which can look “trend‐like” on decadal time scales. A major challenge is to quantify the predictable, or deterministic, component of past ozone changes. Over the coming century, changes in climate will affect the expected recovery of ozone. For policy reasons it is important to be able to distinguish and separately attribute the effects of ozone‐depleting substances and greenhouse gases on both ozone and climate. While the radiative‐chemical effects can be relatively easily identified, this is not so evident for dynamics — yet dynamical changes (e.g., changes in the Brewer‐Dobson circulation) could have a first‐order effect on ozone over particular regions. Understanding the predictability and robustness of such dynamical changes represents another major challenge. Chemistry‐climate models have recently emerged as useful tools for addressing these questions, as they provide a self‐consistent representation of dynamical aspects of climate and their coupling to ozone chemistry. We can expect such models to play an increasingly central role in the study of ozone and climate in the future, analogous to the central role of global climate models in the study of tropospheric climate change.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Tropospheric ozone profiles near equator and meteorological parameters

This is a study of ozone profile shapes in the 800 to 100 millibar range obtained with balloonsonde data over Trivandrum (8.5° N) during 1975–76 and possible associations of these shapes to some meteorological parameters.Whereas monotonic ozone profiles were noted with clear weather conditions, those associated with cloud cover show three basic anomalous features. Some bulges of increased values are observed in the range of 800 to 500 mb. In the 500–100 mb range, short range or localized cloud cover or passing weather disturbances are associated with fluctuation patterns in the ozone profile and an average depleted value of ozone. The fluctuations are also associated with changing wind speed and direction at these heights.Possible causative mechanisms are discussed. Lightning associated with thundestorm, producing additional CO and NO are sought to interpret the bulges at lower heights. The decrease in values as well as the fluctuation patterns are suggested as due to possible incursion of water vapour from troposphere to stratosphere in the tropical region and dynamical effects associated with it.     

Distributions of O3, CO and NMHCs over the rural sites in central India

The surface level measurements of O₃, CO, CH₄ and light NMHCs were made at eight different rural sites in the central part of India during February, 2004. The online analyzer was used for in-situ measurement of O₃ while air samples were collected for the analyses of CO, CH₄ and NMHCs using the gas chromatography techniques. The average mixing ratios of O₃, which were in the range of 60–90 ppbv, are significantly higher compared to the typical values reported for urban sites of India. The increase rates of O₃ in the forenoon hours were estimated to be in the range of about 8.8–10 ppbv h⁻¹. The slopes of ∆O₃/∆CO, which is an indicator of the efficiency of photochemical production, were in the range of 0.24–0.33 ppbv ppbv⁻¹. However, levels of primary pollutants e.g., NMHCs, CO, etc. at these sites were much lower than urban sites, but higher compared to previously observed values surrounding marine region of India. The estimated ratios of NMHCs and CO indicate fossil fuel combustion process as the dominant source of primary pollutants in this corridor.