ROx Budgets and O3 Formation during Summertime at Xianghe Suburban Site in the North China Plain

Photochemical smog characterized by high concentrations of ozone (O3) is a serious air pollution issue in the North China Plain (NCP) region, especially in summer and autumn. For this study, measurements of O3, nitrogen oxides (NOx), volatile organic compounds (VOCs), carbon monoxide (CO), nitrous acid (HONO), and a number of key physical parameters were taken at a suburban site, Xianghe, in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O3 formation and find an optimal way to control O3 pollution. Here, the radical chemistry and O3 photochemical budget based on measurement data from 1-23 July using a chemical box model is investigated. The daytime (0600-1800 LST) average production rate of the primary radicals referred to as ROx (OH + HO2+ RO2) is 3.9 ppbv h-1. HONO photolysis is the largest primary ROx source (41％). Reaction of NO2 + OH is the largest contributor to radical termination (41％), followed by reactions of RO2 + NO2 (26％). The average diurnal maximum O3 production and loss rates are 32.9 ppbv h-1 and 4.3 ppbv h-1, respectively. Sensitivity tests without the HONO constraint lead to decreases in daytime average primary ROx production by 55％ and O3 photochemical production by 42％, highlighting the importance of accurate HONO measurements when quantifying the ROx budget and O3 photochemical production. Considering heterogeneous reactions of trace gases and radicals on aerosols, aerosol uptake of HO2 contributes 11％ to ROx sink, and the daytime average O3 photochemical production decreases by 14％. The O3-NOx-VOCs sensitivity shows that the O3 production at Xianghe during the investigation period is mainly controlled by VOCs.     

Variations in surface ozone and NOx at Kannur: a tropical, coastal site in India

Continuous measurements of surface ozone (O₃), NOx (NO + NO₂) and meteorological parameters have been made in Kannur (11.9?°N, 75.4?°E, 5?m asl), India from November 2009 to October 2010. It was observed that O₃ and NOx showed distinct diurnal and seasonal variabilities at this site. The annual average diurnal profile of O₃ showed a peak of (30.3?±?10.4) ppbv in the late afternoon and a minimum of (3.2?±?0.7) ppbv in the early morning. The maximum value of O₃ mixing ratio was observed in winter (44?±?3.1) ppbv and minimum during monsoon (18.46?±?3.5) ppbv. The rate of production of O₃ was found to be higher in December (10.1?ppbv/h) and lower in July (1.8?ppbv/h) during the time interval 0800?C1000?h. A correlation coefficient of 0.52 for the relationship between O₃ and [NO₂]/[NO] reveals the role of NO₂ photolysis that generates O₃ at this site. The correlation between O₃ and meteorological parameters indicate the influence of seasonal changes on O₃ production. Investigations were further extended to explore the week day weekend variations in O₃ mixing ratio at an urban site reveals the enhancement of O₃. The variations of O₃ mixing ratio with seasonal air mass flows were elucidated with the aid of backward air trajectories. This study also indicates how vapor phase organic species present in the ambient air at this location may influence the complex chemistry involving (VOCs) that enhances the production of O₃ at this location.     

Distributions of ozone and related trace gases at an urban site in western India

Continuous in-situ measurements of surface ozone (O₃), carbon monoxide (CO) and oxides of nitrogen (NOx) were conducted at Udaipur city in India during April 2010 to March 2011. We have analyzed the data to investigate both diurnal and seasonal variations in the mixing ratios of trace gases. The diurnal distribution of O₃ showed highest values in the afternoon hours and lower values from evening till early morning. The mixing ratios of CO and NOx showed a sharp peak in the morning hours but lowest in the afternoon hours. The daily mean data of O₃, CO and NOx varied in the ranges of 5–51 ppbv, 145–795 ppbv and 3–25 ppbv, respectively. The mixing ratios of O₃ were highest of 28 ppbv and lowest 19 ppbv during the pre-monsoon and monsoon seasons, respectively. While the mixing ratios of both CO and NOx showed highest and lowest values during the winter and monsoon seasons, respectively. The diurnal pattern of O₃ is mainly controlled by the variations in photochemistry and planetary boundary layer (PBL) depth. On the other hand, the seasonality of O₃, CO and NOx were governed by the long-range transport associated mainly with the summer and winter monsoon circulations over the Indian subcontinent. The back trajectory data indicate that the seasonal variations in trace gases were caused mainly by the shift in long-range transport pattern. In monsoon season, flow of marine air and negligible presence of biomass burning in India resulted in lowest O₃, CO and NOx values. The mixing ratios of CO and NOx show tight correlations during winter and pre-monsoon seasons, while poor correlation in the monsoon season. The emission ratio of ?CO/?NOx showed large seasonal variability but values were lower than those measured over the Indo Gangetic Plains (IGP). The mixing ratios of CO and NOx decreased with the increase in wind speed, while O₃ tended to increase with the wind speed. Effects of other meteorological parameters in the distributions of trace gases were also noticed.     

长江三角洲区域本底大气中致酸气体体积分数变化特征

利用2003-12—2004-11浙江临安区域大气本底站大气NOx、SO2体积分数的连续观测资料,分析其季节变化和日变化特征。结果表明：长江三角洲区域本底大气中致酸气体NOx、SO2体积分数值均为冬季最高,分别为23.81×10^-9和37.3×10^-9,主要受来自东北方向宁、沪区域城市群的相对高浓度污染物随气团传输影响;夏季最低,主要是局地源的贡献。降水对SO2去除作用明显,对NOx去除效果不大。NOx体积分数值冬季的日变化最为明显,呈现出一低一高的双峰型,09：00出现较高体积分数值,18：00出现最高体积分数值;而夏季为单峰型日变化,07：00出现最高体积分数值。SO2冬、春季的日变化明显,最高体积分数值出现在06：00左右,最低体积分数值出现在15：00左右。该区域NO2全年空气质量达到《环境空气质量标准》（GB 30952—1996）一级标准,SO2冬、春季超标较多,受到人类活动影响较明显。NO2和SO2空气污染指数在12月最大,分别为50和93。该区域NO2和SO2并未出现“周末效应”。     

Impacts of Future NOx and CO Emissions on Regional Chemistry and Climate over Eastern China

A coupled chemical/dynamical model (SOCOL-SOlar Climate Ozone Links) is applied to study the impacts of future enhanced CO and NOx emissions over eastern China on regional chemistry and climate. The result shows that the increase of CO and NOx emissions has significant effects on regional chemistry, including NOx, CO, O₃, and OH concentrations. During winter, the CO concentration is uniformly increased in the northern hemisphere by about 10 ppbv. During summer, the increase of CO has a regional distribution. The change in O₃, concentrations near eastern China has both strong seasonal and spatial variations. During winter, the surface O₃, concentrations decrease by about 2 ppbv, while during summer they increase by about 2 ppbv in eastern China. The changes of CO, NOx, and O₃, induce important impacts on OH concentrations. The changes in chemistry, especially O₃, induce important effects on regional climate. The analysis suggests that during winter, the surface temperature decreases and air pressure increases in central-eastern China. The changes of temperature and pressure produce decreases in vertical velocity. We should mention that the model resolution is coarse, and the calculated concentrations are generally underestimated when they are compared to measured results. However, because this model is a coupled dynamical/chemical model, it can provide some useful insights regarding the climate impacts due to changes in air pollutant emissions.     

On the variability and correlation of surface ozone and carbon monoxide observed in Hong Kong using trajectory and regression analyses

This paper investigates, the variability and correlation of surface ozone (Os) and carbon monoxide (CO) observed at Cape D'Aguilar in Hong Kong from 1 January 1994 to 31 December 1995. Statistical analysis shows that the average O3 and CO mixing ratios during the two years are 32±17ppbv and 305±191 ppbv, respectively. The O3/CO ratio ranges from 0.05 to 0.6 ppbv/ppbv with its frequency peaking at 0.15. The raw dataset is divided into six groups using backward trajectory and cluster analyses. For data assigned to the same trajectory type, three groups are further sorted out based on CO and NOX mixing ratios. The correlation coefficients and slopes of O3/CO for the 18 groups are calculated using linear regression analysis. Finally, five kinds of air masses with different chemical features are identified: continental background (CB), marine background (MB), regional polluted continental (RPC), perturbed marine (P*M), and local polluted (LP) air masses. Further studies indicate that O3 and CO in the conti     

Estimates of the Chemical Budget for Ozone at Waliguan Observatory

Waliguan Observatory (WO) is an in-land Global Atmosphere Watch (GAW) baseline station on the Tibetan plateau. In addition to the routine GAW measurement program at WO, measurements of trace gases, especially ozone precursors, were made for some periods from 1994 to 1996. The ozone chemical budget at WO was estimated using a box model constrained by these measured trace gas concentrations and meteorological variables. Air masses at WO are usually affected by the boundary layer (BL) in the daytime associated with an upslope flow, while it is affected by the free troposphere (FT) at night associated with a downslope flow. An anti-relationship between ozone and water vapor concentrations at WO is found by investigating the average diurnal cycle pattern of ozone and water vapor under clear sky conditions. This relationship implies that air masses at WO have both the FT and BL characteristics. Model simulations were carried out for clear sky conditions in January and July of 1996, respectively. The chemical characteristics of mixed air masses (MC) and of free tropospheric air masses (FT) at WO were investigated. The effects of the variation in NO_x and water vapor concentrations on the chemical budget of ozone at WO were evaluated for the considered periods of time. It was shown that ozone was net produced in January and net destroyed in July for both FT and MC conditions at WO. The estimated net ozone production rate at WO was –0.1 to 0.4 ppbv day^–1 in FT air of January, 0.0 to 1.0 ppbv day^–1 in MC air of January, –4.9 to –0.2 ppbv day^–1 in FT air of July, and –5.1 to 2.1 ppbv day^–1 in MC air of July.     

A Possible Photochemical Link Between Stratospheric and Near-Surface Ozone on Swiss Mountain Sites in Late Winter

Record high near-surface ozone concentrations at two elevated sites (Chaumont, 1140 m asl, and Rigi, 1030 m asl) in Switzerland were observed simultaneously with extremely low total ozone during a fair weather period in mid-February 1993. An analysis of ozone, temperature, humidity, and wind profiles suggests that the surface ozone peaks were most possibly generated within the region in a layer between about 1000 and 1500 m asl. Mean diurnal cycles of ozone concentration during the period shows a strong increase from late morning to late afternoon at Chaumont and at the same time a decrease at the high alpine site Jungfraujoch (3580 m asl). The different diurnal ozone cycles can both be explained photochemically by taking into account the large difference in NOx concentrations (about two orders of magnitude) between the sites. Photochemical processes are also indicated by the diurnal cycles of NO2 and NO concentration. As a strong photochemical activity is not expected in mid-February at 47°N, we hypothesize that the extremely low total ozone played a role. Total ozone controls the amount of UV-B radiation reaching the troposphere and thus influences photochemical processes. Using a radiation model, we calculated an increase in ozone photolysis at Chaumont and Jungfraujoch of 73% and 83%, respectively, on the day with the lowest total ozone (243 DU) compared to average February conditions (335 DU). It is suggested that total ozone changes have the potential to stimulate photochemistry sufficiently to produce the observed surface ozone peaks at Chaumont and Rigi of 61 and 64 ppbv, respectively. A fog layer just below Chaumont during these days probably also influenced photochemistry, but on a smaller spatial scale. Our empirical results on the influence of changing UV radiation on tropospheric photochemistry are in close agreement with model studies of other groups. Although this case study represents unique conditions, a distinct anticorrelation between near-surface ozone at Chaumont and total ozone also appears in other years (1992–1997) when selecting fair weather days in mid-February. However, other influences cannot be excluded. The selected days provide evidence of a significant photochemical source of ozone in the mid-latitude lower troposphere in late winter.     

The annual cycle of peroxides and ozone in marine air at Cape Grim, Tasmania

The concentration of gas-phase peroxides has been measured almost continuously at the Cape Grim baseline station (41° S) over a period of 393 days (7702 h of on-line measurements) between February 1991 and March 1992. In unpolluted marine air a distinct seasonal cycle in concentration was evident, from a monthly mean value of>1.4 ppbv in summer (December) to <0.2 ppbv in winter (July). In the summer months a distinct diurnal cycle in peroxides was also observed in clean marine air, with a daytime build-up in concentration and decay overnight. Both the seasonal and diurnal cycles of peroxides concentration were anticorrelated with ozone concentration, and were largely explicable using a simple photochemical box model of the marine boundary layer in which the central processes were daytime photolytic destruction of ozone, transfer of reactive oxygen into the peroxides under the low-NO_x ambient conditions that favour self-reaction between peroxy radicals, and continuous heterogeneous removal of peroxides at the ocean surface. Additional factors affecting peroxides concentrations at intermediate timescales (days to a week) were a dependence on air mass origin, with air masses arriving at Cape Grim from higher latitudes having lower peroxides concentrations, a dependence on local wind speed, with higher peroxides concentrations at lower wind speeds, and a systematic decrease in peroxides concentration during periods of rainfall. Possible physical mechanisms for these synoptic scale dependencies are discussed.     

Simulated Impacts of Sulfate and Nitrate Aerosol Formation on Surface-Layer Ozone Concentrations in China

The authors quantify the impacts of sulfate and nitrate aerosol formation on surface-layer 03 concentrations over China using the one-way nested-grid capa- bility of the global three-dimensional Goddard Earth Ob- serving System chemical transport model （GEOS-Chem）. Chemical reactions associated with sulfate formation are simulated to generally increase 03 concentrations in China. Over the North China Plain （NCP） and the Si- chuan Basin （SCB）, where simulated sulfate concentra- tions are the largest, ozone concentrations show maximum increases in spring by 1.8 ppbv （3.2%） in the NCP and by 2.6 ppbv （3.7%） in the SCB. On the contrary, nitrate formation is simulated to reduce 03 concentrations by up to 1.0 ppbv in eastern China, with the largest reduc- tions of 1.0 ppbv （1.4%） in summer over the NCE Ac- counting for the formation of both sulfate and nitrate, the surface-layer O3 concentrations over a large fraction of eastern China are simulated to increase in winter, spring, and autumn, dominated by the impact of sulfate forma- tion, but to decrease in summer because of the dominant contribution from nitrate formation.     

Effects of additional HONO sources on visibility over the North China Plain

The objective of the present study was to better understand the impacts of the additional sources of nitrous acid （HONO） on visibility, which is an aspect not considered in current air quality models. Simulations of HONO contributions to visibility over the North China Plain （NCP） during August 2007 using the fully coupled Weather Research and Forecasting/Chemistry （WRF/Chem） model were performed, including three additional HONO sources： （1） the reaction of photo-excited nitrogen dioxide （NO~） with water vapor; （2） the NO2 heterogeneous reaction on aerosol surfaces; and （3） HONO emissions. The model generally reproduced the spatial patterns and diurnal variations of visibility over the NCP well. When the additional HONO sources were included in the simulations, the visibility was occasionally decreased by 20%-30% （3-4 km） in local urban areas of the NCP. Monthly-mean concentrations of NO3, NH＋, SO]- and PM2.5 were increased by 20%-52% （3-11μg m-3）, 10%-38%, 6%-10%, and 6%-11% （9-17 μg m-3）, respectively; and in urban areas, monthly-mean accumulation- mode number concentrations （AMNC） and surface concentrations of aerosols were enhanced by 15%-20% and 10%-20%, respectively. Overall, the results suggest that increases in concentrations of PM2.5, its hydrophilic components, and AMNC, are key factors for visibility degradation. A proposed conceptual model for the impacts of additional HONO sources on visibility also suggests that visibility estimation should consider the heterogeneous reaction on aerosol surfaces and the enhanced atmospheric oxidation capacity due to additional HONO sources, especially in areas with high mass concentrations of NOx and aerosols.     

Ozone Concentrations in Rural Regions of the Yangtze Delta in China

Elevated concentrations of ozone have been observed at six non-urban, surface monitoring sites in the Yangtze Delta of China during a 16-month field experiment carried out in 1999 and 2000 as part of the joint Chinese-American China-MAP Project (the Yangtze Delta of china as an Evolving Metro-Agro-Plex). The average daytime (0900–1600 h) ozone levels for the monitoring period at sites ranged from 35 to 47 ppbv (parts per billion by volume) and the mean ozone levels from 26 to 35 ppbv. Observed data show seasonal variation obviously, with highest mixing ratios of ozone in May. Average daytime ozone levels in May at sites were between 60 and 79 ppbv. High ozone concentrations were most prevalent during the late spring. Frequency counts of hourly mean ozone concentration over 60 ppbv and 40 ppbv appeared peak values of 22–39% and 42–74% in May at sites. Even higher daytime ozone levels were observed during two regional episodes, in which average daytime (0900–1600 h) ozone concentrations during 10 May and 23 May 2000 were 68 to 81 ppbv, during Oct. 18 and Oct. 28, 1999 were 59 to 67 ppbv at sites. Peak value of ozone mixing ratio appearing in late spring, instead of in summer, was attributed to summer monsoon. Backward trajectories showed that ozone episodes associated with meteorological conditions. Also many high ozone levels associated with high CO levels and high CO to NO _x ratios, which suggests a contribution from sources of emission involving incomplete combustion.     

Observational study of surface ozone at an urban site in East China

In this study, we present the observational data of near surface ozone and some meteorological parameters during 2004, at an urban site (36°42′ N, 117°08′ E, 34.5 m a.s.l.) of Jinan, China. Hourly ozone concentrations exceeding the standard value of China, 100 ppbv, were observed for 65 h (in 23 days) from April to October, and values exceeding US NAAQS (National Ambient Air Quality Standard) for 1 h ozone, 120 ppbv, were observed for 15 h (in 7 days) from late May to early July. Ozone formation presented the phenomenon of “weekend effect”, especially in summer. Monthly variation of ozone coincided with temperature except for July and August. The low ozone levels in July and August may be due to the short sunshine duration and much rainfall during this period. Among these meteorological parameters, daily averaged ozone shows a significant correlation with temperature (r = 0.66) in the year and with relative humidity (r = − 0.75) in summer. Throughout the year, high ozone concentrations were mainly associated with the wind from 180 to 247.5°, while high ozone concentration seemed to have no obvious correlation with a given wind direction in summer. An anomalous nocturnal high ozone episode during 23–25 May 2004 was investigated. Growth fractions of ozone during the nighttime episode were 62.2% and 71.1% for 23 and 24 May, respectively. Synoptic analysis shows that favorable synoptic condition had presumably elevated the background ozone level in this region. Backward trajectory analysis shows that the increase of ozone concentration and the relatively constant high ozone concentrations during the night of May 23 might originate from the transport of ozone rich air mass above boundary layer. Transport of ozone from Yangtze Delta and East Central China might be a significant process for the high ozone level during night May 24 at Jinan.     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

飞机排放的NOx对中国地区NOx和臭氧的影响

根据2000年亚音速飞机排放的NO_x,利用三维全球化学输送模式(OSLOCTM2)研究亚音速飞机排放的NO_x对中国地区NO_x和臭氧的影响。模式结果表明:亚音速飞机排放的NO_x明显地影响中国北方地区,在1月份,250hPa高度NO_x的浓度增加大约50pptv,最大的相对变化为60％;在4月份,250hPa高度臭氧增加8ppbv,相对变化为5％。NO_x的增加主要是由于输送过程引起的,但臭氧的增加则是化学过程生成的结果。由于中国地区亚音速飞机排放的NO_x造成的NO_x的增加不超过10pptv,而且臭氧增加小于0.4ppbv。即使中国地区亚音速飞机排放的NO_x增加一倍,这个影响仍然比较小。     

边界层臭氧浓度变化特征及相关因子分析

根据广州市城区麓湖、郊区花都测站的2004年污染物监测数据和气象资料,采用统计分析软件SPSS和Excel分析了广州市臭氧浓度的时间变化特征,包括臭氧浓度的年季变化、周变化及日变化特征,并分析了O3与污染物CO、NOx(NO和NO2)、SO2、PM10以及与气象条件之间的相关性。结果表明:广州市臭氧浓度一年出现2个峰值,分别为6月和10月并且郊区浓度大于城区;一周之中最大浓度出现在周末;O3日平均浓度与NOx、NO、CO、相对湿度负相关性较显著,与PM10和气温正相关性较显著;在气温较高、湿度较低的晴朗少云天气时,易造成广州市臭氧的高浓度。     

Temporal Surface Ozone Patterns in Urban Manitoba, Canada

This study examined temporal surface ozone patternsfor two urban centres in Manitoba,Canada by analyzing hourly concentrations at theWinnipeg downtown (1995–1999), Winnipegresidential (1995–1999) and Brandon industrial(1998–1999) monitoring sites. The characteristicannual ozone cycle and diurnalcycles for June and December were attributable to: (1) theannual and diurnal solar radiation cycles,(2) temporal variations in the emissions of precursorchemical compounds, in particular the source strength ofnitrogen oxides, (3) temporal variationsin the height of the mixed layer, which determinethe degree of dilution of these emissions byatmospheric dispersion, and (4) an in situvolatile organic compound sensitive photochemicalregime, which resulted in decreased concentrations ofozone in response to increasedconcentrations of nitrogen oxides. Onlyone exceedance of the maximum acceptable level of82 ppb was recorded in the study period; itoccurred at the Brandon monitoring site on June 6, 1999.The sequence of weather and the hourly concentrationsof ozone and nitrogen oxides indicatedthat: (1) ozone fumigation, with the transition fromthe nocturnal boundary layer to the daytime mixed layer, mayhave supplemented photochemical ozone formation duringthe morning hours, and (2) during theevening hours, the post cold-frontal downward flux ofozone rich air, which was in the region dueto atmospheric transport, stratosphere-troposphere-exchangeor, possibly, due to the multiplicityof thunderstorms in the area in lateafternoon – early evening, may have been the main cause ofthis rare exceedance event.     

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.     

Enhancements of CO and O3 from burnings in sugar cane fields

The manual harvest of sugar cane requires the burning of its foliage. This burning has strongly increased in Brazil after the National Alcohol Program was started which substituted automobile gasoline engines for alcohol engines. Presently, the source strength per unit area of this rural pollution is comparable to the well-known biomass burning source in Amazonia. The observed concentrations of CO and O₃ in the rural area of the state of São Paulo during the 1988 burning season were twice as large as those reported from an aircraft experiment of 1985 for biomass burnings of the tropical rain forest. Results are reported from airplane measurements and from three fixed ground stations. Mixing ratios of ozone and carbon monoxide in the height range below 6 km are normally less than 40 and 100 ppbv, (parts per billion by volume), respectively, in the absence of burnings. A strong O₃ and CO layer was observed during the burning period with peak concentrations of 80 ppbv of ozone and 580 ppbv of CO at about 2 km. The concentrations of CH₄ and CO₂ were also large, 1756 ppbv and 409 ppmv, respectively, at 1500 m. During the dry season period of the experiment, the ground based O₃ average diurnal variations obtained at the rural sites were practically identical to the typical urban variation observed at São José dos Campos, with daytime ozone values between 45 and 60 ppbv. A second three-day airplane excursion to the surgar cane fields in the wet season of 1989 has produces results to be contrasted with the dry (burning) season of 1988 and 1989. Carbon monoxide concentrations were below 100 ppbv at all heights and ozone concentrations were around 30–40 ppbv. The maximum daytime concentrations at the ground station Bauru was 25 ppbv of O₃, and at Jaboticabal it was 35 ppbv of O₃, only one half of what was observed in the dry season.Universidade Estadual de São Paulo.