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.     

NOx or VOC Limitation in East German Ozone Plumes?

The ozone forming potential of VOCs and NO_x for plumes observed from several cities and a power plant in eastern Germany was investigated. A closed box model with a gas phase photochemical reaction mechanism was employed to simulate several scenarios based upon aircraft observations. In several of the scenarios, the initial concentrations of NO_x, VOCs, and SO₂, were reduced to study the factors limiting the O₃ production. Ozone production was limited by the initial VOC concentrations for all of the simulated plumes. Higher O₃ concentrations were produced with reduced initial NO_x. In one sample with high SO₂ mixing ratios (>100 ppb), SO₂ was also identified as a significant contributor to the production of O₃.     

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.     

Daily, weekly and seasonal relationships among VOCs, NOx x and O3 in a semi-urban area near Barcelona

Daily, weekly, and seasonal patterns of O₃, NOx _x and VOCs and their relationship to meteorological conditions were studied in a semi-urban site near Barcelona by means of five-day long campaigns that included weekend and labor days in December, March, June, and October. The plant protection thresholds for ozone and NO₂ were exceeded, respectively, on all the studied days in summer and on all the studied days. Ozone formation was predominantly local and relied on photochemical processes with VOCs playing a controlling role. Formaldehyde, acetaldehyde, methanol, toluene, isoprene, and acetone (in this order) presented the highest O₃ formation potential during the studied periods. These results highlight the important role in O₃ formation played by VOC species such as acetaldehyde, methanol, and acetone, that all have a significant biogenic component. Thus, these VOCs must be taken into account in the discussion of any ozone abatement strategy.     

Background ozone and anthropogenic ozone enhancement at niwot ridge,Colorado

The mixing ratios for ozone and NO_x (NO+NO₂) have been measured at a rural site in the United States. From the seasonal and diurnal trends in the ozone mixing ratio over a wide range of NO_x levels, we have drawn certain conclusions concerning the ozone level expected at this site in the absence of local photochemical production of ozone associated with NO_x from anthropogenic sources. In the summer (June 1 to September 1), the daily photochemical production of ozone is found to increase in a linear fashion with increasing NO_x mixing ratio. For NO_x mixing ratios less than 1 part per billion by volume (ppbv), the daily increase is found to be (17±3) [NO_x]. In contrast, the winter data (December 1 to March 1) indicate no significant increase in the afternoon ozone level, suggesting that the photochemical production of ozone during the day in winter approximately balances the chemical titration of ozone by NO and other pollutants in the air. The extrapolated intercept corresponding to [NO_x]=0 taken from the summer afternoon data is 13% less than that observed from the summer morning data, suggesting a daytime removal mechanism for O₃ in summer that is attributed to the effects of both chemistry and surface deposition. No significant difference is observed in the intercepts inferred from the morning and afternoon data taken during the winter.The results contained herein are used to deduce the background ozone level at the measurement site as a function of season. This background is equated with the natural ozone background during winter. However, the summer data suggest that the background ozone level at our site is elevated relative to expected natural ozone levels during the summer even at low NO_x levels. Finally, the monthly daytime ozone mixing ratios are reported for 0[NO_x]0.2 ppbv, 0.3 ppbv[NO_x]0.7 ppbv and 1 ppbv[NO_x]. These monthly ozone averages reflect the seasonal ozone dependence on the NO_x level.     

Photochemistry in the Arctic Free Troposphere: Ozone Budget and Its Dependence on Nitrogen Oxides and the Production Rate of Free Radicals

Local ozone production and loss rates for the arctic free troposphere (58–85° N, 1–6 km, February–May) during the TroposphericOzone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1–3 km layer and a factor of 7 in the 3–6 kmlayer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1–3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NO_x mixing ratiosup to 300 pptv in February and for NO_x mixing ratios up to 500 pptv in May. These NO_x limits are an order of magnitude higher thanmedian NO_x levels observed, illustrating the strong dependence ofgross ozone production rates on NO_x mixing ratios for the majority of theobservations. The threshold NO_x mixing ratio needed for netpositive ozone production was also calculated to increase from NO_x 10pptv in February to 25 pptv in May, suggesting that the NO_x levels needed to sustain net ozone production are lower in winter than spring. This lower NO_x threshold explains how wintertime photochemical ozone production can impact the build-up of ozone over winter and early spring. There is also an altitude dependence as the threshold NO_x neededto produce net ozone shifts to higher values at lower altitudes. This partly explains the calculation of net ozone destruction for the 1–3 km layerand net ozone production for the 3–6 km layer throughout the campaign.     

High atmospheric NO x levels and multiple photochemical steady states

Previous zero-dimensional photochemical calculations indicate that multiple tropospheric steady states may exist, in which different NO _x (NO+NO₂) levels could be supported by the same source of NO _x . To investigate this possibility more closely, a one-dimensional photochemical model has been used to estimate the rate of removal of atmospheric NO _x compounds at different NO _x levels. At low NO _x levels NO _x is photochemically converted to HNO₃, which is removed by either wet or dry deposition. At high NO _x levels formation of HNO₃ is inhibited, and NO _x is removed by a variety of other processes, including rainout of N₂O₄ and N₂O₅, surface deposition of NO and NO₂, and direct dissolution of NO and NO₂ in rainwater. Multiple steady states are possible if surface deposition of NO _x is relatively inefficient. The NO _x source required to trigger high atmospheric NO _x levels is approximately 10 to 15 times the present global emission rate-less than half the source strength predicted by the zero-dimensional model. NO _x mixing ratios in excess of 10^-7 would cause severe damage to the ozone layer and could result in either a climatic warming or cooling, depending upon the amount of NO₂ present.     

Evaluation of the use of photochemical indicators to assess ozone—NOx—VOC sensitivity in the Southwestern Iberian Peninsula

Understanding the chemical links between ozone (O₃) and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), is important for designing effective photochemical smog reduction strategies. This chemical relationship will determine which precursor (NOx or VOC) emission reduction will be more effective for decreasing the ozone formation. Under certain conditions, ozone levels decrease as a result of a reduction in NOx emissions but do not respond significantly to changes in VOC emissions (NOx-sensitive condition), while under other conditions ozone concentrations decrease in response to reductions in VOCs and may even increase when NOx emissions are reduced (VOC-sensitive conditions). Indicator species can be used to assess the sensitivity of ozone to changes in the emissions of its precursors. These indicators are species or species ratios involved in ozone photochemistry which reflect the primary chemical process through which the ozone was formed. In this work we use the MM5-CAMx model system to explore the behaviour of various indicator species during two meteorological situations featuring different atmospheric conditions in a complex terrain area. The results show that indicators based on nitrogen compounds (i.e,. NOy and NOz) are suitable for defining the transition range from VOC- to NOx-sensitive chemistry, and that despite the uncertainties associated with the use of chemical indicators, the ratios O₃/NOy and O₃/NOz may provide a simple and useful way to summarize the response of ozone to changes in NOx and VOC emissions in Southwestern Spain.     

基于CMAQ-MCM模型的长三角地区夏季臭氧和大气氧化性影响的研究

传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O₃））前体物的氧化反应,具有一定的不确定性,导致模拟结果产生偏差.针对该问题,本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM）,模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O₃和其前体物随时间的变化趋势.对模拟的O₃日最大8 h平均浓度的统计分析表明,徐州表现最好（标准平均误差=-0.15,标准平均偏差=0.23）.在长三角地区,居民源对挥发性有机物（VOCs）的贡献最大,占39.08%,其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小,约为2.11%.对活性氧化氮（NO_y）的分析表明,其主要组分是NO_x（80%）,其次是硝酸（HNO₃）（<10%）.O₃的空间分布与NO_y和NO_x非常相似.HCHO等其他氧化产物的分布与NO_x相似,这很可能是由于在高NO_x条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似,表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.     

Tropospheric ozone and oxides of nitrogen over the north-western Pacific in summer

In summer, atmospheric ozone was measured from an aircraft platform simultaneously with nitric oxide (NO), oxides of nitrogen (NO _y ), and water vapor over the Pacific Ocean in east Asia from 34° N to 19° N along the longitude of 138±3°E. NO _y was measured with the aid of a ferrous sulfate converter. The altitude covered was from 0.5 to 5 km. A good correlation in the smoothed meridional distributions between ozone and NO _y was seen. In particular, north of 25° N, ozone and NO _y mixing ratios were considerably higher than those observed in tropical marine air south of 25° N. NO _y and O₃ reached a minimum of 50 pptv and 4 ppbv respectively in the boundary layer at a latitude of 20° N. The NO concentration between 2 and 5 km at the same latitude was 30 pptv. The profiles of ozone and water vapor mixing ratios were highly anti-correlated between 25° N and 20° N. In contrast, it was much poorer at the latitude of 33° N, suggesting a net photochemical production of ozone there.     

The role of precursor emissions on ground level ozone concentration during summer season in Poland

Three online coupled chemical transport model simulations were analyzed for three summer months of 2015 in Poland. One of them was run with default emission inventory, the other two with NO_x and VOC emissions reduced by 30%, respectively. Obtained ozone concentrations were evaluated with data from air quality measurement stations and ozone sensitivity to precursor emissions was estimated by ozone concentration differences between simulations and with the use of indicator ratios. They were calculated based on modeled mixing ratios of ozone, total reactive nitrogen and its components, nitric acid and hydrogen peroxide. The results show that the model overestimates ozone concentrations with the largest errors in the morning and evening, which is primarily related to the way vertical mixing is resolved by the model. Better model performance for ozone is achieved in rural than urban environment, as PBL and mixing mechanisms play more significant role in urban areas. Modeled ozone shows mixed sensitivity to precursor concentrations, similarly to other European regions, but indicator ratios have different values than are found in literature, particularly H₂O₂/HNO₃ is larger than in southern Europe. However, indicator ratios often differ between locations and transition values need to be established individually for a given region.     

Impact of precursor levels and global warming on peak ozone concentration in the Pearl River Delta Region of China

The relationship between the emission of ozone precursors and the chemical production of tropospheric ozone(O3) in the Pearl River Delta Region(PRD) was studied using numerical simulation.The aim of this study was to examine the volatile organic compound(VOC)-or nitrogen oxide(NOx =NO+NO2)limited conditions at present and when surface temperature is increasing due to global warming,thus to make recommendations for future ozone abatement policies for the PRD region.The model used for this application is the U.S.Environmental Protection Agency’s(EPA’s) third-generation air-quality modeling system;it consists of the mesoscale meteorological model MM5 and the chemical transport model named Community Multi-scale Air Quality(CMAQ).A series of sensitivity tests were conducted to assess the influence of VOC and NOx variations on ozone production.Tropical cyclone was shown to be one of the important synoptic weather patterns leading to ozone pollution.The simulations were based on a tropicalcyclone-related episode that occurred during 14-16 September 2004.The results show that,in the future,the control strategy for emissions should be tightened.To reduce the current level of ozone to meet the Hong Kong Environmental Protection Department(EPD) air-quality objective(hourly average of 120 ppb),emphasis should be put on restricting the increase of NOx emissions.Furthermore,for a wide range of possible changes in precursor emissions,temperature increase will increase the ozone peak in the PRD region;the areas affected by photochemical smog are growing wider,but the locations of the ozone plume are rather invariant.     

Chemistry–Climate Interactions of Stratospheric and Mesospheric Ozone in EMAC Long-Term Simulations with Different Boundary Conditions for CO2, CH4, N2O,and ODS

Abstract

To evaluate future climate change in the middle atmosphere and the chemistry–climate interaction of stratospheric ozone, we performed a long-term simulation from 1960 to 2050 with boundary conditions from the Intergovernmental Panel on Climate Change A1B greenhouse gas scenario and the World Meteorological Organization Ab halogen scenario using the chemistry–climate model ECHAM5/MESSy Atmospheric Chemistry (EMAC). In addition to this standard simulation we performed five sensitivity simulations from 2000 to 2050 using the rerun files of the simulation mentioned above. For these sensitivity simulations we used the same model setup as in the standard simulation but changed the boundary conditions for carbon dioxide (CO₂), methane (CH₄), nitrous oxide (N₂O), and ozone-depleting substances (ODS). In the first sensitivity simulation we fixed the mixing ratios of CO₂, CH₄, and N₂O in the boundary conditions to the amounts for 2000. In each of the four other sensitivity simulations we fixed the boundary conditions of only one of CO₂, CH₄, N₂O, or ODS to the year 2000.

In our model simulations the future evolution of greenhouse gases leads to significant cooling in the stratosphere and mesosphere. Increasing CO₂ mixing ratios make the largest contributions to this radiative cooling, followed by increasing stratospheric CH₄, which also forms additional H₂O in the upper stratosphere and mesosphere. Increasing N₂O mixing ratios makes the smallest contributions to the cooling. The simulated ozone recovery leads to warming of the middle atmosphere.

In the EMAC model the future development of ozone is influenced by several factors. 1) Cooler temperatures lead to an increase in ozone in the upper stratosphere. The strongest contribution to this ozone production is cooling due to increasing CO₂ mixing ratios, followed by increasing CH₄. 2) Decreasing ODS mixing ratios lead to ozone recovery, but the contribution to the total ozone increase in the upper stratosphere is only slightly higher than the contribution of the cooling by greenhouse gases. In the polar lower stratosphere a decrease in ODS is mainly responsible for ozone recovery. 3) Higher NO_x and HO_x mixing ratios due to increased N₂O and CH₄ lead to intensified ozone destruction, primarily in the middle and upper stratosphere, from additional NO_x; in the mesosphere the intensified ozone destruction is caused by additional HO_x. In comparison to the increase in ozone due to decreasing ODS, ozone destruction caused by increased NO_x is of similar importance in some regions, especially in the middle stratosphere. 4) In the stratosphere the enhancement of the Brewer-Dobson circulation leads to a change in ozone transport. In the polar stratosphere increased downwelling leads to additional ozone in the future, especially at high northern latitudes. The dynamical impact on ozone development is higher at some altitudes in the polar stratosphere than the ozone increase due to cooler temperatures. In the tropical lower stratosphere increased residual vertical upward transport leads to a decrease in ozone.     

Hydrocarbon reactivity and ozone formation in Europe

Several studies have shown that in qualitative terms VOCs can be ranked in terms of their importance to ozone formation in Europe, using a so-called photochemical ozone creation potential (POCP). However, all studies showed significant variability in the quantitative POCP values assigned to each VOC species. In this paper, we make use of a complex photochemical oxidant model to quantify how the reaction time-scales of emitted VOC and their reaction products vary with geographical location and time of year. The model is used to evaluate monthly POCP values for 9 hydrocarbon and oxygenated VOC compounds for a cross-section across Europe. Calculations are presented to illustrate the gradients in POCP values of one species,n-butane, across the whole of Europe for April and June 1989. We discuss some of the factors responsible for these variations.     

武汉市2018年4—9月臭氧及其前体物非线性关系研究

近年来武汉市臭氧污染日益严峻,成为影响空气质量达标的瓶颈,弄清臭氧及其前体物非线性关系是臭氧防控的关键和基础.本研究基于武汉中心城区2018年4—9月臭氧及其前体物在线观测数据,分析出武汉市臭氧浓度受前体物和气象条件等因素的共同影响,呈较为明显的季节变化和日变化特征.观测期间武汉市大气挥发性有机物（VOCs）平均体积分数为32.5×10^-9,烷烃是武汉市VOCs的主要组分,其次是含氧VOCs （OVOCs）和卤代烃.利用基于观测的模型定量分析臭氧与前体物之间的关系,发现削减VOCs会引起臭氧生成潜势的显著下降,而削减氮氧化物则会使臭氧生成潜势升高,说明武汉市臭氧生成处于VOCs控制区.在人为源VOCs中,间/对二甲苯和邻二甲苯的相对增量反应活性（RIR）最高,是影响臭氧生成的关键组分.     

Study of Ozone and NO2 over Gadanki – a rural site in South India

We have studied long-term changes in tropospheric NO₂ over South India using ground-based observations, and GOME and OMI satellite data. We have found that unlike urban regions, the region between Eastern and Western Ghat mountain ranges experiences statistically significant decreasing trend. There are few ground-based observatories to verify satellite based trends for rural regions. However, using a past study and recent measurements we show a statistically significant decrease in NO_X and O₃ mixing ratio over a rural location (Gadanki; 13.48° N, 79.18° E) in South India. In the ground-based records of surface NO_X, the concentration during 2010–11 is found to be lower by 0.9 ppbv which is nearly 60 % of the values observed during 1994–95. Small but statistically significant decrease in noon-time peak ozone concentration is also observed. Noon-time peak ozone concentration has decreased from 34?±?13 ppbv during 1993–96 to 30?±?15 ppbv during 2010–11. NO_X mixing ratios are very low over Gadanki. In spite of low NO_X values (0.5 to 2 ppbv during 2010–11), ozone mixing ratios are not significantly low compared to many cities with high NO_X. The monthly mean ozone mixing ratio varies from 9 ppbv to 37 ppbv with high values during Spring and low values during late Summer. Using a box-model, we show that presence of VOCs is also very important in addition to NO_X in determining ozone levels in rural environment and to explain its seasonal cycle.     

A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.     

Convective Redistribution of Ozone and Oxides of Nitrogen in the Troposphere over Europe in Summer and Fall

The fluxes of ozone and NO_x out of the atmospheric boundary layer (ABL) over Europe are calculated in a mesoscale chemical transport model (MCT) and compared with the net chemical production or destruction of ozone and the emissions of precursors within the ABL for two 10 days' periods which had quite different synoptic situations and levels of photochemical activity (1–10 July 1991 (JUL91) and 26 October–4 November 1994 (ON94)). Over the European continent, about 8% of the NO_x emissions were brought from the ABL to the free troposphere as NO_x, while about 15% of the NO_x emissions were brought to the free troposphere as NO_y–NO_x, i.e. as PAN or HNO₃. The convection dominates over the synoptic scale vertical advection as a transport mechanism both for NO_x and NO_y out of the boundary layer in the summertime high pressure situation (JUL91), while in the fall situation (ON94) the convective part was calculated to be the smallest. NO_x was almost completely transformed to NO_y–NO_x or removed within the ABL. Also for NO_y the major part of the atmospheric cycle is confined to the ABL both for JUL91 and ON94. The vertical transport time out of the ABL is of the order of 100h both for the total model domain and over the European continent. The net convective exchange of ozone from the ABL is not a dominant process for the amount of ozone in the ABL averaged over 10 days and the whole domain, but convection reduces the maximum ozone concentration in episodes significantly. The ozone producing efficiency of NO_x is calculated to increase with height to typically 15–20 in the upper half of the troposphere from around 5 in the ABL, but in the middle free troposphere the concentration of NO_x is often too low to cause net chemical formation of ozone there.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Radiative forcing from surface NO x emissions: spatial and seasonal variations

The global three-dimensional Lagrangian chemistry-transport model STOCHEM has been used to follow changes in the tropospheric distributions of methane CH₄ and ozone O₃ following the emission of pulses of the oxides of nitrogen NO _x . Month-long emission pulses of NO _x produce deficits in CH₄ mixing ratios that bring about negative radiative forcing (climate cooling) and decay away with e-folding times of 10–15 years. They also produce short-term excesses in O₃ mixing ratios that bring about positive radiative forcing (climate warming) that decay over several months to produce deficits, with their attendant negative radiative forcing (climate cooling) that decays away in step with the CH₄ deficits. Total time-integrated net radiative forcing is markedly influenced by cancellation between the negative CH₄ and long-term O₃ contributions and the positive short-term O₃ contribution to leave a small negative residual. Consequently, total net radiative forcing from NO _x emission pulses and the global warming potentials derived from them, show a strong dependence on the magnitudes, locations and seasons of the emissions. These dependences are illustrated using the Asian continent as an example and demonstrate that there is no simple robust relationship between continental-scale NO _x emissions and globally-integrated radiative forcing. We find that the magnitude of the time-integrated radiative forcing from NO _x -driven CH₄ depletion tends to approach and outweigh that from ozone enhancement, leaving net time-integrated radiative forcings and global warming potentials negative (climate cooling) in contrast to the situation for aircraft NO _x (climate warming). Control of man-made surface NO _x emissions alone may lead to positive radiative forcing (climate warming).