Surface ozone measurements in the Venezuelan tropical savannah

A one-year set of surface ozone measurements in a four-station network located in the Venezuelan savannah is reported. The diurnal ozone variation is typical of continental stations with a maximum in the afternoon, when vertical turbulent mixing is strongest. The annual O₃ average concentration, based on the monthly averages of daily maxima, was 17±2 ppb, which is in good agreement with values reported for similar latitudes. The boundary-layer ozone levels did not fall below 8 ppb, in contrast with previous sporadic measurements made in tropical latitudes. No evidence was found that mesoscale O₃ downdrafts in the ITCZ in the South American continent are an important source of surface ozone. Finally, it is suggested that the relatively high ozone levels observed at the end of the dry season are probably of photochemical origin.     

The Influence of Selected Meteorological Parameters on the Concentration of Surface Ozone in the Central Region of Poland

Abstract?This paper presents the results of measurements of the concentration of surface ozone and concurrent standard meteorological parameters: total solar radiation, temperature, relative humidity, pressure, wind speed, and vertical and horizontal components of the wind. The data were collected from 2005 to 2010 at stations located in central Poland (Mazowieckie voivodeship): Warszawa (urban), Legionowo (suburban), Granica and Belsk (rural). Furthermore, Granica is situated in the forested area of Kampinoski National Park. Continuously measured surface ozone concentrations demonstrated the well-known diurnal cycle of surface ozone concentration with a maximum in the afternoon and a minimum in the early morning hours. The averaged diurnal variations over six years reveal that the highest concentrations appear at rural stations (Belsk: 55?µg?m^?3 and Granica: 50?µg?m^?3) and the lowest at the urban station (Warszawa: 41?µg?m^?3). The threshold for high levels of surface ozone (120?µg?m^?3 per 8?h) was exceeded most often at Granica and Belsk. The occurrence of the ozone “weekend effect,” especially at urban stations, has been identified. The difference between weekend and weekday surface ozone concentrations at urban and rural stations was as high as 6.5?µg?m^?3 and approximately 2?µg?m^?3, respectively. Using appropriate statistical tools, it has been shown that meteorological conditions have a significant influence on ozone concentration. High correlation coefficients were found between ozone concentration and solar radiation, temperature, relative humidity, and wind speed. The forward stepwise regression model explains up to 75% of the variations in daily surface ozone concentration in terms of meteorological variability in summer and up to 70% in winter. At the same time, a multilayer perceptron neural network model was used to reconstruct the concentration of surface ozone. High correlation coefficients (up to 0.89) indicate that, on the basis of standard meteorological parameters and NO₂ concentration, we can determine ozone concentration with high accuracy.     

High-Latitude Springtime Photochemistry. Part Ii: Sensitivity Studies of Ozone Production

A seven-year record of surface ozone measurements from Denali NationalPark, Alaska shows a persistent spring maximum. These data, combined withmeasurements of NO_x, hydrocarbons, O₃, and PANfrom a continental site in Alaska during the spring of 1995 are used as thebasis for a sensitivity study to explore tropospheric photochemistry in thisregion. Because of the relatively high concentrations of NO_x(mean of 116, median of 91 pptv), the net tendency was for photochemicalozone production. The range of net O₃ production for averageconditions measured at this site during spring is between 0.96–3.9ppbv/day depending on the assumptions used; in any case, this productionmust contribute to the observed springtime maximum in O₃.Model calculations showed that of the anthropogenic ozone precursors, onlyNO_x had a strong effect on the rate of ozone production; themeasured concentrations of anthropogenic hydrocarbons did not significantlyaffect the ozone budget. Naturally produced biogenic hydrocarbons, such asisoprene, may also have a significant effect on ozone production, even atconcentrations of a few 10's of pptv. An observed temperature-isoprenerelationship from a boreal site in Canada indicates that isoprene may bepresent during the Alaskan spring. Measurements of isoprene taken duringthe spring of 1996 suggest that reactive biogenic hydrocarbon emissionsbegin before the emergence of leaves on deciduous trees and that theconcentrations were sufficient to accelerate ozone production.     

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.     

What Causes the Springtime Tropospheric Ozone Maximum over Northeast Asia？

Scientists have long debated the relative importance of tropospheric photochemical production versus stratospheric influx as causes of the springtime tropospheric ozone maximum over northern mid-latitudes. This paper investigates whether or not stratospheric intrusion and photochemistry play a significant role in the springtime ozone maximum over Northeast Asia,where ozone measurements are sparse.We examine how tropospheric ozone seasonalities over Naha(26°N,128°E),Kagoshima(31°N,131°E),and Pohang(36°N,129°E),which are located on the same meridional line,are related to the timing and location of the jet stream.The ozone seasonality shows a gradual increase from January to the maximum ozone month,which corresponds to April at Naha,May at Kagoshima,and June at Pohang.In order to examine the occurrence of stratospheric intrusion,we analyze a correlation between jet stream activity and tropospheric ozone seasonality.From these analyses,we did not find any favorable evidence supporting the hypothesis that the springtime enhancement may result from stratospheric intrusion.According to trajectory analysis for vertical and horizontal origins of the airmass,a gradual increasing tendency in ozone amounts from January until the onset of monsoon was similar to the increasing ozone formation tendency from winter to spring over mainland China,which has been observed during the build-up of tropospheric ozone over Central Europe in the winter-spring transition period due to photochemistry.Overall,the analyses suggest that photochemistry is the most important contributor to observed ozone seasonality over Northeast Asia.     

东亚太平洋地区近地面臭氧的季节和年际变化特征及其与东亚季风的关系

利用东亚清洁背景站近地面臭氧观测资料,结合风场和降水资料,分析东亚各地区臭氧的多年季节变化特征,并探讨东亚太平洋地区臭氧的季节和年际变化与季风的关系以及影响近地层臭氧的主要因子。结果表明：东亚大部分地区与北半球背景站观测一致,近地层臭氧季节变化表现为春季最高、夏季最低的特征;但在东亚中纬度33～43°N,臭氧表现为夏季最高,而在东亚20°N以南地区臭氧则表现为冬末、春初最高。东亚太平洋沿岸近地面臭氧的季节变化主要受东亚冬、夏季风环流的季节变化控制。该地区不同纬度上春季峰值出现时间的差异与亚洲大陆春季不同时期污染物输送路径的差异有关。对东亚太平洋沿岸对流层顶附近位势涡度、高空急流和垂直环流季节变化的分析表明,冬春季可能是平流层向对流层输送的最强期,对近地面臭氧贡献最大。初夏至秋季（5-11月）,平流层向对流层输送较弱,对近地面臭氧贡献较小。东亚太平洋地区夏季风爆发的时间和强度以及季风环流型的年际差异是导致该地区春、夏季臭氧年际变化的主要原因;而季风降水和云带位置以及平流层一对流层交换是造成臭氧年际变化的其他原因。     

Validation of Ground-Based Visible Measurements of Total Ozone by Comparison with Dobson and Brewer Spectrophotometers

Comparisons of total column ozone measurements from Dobson, Brewer and SAOZ instruments are presented for the period 1990 to 1995 at seven stations covering the mid- and the high northern latitudes, as well as the Antarctic region. The main purpose of these comparisons is to assess, by reference to the well established Dobson network, the accuracy of the zenith-sky visible spectroscopy for the measurement of total ozone. The strengths and present limitations of this latter technique are investigated. As a general result, the different instruments are found to agree within a few percent at all stations, the best agreement being obtained at mid-latitudes. On average, for the mid-latitudes, SAOZ O₃ measurements are approximately 2% higher than Dobson ones, with a scatter of about 5%. At higher latitudes, both scatter and systematic deviation tend to increase. In all cases, the relative differences between SAOZ and Dobson or Brewer column ozone are characterised by a significant seasonal signal, the amplitude of which increases from about 2.5% at mid-latitude to a maximum of 7.5% at Faraday, Antarctica. Although it introduces a significant contribution to the seasonality at high latitude, the temperature sensitivity of the O₃ absorption coefficients of the Dobson and Brewer instruments is shown to be too small to account for the observed SAOZ/Dobson differences. Except for Faraday, these differences can however be largely reduced if SAOZ AMFs are calculated with realistic climatological profiles of ozone, pressure and temperature. Other sources of uncertainties that might affect the comparison are investigated. Evidence is found that the differences in the air masses sampled by the SAOZ and the other instruments contribute significantly to the scatter, and the impact of the tropospheric clouds on SAOZ measurements is displayed.     

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.     

Long-term measurements of surface ozone in the German Democratic Republic

The ozone concentration near the earth's surface has been measured at some stations in the GDR for more than 30 yr using the wet chemical method. Even at rural stations the ozone data show a significant linear increase by about 1–3% yr^–1. The ozone increase being stronger in summer than in winter is assumed to be due to photochemical ozone production from increasing anthropogenic emissions of trace gases that are transported over long distances. A weaker ozone increase by only about 0.2% per year was observed in the free troposphere (5.5 km) from balloon-soundings at Lindenberg within the period 1975–1984. If the ozone trends continue, the ozone concentration near the surface and its seasonal amplitude will have doubled around the turn of the century as compared to the mid-fifties.     

Measurements of arctic total ozone during the polar winter

Abstract

Ground‐based measurements of total ozone were made during the polar night from Arctic stations in the winters of 1987–88 and 1988–89. The measurements were made with automated Brewer ozone spectrophotometers using the moon as a light source. Data were obtained from Alert and Resolute in Canada for both winters and from Heiss Island, USSR, for the second winter. The method of measurement is briefly reviewed and data from the three stations are presented. The ground‐based total ozone measurements are compared with the integrated values derived from ozonesonde profiles.     

Periodic variability of surface ozone concentration over western and central Europe from observational data

Characteristics of periodic variability of surface ozone concentration at 98 western and central European stations participating in the EMEP program for at least 7 (up to 14) years are determined. Daily and hourly model concentrations of surface ozone for each station are given in an analytical form that presents a sum of a constant constituent and basic harmonics that determine ozone concentration variability throughout a year and a day. A 12-month harmonic, whose maximum is observed in the spring period (in Northern Europe it is observed 1 to 2 months earlier than in Southern Europe) dominates in the energy spectrum of seasonal variability of daily mean ozone concentration at most stations. The energy part of higher (6-and 4-month) harmonics is the largest at the stations close to the sea and ocean coasts. Higher harmonics largely influence the time of the ozone extremum formation, shifting it towards the summer, or even forming a second (summer) maximum, whose magnitude at a number of stations (in Italy, Hungary, in the south of Germany, and in some others) exceeds the spring maximum. A 24-hour harmonic dominates in the energy spectrum of daily ozone variability. The maps of a “normal” distribution of surface ozone fields and their standard deviations for different seasons and time of the day have been compiled based on the model characteristics. The “norms” derived can be used to detect anomalies in the temporal trend of the surface ozone and to validate its climate changes.     

大尺度山地上空的臭氧低值及地面加热

首次利用Ｎｉｍｂｕｓ－７卫星上搭载的臭氧观测光谱仪（ＴＯＭＳ）资料,分析研究了大尺度山地（青藏高原、洛基山脉和安第斯山脉）上空臭氧总量的分布和季节变化规律,指出了大尺度山地对大气臭氧的减少作用。从全球大气臭氧总量分布和纬向偏差分布可以看出：在上述３个大尺度山地上空均存在着明显的臭氧低值扰动,该扰动区夏季强于冬季。在这３个区域中,青藏高原上空的臭氧低值扰动为最强。分析同时指出：上述大尺度山地上空臭氧季节变化的极小值在秋季,极大值在春季。但上述地区臭氧总量与同纬度其它地区臭氧总量的偏差在春季或初夏达到极小值。为分析这种大尺度山地对臭氧减少作用的原因,本文分析了青藏高原地面热源与臭氧总量的关系,指出：大尺度山地表面对大气的加热与该地区臭氧减少之间存在着良好的反相关;在地面对大气的感热加热、潜热加热和有效长波辐射加热中,以感热加热与臭氧减少的关系为最好。     

拉萨地区1998年夏季臭氧总量及垂直廓线的观测研究

该文根据1998年6~10月上旬在拉萨地区进行的臭氧总量及臭氧垂直廓线的观测结果, 并结合同期同纬度其他两个臭氧站数据资料, 证实了以拉萨地区为代表的青藏高原在夏季存在“臭氧低谷”的现象.分析表明, 地基和卫星观测的臭氧总量有一定误差. Umkehr观测反演结果表明夏季拉萨地区平流层臭氧分布和同纬度其他地区相比略有不同; 在对流层, 探空资料显示了该地区对流层臭氧有低值分布的特征.     

Identifying the Origin of Anomalous High Tropospheric Ozone in the Ozonesonde Data at Uccle by Comparison with Nearby De Bilt

Abstract

The ozonesonde stations at Uccle (Belgium) and De Bilt (Netherlands), separated by only 175?km, offer a unique opportunity to test the influence of different ozonesonde types and different correction strategies, as well as to detect the presence of inhomogeneities in the ozonesonde time series resulting from changes in sounding equipment (solution, radiosonde, ozonesonde, interface, sounding software, etc.). In particular, we highlight a 2.5 year period (beginning of 2007 to mid-2009) of anomalous high tropospheric ozone values measured by ozonesondes at Uccle and compare these with the observations from De Bilt. Because the ozone deviations are only observed in the free troposphere where ozone concentrations are relatively low, and not in the boundary layer or the stratosphere, this issue is directly related to the sensitivity of ozonesondes. Therefore, the effect of every instrumental change, even though small, during this 2.5 year anomalous period is analyzed considering a change in the radiosounding equipment, different ozonesonde batches, operational differences at the stations, differences on ascent and descent during the anomalous period; an environmental cause is also examined. Unfortunately, one single, specific cause for the observed high tropospheric ozone values at Uccle could not be identified. There are two explanations consistent with the observations and not ruled out by the analysis here: 1) the majority of the ozonesondes used at Uccle between March 2007 and August 2009 needed longer conditioning of their sensors and, therefore, behaved more accurately at low ozone concentrations during their descent or when used a second time, and 2) an environmental origin arising from a local difference in the air mass between Uccle and De Bilt and between the ascent and descent.     

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.     

High-Latitude Springtime Photochemistry. Part I: NOx, PAN and Ozone Relationships

Springtime measurements of NO_x, ozone, PAN,J(NO₂), and other compounds were made near Ny-Ålesund,Svalbard (78°54N, 11°53E), in 1994 and Poker Flat,Alaska (65°08N, 147°29W), in 1995. At Svalbard medianmixing ratios for PAN and NO_x of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NO_x were 79.5 and 85.9 pptv, respectively. These data areused to estimate thermal PAN decomposition using several differentapproaches. At Svalbard PAN decomposition was very small, while at PokerFlat up to 30 pptv/h PAN decomposed. At both sites the NO_x/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NO_x source. In-situozone production was calculated from the measured NO, NO₂,O₃, J(NO₂), and temperature data, using thesteady state assumption Median ozone production was 605 pptv/h at PokerFlat, and one order of magnitude smaller at Svalbard during the daytime.Only at Poker Flat could a direct influence on the diurnal ozone cycle beobserved from in-situ production. These results imply that PAN decompositionis a major source of NO_x in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.     

A Eulerian air pollution model for Europe with nonlinear chemistry

A long-range transport model with nonlinear chemical reactions is described. The model contains 35 pollutants and 70 chemical reactions. This is a Eulerian model defined on a space domain containing the whole of Europe. The spherical space domain (corresponding to the Earth's surface covered by the model) is mapped into a square plane domain and discretized by using a 32×32 grid. The grid increments are equidistant (both along the Ox axis and along the Oy axis). The choice of values of the physical parameters involved in the model and the numerical treatment of the model are shortly discussed. The model is tested with meteorological data for 1985 and 1989. The numerical results are compared with measurements at stations located in different European countries. Extensive comparisons of ozone concentrations for July 1985 with measurements taken at 24 European stations are also carried out. Results concerning three episodes in July 1985 as well as results obtained in the study of the sensitivity of the ozone concentrations to variations of NO _x and/or anthropogenic VOC emissions are presented. The advantages and the limitations of such a model are discussed. The model is continuously improved by adding new modules to it. The plans for improvements in the near future are outlined.     

Comparison of Measured Ozone Production Efficiencies in the Marine Boundary Layer at Two European Coastal Sites under Different Pollution Regimes

Ozone production efficiencies (E_N), which can be defined as the netnumber of ozone molecules produced per molecule of NO_xoxidised, have been calculated from measurements taken during three intensive field campaigns (one in the spring, EASE 96, and two in the summer, EASE 97 and TIGER 95), at two European coastal sites (Mace Head, Ireland (EASE) and Weybourne, Norfolk (TIGER)) impacted by polluted air masses originating from both the U.K. and continental Europe, as well as relatively clean oceanic air masses from the Arctic and Atlantic. From a detailed wind sector analysis of the EASE 96 and 97 data it is clear that two general types of pollution regime were encountered at Mace Head. The calculated ozone production efficiency in clean oceanic air masses was approximately 65, which contrasted to more polluted air, from the U.K. and the continental European plume, where the efficiency decreased to between 4 and 6. The latter values of E_Nagree well with literature measurements conducted downwind of various urban centres in the U.S. and Europe, which are summarised in a wide-ranging review table. The E_N value calculated for clean oceanic air is effectivelyan upper limit, owing to the relatively rapid deposition of HNO₃ tothe ocean. Consideration of the variation of E_N with NO_x forthe three campaigns suggests that ozone production efficiency is relatively insensitive to both geographical location and season. The measuredE_N values are also compared with values derived from steady-state expressions. An observed anti-correlation between E_N and measured ozone tendencyis briefly discussed.