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1.
Reactive halogen species (RHS = X, XO, HOX, OXO; X = Cl, Br, I) are known to have an important influence on the chemistry in the polar boundary layer (BL), where they are responsible for ozone depletion events in spring. Recent field campaigns at Mace Head, Ireland, and the Dead Sea, Israel, identified for the first time iodine oxide (IO) at mixing ratios of up to 6.6 ppt and 90 ppt bromine oxide (BrO), respectively, by DOAS also at lower latitudes. These results intensified the discussion about the role of the RHS in the mid-latitude BL.Photochemical box model calculations show that the observed IO mixing ratios can destroy ~0.45 ppb ozone per hour. This is comparable to the rates of the known O3-loss processes in the boundary layer. The model studies also reveal that IO, at these levels, has a strong influence on the BL photochemistry, increasing the OH/HO2- and the NO2/NO - ratios. In combination these changes lead to a reduction of the photochemical ozone formation, which - in addition - reduces ozone mixing ratios by up to 0.15 ppb/h.The studies for the Dead Sea case give no information on the heterogeneous process responsible for the bromine release, but they show that a total of 2 – 4 ppb of total bromine have to be released to explain the observed complete depletion of 60 ppb ozone in 2 – 3 hours.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
The halogen ions Br- and Cl- together with NO3 -, SO4 =, MSA- (methane sulfonate), Na+ and NH4 + were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m-3 (0.14 nmol m-3) was observed for the whole campaign, while maximum concentrations of 80 ng m-3 (1 nmol m-3) were detected during two total O3-depletion events (O3 drop to mixing ratios below the detection limit of < 2 ppb). Anticorrelation between f-Br and O3 was also seen during minor O3-depletion episodes (sudden drop in O3 by at least 10 ppb, but O3 still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O3-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O3-depletion periods. At O3 concentrations < 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.  相似文献   

5.
At Amphitrite Point, ozone (O3) mixing ratios are observed to drop steadily to 5–15?ppb over a period of 12 hours or less with a frequency approaching one event per week (with highest frequencies occurring in summer and fall). Analysis of 47 such O3 depletion events reveals that low O3 episodes are a predominantly nocturnal phenomenon associated with anticyclonic conditions characterized by light onshore or alongshore winds and an absence of fog and mist. Back-trajectories show air carried to the Amphitrite Point Observatory (APO) during depletion events remains in the marine boundary layer and is not brought to the surface from aloft. There is no strong correlation with other “criteria” pollutants (CO, NOx, SO2, PM2.5) that might be indicative of a mechanism for O3 destruction linked to human, terrestrial, or marine pollutant sources. However, CO2 mixing ratios are observed to increase, coincident with O3 depletion. Together, these results point to a natural marine boundary layer phenomenon in which O3 destruction dominates O3 production and/or replenishment by vertical mixing. While there are several candidate mechanisms, the conditions for O3 depletion (and CO2 buildup) to occur are set by meteorology and, in particular, development of a stable marine boundary layer in which vertical mixing is suppressed. Support for this interpretation is provided by simultaneous increases in CO2 in the stable marine boundary that are indicative of an important role played by marine biogenic processes (respiration). Future research should be directed at elucidating the chemical mechanisms responsible for O3 destruction in the coastal zone, which means that there would be a need for a much broader range of measurements at APO (including halogenated species) as well as offshore measurements of both chemical and marine boundary layer meteorological variables.  相似文献   

6.
During the BERLIOZ field phase on 20 July 1998 a 40 km wide ozone-plume 30 to 70 km north of Berlin in the lee of the city was detected. The ozone mixing ratio inside the plume was app. 15 ppb higher than outside, mainly caused by high ozone precursor emissions in Berlin, resulting in a net chemical ozone production of 6.5 ppb h–1, which overcompensates ozone advection of –3.6 ppb h–1 andturbulent diffusion of –1.1 ppb h–1. That means, although moreozone leaves the control volume far in the lee of Berlin than enters it at the leeside cityborder and although turbulent diffusion causes a loss of ozone in the leeside control volume the chemical production inside the volume leads to a net ozone increase. Using a semi-Lagrangian mass budget method to estimate the net ozone production, 5.0 ppb h–1 are calculated for theplume. This means a fraction of about 20% of ozone in the plume is producedby local emissions, therefore called `home made' by the Berlin emissions. For the same area KAMM/DRAIS simulations using an observation based initialisation, results in a net production rate between 4.0 and 6.5 ppbh–1, while the threefold nested EURAD model gives 6.0 ppbh–1. The process analysis indicates in many cases goodagreement (10% or better) between measurements and simulations not only in the ozone concentrations but also with respect to the physical and chemical processes governing the total change. Remaining differences are caused by different resolution in time and space of the models and measurements as well as by errors in the emission calculation.The upwind-downwind differences in PAN concentrations are partly similar to those of ozone, because in the BERLIOZ case they are governed mainly by photochemical production. While in the stable boundary layer at night and windward of Berlin 0.1 to 0.3 ppb are detected, in the centre of the plume at noon concentrations between 0.75 ppb and 1.0 ppb are measured. The O3/PAN ratio is about 80 to 120 and thus due to the relatively lowPAN concentrations significantly higher than found in previous studies. The low PAN formation on 20 July, was mainly restricted by the moderate nonmethane hydrocarbon levels, whereas high PAN concentrations of 3.0 ppb on 21 July, are caused by local production in the boundary layer and by large scale advection aloft.  相似文献   

7.
Ozone photochemical production and loss in very different environments at Waliguan baseline station and Lin'an background station were simulated by using the measurement data and photochemical box model.The results show that net ozone photochemical production rate is negative,about 0.5 ppb/d,at Waliguan baseline sation,because of very low precursor concentrations.But at Lin'an background station,the net photochemical ozone production is positive,about 2-3 ppb/h.which is very closed with the measurement at Lin'an.That means ozone production was controlled by photochemical reactions at Lin'an background station,because of the higher precursor concentrations.The net destruction rate,at Waliguan Mt.,is not large,so that future increase in anthropogenic emission of reactive nitrogen will lead to larger production rates of steady-state O3 concentration.  相似文献   

8.
During the summer (8 June through 3 September) of 2008, 9 ozone profiles are examined from Dakar, Senegal (14.75°N, 17.49°W) to investigate ozone (O3) variability in the lower/middle troposphere during the pre-monsoon and monsoon periods. Results during June 2008 (pre-monsoon period) show a reduction in O3 concentrations, especially in the 850–700 hPa layer with Saharan Air Layer (SAL) events. However, O3 concentrations are increased in the 950–900 hPa layer where the peak of the inversion is found and presumably the highest dust concentrations. We also use the WRF-CHEM model to gain greater insights for observations of reduced O3 concentrations during the monsoon periods. In the transition period between 26 June and 2 July in the lower troposphere (925–600 hPa), a significant increase in O3 concentrations (10–20 ppb) occur which we suggest is caused by enhanced biogenic NOX emissions from Sahelian soils following rain events on 28 June and 1 July. The results suggest that during the pre-monsoon period ozone concentrations in the lower troposphere are controlled by the SAL, reducing ozone concentrations through heterogeneous chemical processes. At the base of the SAL we also find elevated levels of ozone, which we attribute to biogenic sources of NOX from Saharan dust that are released in the presence of moist conditions. Once the monsoon period commences, lower ozone concentrations are observed and modeled which we attribute to the dry deposition of ozone and episodes of ozone poor air that is horizontally transported into the Sahel from low latitudes by African Easterly Waves (AEWs).  相似文献   

9.
The ozone forming potential of VOCs and NOx 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 NOx, 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 NOx. In one sample with high SO2 mixing ratios (>100 ppb), SO2 was also identified as a significant contributor to the production of O3.  相似文献   

10.
A seven-year record of surface ozone measurements from Denali NationalPark, Alaska shows a persistent spring maximum. These data, combined withmeasurements of NOx, 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 NOx(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, onlyNOx 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.  相似文献   

11.
In part two of this series of papers on the IMS model, we present the chemistry reaction mechanism usedand compare modelled CH4, CO, and O3 witha dataset of annual surface measurements. The modelled monthly and 24-hour mean tropospheric OH concentrationsrange between 5–22 × 105 moleculescm–3, indicating an annualaveraged OH concentration of about 10 × 105 moleculescm–3. This valueis close to the estimated 9.7 ± 0.6 × 105 moleculescm–3 calculated fromthe reaction of CH3CCl3 with OH radicals.Comparison with CH4 generally shows good agreementbetween model and measurements, except for the site at Barrow where modelledwetland emission in the summer could be a factor 3 too high.For CO, the pronounced seasonality shown in the measurements is generally reproduced by the model; however, the modelled concentrations are lower thanthe measurements. This discrepancy may due to lower the CO emission,especially from biomass burning,used in the model compared with other studies.For O3, good agreement between the model and measurements is seenat locations which are away from industrial regions. The maximum discrepancies between modelled results and measurementsat tropical and remote marine sites is about 5–10 ppbv,while the discrepancies canexceed 30 ppbv in the industrial regions.Comparisons in rural areas at European and American continental sites arehighly influenced by the local photochemicalproduction, which is difficult to model with a coarse global CTM.The very large variations of O3 at these locations vary from about15–25 ppbv in Januaryto 55–65 ppbv in July–August. The observed annual O3amplitude isabout 40 ppbv compared with about 20 ppbv in the model. An overall comparison of modelled O3 with measurements shows thatthe O3seasonal surface cycle is generally governed bythe relative importance of two key mechanisms that drivea springtime ozone maximum and asummertime ozone maximum.  相似文献   

12.
Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O3 concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO3 ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO3 values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O3 mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O3 levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O3 and Ox(= O3 + NO2)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.  相似文献   

13.
Long Path Different Optical Absorption measurements of theconcentrations of O3, NO2, NO3 andSO2 were carried out at Cape Arkona, Island Rügen, nearthe well-known long-term ozone registration. A statistical analysis ofdifferent trace gas concentrations for all seasons is presented. Daytimedata, wind speed and sector-classified results are used to estimaterepresentative ozone concentrations. Comparison of the long path ozonemeasurements with point measurements at Cape Arkona shows ozoneconcentration differences.  相似文献   

14.
The mixing ratios of surface O3 were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O3 mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O3 mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O3 follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O3 concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O3 exposures are lower than the critical level of O3 and suggest that the present level of O3 does not have any impact on reduction in crop yields.  相似文献   

15.
A 2-D global chemistry-transport model is set up in this paper.The model simulates the atmospheric ozone distributions well with specified dynamical conditions.The analysis of ozone variation mechanism shows that ozone is chemically in quasi-equilibrium except for the polar night region where the variation of ozone concentration is under the control of dynamical processes,that the oxygen atoms which produce ozone are mainly provided by the photolysis of O2 in the upper stratosphere and by the photolysis of NO2 in the lower stratosphere and the troposphere.and that the ozone is destroyed mainly by NOx:the reactions between NOx and O3 and the odd oxygen cycle contribute 80% to more than 90% of the ozone destruction.  相似文献   

16.
Satellite measurements of tropospheric column O3 and NO2 in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O3 is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO2 is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O3 and NO2 fields. The analysis of the model results show that the industrial emission of NOx (NO + NO2) contributes about 50%–80% to tropospheric column NO2 in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NOx to tropospheric column O3 ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NOx emissions have a small effect on tropospheric O3 in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NOx on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.  相似文献   

17.
Measurements of surface ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), oxides of nitrogen (NOx=NO+NO2) and meteorological parameters have been made at Agra (North Central India, 27°10??N, 78°05??E) in post monsoon and winter season. The diurnal variation in O3 concentration shows daytime in situ photochemical production with diurnal maximum in noon hours ranging from 51 to 54 ppb in post monsoon and from 76 to 82 ppb in winter, while minimum (16?C24 ppb) during nighttime and early morning hours. Average 8-h O3 concentration varied from 12.4 to 83.9 ppb. The relationship between meteorological parameters (solar radiation intensity, temperature, relative humidity, wind speed and wind direction) and surface O3 variability was studied using principal component analysis (PCA), multiple linear regression (MLR) and correlation analysis (CA). PCA and MLR of daily mean O3 concentrations on meteorological parameters explain up to 80 % of day to day ozone variability. Correlation with meteorology is strongly emphasized on days having strong solar radiation intensity and longer sunshine time.  相似文献   

18.
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).  相似文献   

19.
Anomalies found in the isotope ratios of ozone are traceable to the ozone formation process. Metastable electronic states may be responsible for the preferred production of the heavy molecules. While laboratory isotope data and first tropospheric results agree well in the magnitude of isotope enrichments, stratospheric measurements show often higher values. Only through the collection of ozone samples can sufficiently large amounts of gas be obtained to analyze the three isotopes 48O3, 49O3, and 50O3. Collector systems have been developed and successfully operated in the troposphere and in the stratosphere. They will play in the future an important role in atmospheric oxygen isotope studies.  相似文献   

20.
Surface O3 concentration and its precursors have been observed at Longfengshan station,Heilongjiang Province for a period of one year from August 13,1994 to July 30,1995. Relationship between surface O3 and the meteorological conditions during this period is analyzed in this study.Observation results show that diurnal variation of surface O3 follows a pattern of double-peaks with amplitude of 27-28 ppb under fine days in summer and autumn.Although the diurnal variation is small(14 ppb),it is still detectable when it is overcast.Diurnal variation of O3 is irregular under rainy days.Surface O3 concentration rises when wind speed starts to increase at 0800 BT(Beijing Time)from 0 to 6 m s-1in autumn,winter and summer.Relative high surface O3 concentration is noticed frequently when S,SSW,SW and WSW wind are encountered at the station during all seasons.At 0800 BT and 1400 BT the surface O3 concentration increases with the increase of global radiation accordingly during fine days in winter,spring and autumn.During fine days average peak of O3 concentration in summer is 20 ppb higher than that in winter while the average peak of global radiation in summer is almost twice as high as that in winter.The average surface O3 concentration under fine days in autumn at Longfengshan station is 14 ppb lower in comparison to the observation results from Lin'an station where Lin'an is at about the same longitude and lower latitude,with same environment,which is mainly caused by the difference of global radiation due to different latitudes in these two areas(difference of average peak global radiation about 100 W m-2).  相似文献   

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