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1.
Aircraft observations of oxides of nitrogen (NO y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO y defined here is the sum of NO, NO2, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:
  1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
  2. Over the Sea of Japan, tropospheric NO y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
  3. NO y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO y mixing ratio was about 200 pptv.
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2.
Surface NO and NO2 mixing ratios were measured aboard the research vessel Polarstern during the mission ANT VII/1 from 24 September to 5 October 1988. The measurements were taken along the meridian at 30° W in the Atlantic region covering latitudes between 30° N and 30° S. The average mixing ratios were about 12 pptv NO/30 pptv NO2 in the Northern Hemisphere and about 7 pptv NO/22 pptv NO2 in the Southern. Elevated mixing ratios of 20 pptv NO/70 pptv NO2 were found at 12° N (probably due to air masses originating from the surface of West Africa) and in the region of the ITCZ between 8° N and 5° N. Because of probable contamination by the ship, the measured mixing ratios mostly represent upper limits.  相似文献   

3.
Measurements of NOx (NO +NO2) and the sum of reactive nitrogenconstituents, NOy, were made near the surface atAlert (82.5°N), Canada during March and April1998. In early March when solar insolation was absentor very low, NOx mixing ratios were frequentlynear zero. After polar sunrise when the sun was abovethe horizon for much or all of the day a diurnalvariation in NOx and NOy was observed withamplitudes as large as 30–40 pptv. The source ofactive nitrogen is attributed to release from the snowsurface by a process that is apparently sensitized bysunlight. If the source from the snowpack is a largescale feature of the Arctic then the diurnal trendsalso require a competing process for removal to thesurface. From the diurnal change in the NO/NO2ratio, mid-April mixing ratios for the sum of peroxyand halogen oxide radicals of 10 pptv werederived for periods when ozone mixing ratios were inthe normal range of 30–50 ppbv. Mid-day ozoneproduction and loss rates with the active nitrogensource were estimated to be 1–2 ppbv/day and in nearbalance. NOy mixing ratios which averaged only295±66 pptv do not support a large accumulation inthe high Arctic surface layer in the winter and springof 1998. The small abundance of NOy relative tothe elevated mixing ratios of other long-livedanthropogenic constituents requires that reactivenitrogen be removed to the surface during transport toor during residence within the high Arctic.  相似文献   

4.
Springtime measurements of NOx, 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 NOx of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NOx 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 NOx/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NOx 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 NOx in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.  相似文献   

5.
Simultaneousindependent measurements of NOy and NOx(NOx= NO + NO2) by high-sensitivitychemiluminescence systems and of PAN (peroxyacetylnitrate) and PPN (peroxypropionyl nitrate) by GC-ECDwere made at Spitsbergen in the Norwegian Arcticduring the first half year of 1994. The average mixingratio of the sum of PAN and PPN (denoted PANs)increased from around 150 pptv in early winter to amaximum of around 500 pptv in late March, whereasepisodic peak values reached 800 pptv. This occurredsimultaneously with a maximum in ozone which increasedto 45–50 ppbv in March–April. The average NOxmixing ratio was 27 pptv and did not show any cyclethrough the period. The NOy mixing ratio showeda maximum in late March, while the difference betweenNOy and PAN decreased during spring. This is anindication of the dominance of PAN in the NOybudget in the Arctic, but possible changes in theefficiency of the NOy converter could alsocontribute to this. Although most PAN in theArctic is believed to be due to long range transport,the observations indicate local loss and formationrates of up to 1–2 pptv h-1 in April–May.Measurements of carbonyl compounds suggest thatacetaldehyde was the dominant, local precursor ofPAN.Now at 1.  相似文献   

6.
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 NOx mixing ratiosup to 300 pptv in February and for NOx mixing ratios up to 500 pptv in May. These NOx limits are an order of magnitude higher thanmedian NOx levels observed, illustrating the strong dependence ofgross ozone production rates on NOx mixing ratios for the majority of theobservations. The threshold NOx mixing ratio needed for netpositive ozone production was also calculated to increase from NOx 10pptv in February to 25 pptv in May, suggesting that the NOx levels needed to sustain net ozone production are lower in winter than spring. This lower NOx 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 NOx 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.  相似文献   

7.
Hydrogen peroxide, one of the key compounds in multiphase atmospheric chemistry, was measured on an Atlantic cruise (ANT VII/1) of the German research vessel Polarstern from 15 September to 9 October 1988, in rain and ambient air by a chemiluminescence technique. For gas phase H2O2 cryogenic sampling was employed. The presented results show an increase of gas-phase mixing ratios of about 45 pptv per degree latitude between 50° N and 0°, and a maximum of 3.5 ppbv around the equator. Generally higher mixing ratios were observed in the Southern Hemisphere, with a clear diurnal variation. The H2O2 mixing ratio is correlated to the UV radiation intensity and to the temperature difference between air and ocean surface water.  相似文献   

8.
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   

9.
A latitudinal profile (30° W, from 30° N to 30° S) of mixing ratios of nitric acid and particulate nitrate was determined on the Atlantic Ocean during the Polarstern cruise ANT VII/1 from Bremerhaven, Germany, to Rio Grande, Brazil. The detection of HNO3 was performed simultaneously by laser-photolysis fragment-fluorescence (LPFF) and by nylon filter packs. The detection limit was about 30 pptv for a signal accumulation time of 1 h for LPFF and about 5 pptv for the filters at a collection time of 4 h. In general, the mixing ratios of HNO3 in the Northern Hemisphere were found to be significantly higher than those in the Southern Hemisphere. The Atlantic background concentrations frequently varied between 80 pptv and the detection limit. Larger deviations from this trend were found for the more northern latitudes and for episodes like crossings of exhaust plumes from ships or from continental pollutions sources.  相似文献   

10.
Measurements of the sum of peroxy radicals [HO2 + RO2],NOx (NO + NO2) and NOy (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.  相似文献   

11.
A series of 149 measurements of the HCHO mixing ratio were made between 0 and 10 km altitude and 70° N to 60° S latitude during TROPOZ II. The data show a vertical decrease of the HCHO mixing ratio with altitude at all latitudes and a broad latitudinal maximum in the HCHO mixing ratio between 30° N and 30° S at all altitudes. The measured mixing ratios of HCHO are considerably higher than those expected from CH4 oxidation alone, but agree broadly with the average latitude by altitude distribution of HCHO derived by a 2D model including emissions of C1–C7 hydrocarbons. A number of the regional scale deviations of the measured HCHO distribution from the average modelled one can be explained in terms of the local wind field.  相似文献   

12.
A catalytic reduction technique for the measurement of total reactive odd-nitrogen NO y in the atmosphere was evaluated in laboratory and field tests. NO y component species include NO, NO2, NO3, HNO3, N2O5, CH3COO2NO2(PAN), and particulate nitrate. The technique utilizes the reduction of the higher oxides to NO in reaction with CO on a metal catalyst and the subsequent detection of NO by chemiluminescence produced in reaction with O3. The efficiency and linearity of the conversion of the principal NO y species were examined for mixing ratios in the range of 0.1 to 100 parts per billion by volume (ppbv). Results of tests with Au, Ni, and stainless steel as the catalyst in the temperature range of 25–500°C showed Au to be the preferred catalyst. NH3, HCN, N2O, CH4, and various chlorine and sulfur compounds were checked as possible sources of NO y interference with the Au catalyst. The effects of pressure, O3, and H2O on NO y conversion were also examined. The results of the checks and tests in the laboratory showed the technique to be suitable for initial NO y measurements in the atmosphere. The technique was subsequently tested in ambient air at a remote ground-based field site located near Niwot Ridge, Colorado. The results of conversion and inlet tests made in the field and a summary of the NO y data are included in the discussion.  相似文献   

13.
Measurements of NOx,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. NOy changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NOx 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 NOx 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 NOx 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 NOx due to competition from ozone production involving NOx 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 BrOx during ozone depletion events is sensitive to even sub ppbv variations in O3.  相似文献   

14.
The simultaneous measurements of NO, NO2 and HNOA mixing‐ratio profiles carried out on the Stratoprobe balloon flight of 22 July 1974 have been simulated with a time‐dependent model using the measured temperature and ozone profiles. The calculated ratios of NO/NO2, HNO3/NO2 using currently accepted photochemistry are consistent with the measured ratios within the experimental errors of the measurements. The measured NO2/NO ratio is almost a factor of two smaller than predicted, although the discrepancy is still within the experimental errors. A remarkable proportionality in the NO2 and O3 profiles has been noted and is unexplained. A time‐dependent simulation has been employed to convert the measurements into diurnally‐averaged profiles suitable for intercomparison with two‐dimensional stratospheric models and a comparison with constituent profiles from Prinn et al. (1975) is carried out as an example. The NOV mixing ratio, formed from the sum of the NO, NO2 and HNO2 measurements is similar to the NOV mixing ratio from several one‐ and two‐dimensional models used to predict the effects of SST's on the ozone layer. The odd nitrogen mixing ratio is roughly constant from 20 to 35 km at 11 ppbv.  相似文献   

15.
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   

16.
Field measurements of NO and NO2 emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO x detector allowing the determination of minimum flux rates of 2 g N m-2 h-1 for NO and 3 g m-2 h-1 for NO2.The NO and NO2 flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO2, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO2. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO2 emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO2 equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO2. The soil acted as a net sink for ambient air NO and NO2 mixing ratios higher than the equilibrium values and a net source for NO and NO2 mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO2 are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m-2 h-1 for NO2 and 8 g N m-2 h-1 for NO. The NO and NO2 flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO2.Application of mineral fertilizers increased the NO and NO2 emission rates. Highest emission rates were observed for urea followed by NH4Cl, NH4NO3 and NaNO3. The fertilizer loss rates ranged from 0.1% for NaNO3 to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO x emission from soil is estimated to be 11 Tg N yr-1. This figure is an upper limit and includes the emission of 7 Tg N yr-1 from natural unfertilized soils, 2 Tg N yr-1 from fertilized soils as well as 2 Tg N yr-1 from animal excreta. Despite its speculative character, this estimation indicates that NO x emission by soil is important for tropospheric chemistry especially in remote areas where the NO x production by other sources is comparatively small.  相似文献   

17.
A series of ozone transects measured each year from 1987 to 1990 over thewestern Pacific and eastern Indian oceans between mid-November andmid-Decembershows a prominent ozone maximum reaching 50–80 ppbv between 5 and 10 kmin the 20° S–40° S latitude band. This maximum contrasts with ozonemixing ratios lower than20 ppbv measured at the same altitudes in equatorial regions. Analyses witha globalchemical transport model suggest that these elevated ozone values are part ofa large-scale tropospheric ozone plume extending from Africa to the western Pacific acrosstheIndian ocean. These plumes occur several months after the peak in biomassburninginfluence and during a period of high lightning activity in the SouthernHemispheretropical belt. The composition and geographical extent of these plumes aresimilar to theozone layers previously encountered during the biomass burning season in thisregion.Our model results suggest that production of nitrogen oxides from lightningstrokes sustains the NOx (= NO+NO2) levels and the ozonephotochemical productionrequired in the upper troposphere to form these persistent elevated ozonelayers emanating from biomass burning regions.  相似文献   

18.
Abstract

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NOx) has been widely studied. In addition to the atmospheric levels of VOCs and NOx, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NOx are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NOx mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NOx in this environment and at this time of the year.  相似文献   

19.
Using a filter radiometer, the meridional profile of the NO2 photolysis frequency, J(NO2), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b sp=(1–2)×10-5 m-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO2) reached 7.3×10-3 s-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO2) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10-3 s-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO2) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10-5 s-1/mW cm-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).  相似文献   

20.
Simultaneous observations of several chlorine source gases, as well asHCl and ClO, have been performed in the Arctic stratosphere on 1 and 9February 1994, using balloon-borne instrumentation as a contribution toSESAME (Second European Stratospheric Arctic and Mid latitude Experiment).The observed mixing ratios of HCl and N2O show a clearanticorrelation. No severe loss of HCl was observed inside the vortex duringour measurement. These measurements showed that during this period at 20 kmand above, HCl was either in excess, or at least as abundant, asClONO2 and comprised between 50 and 70% of theavailable chlorine, Cly. On 1 February, measurements were madeinside the polar vortex. The air mass sampled on this day showed a clearsignature of diabatic descent, and also enhanced levels of ClO with amaximum of 230 pptv at 22.5 km. A 10 day backward trajectory analysis showedthat these air masses had passed a large region of low temperatures a fewhours prior to the measurement. Temperatures along the back trajectory atthe 475 K and 550 K levels (20.1 and 23.7 km respectively) were cold enoughfor heterogeneous chlorine activation to occur, in agreement with theobserved elevated ClO mixing ratios.  相似文献   

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