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1.
基于美国宇航局NASA/AURA卫星臭氧监测仪OMI数据,分析了2005—2014年长三角地区及其典型城市对流层O_3、NO_2柱浓度和HCHO大气总柱浓度的时空分布特征。结果表明:10 a间,长三角地区对流层O_3柱浓度和HCHO总柱浓度呈现增长趋势,O_3增量为0.23ppbv/10 a,HCHO增量为0.07×10~(16) mol/(cm~2·10 a),对流层NO_2柱浓度呈现降低趋势,减量为0.06×10~(15)mol/(cm~2·10 a);长三角地区对流层O_3柱浓度最大值出现在3、4、5月,而对流层NO_2柱浓度最大值出现在1、12月,HCHO总柱浓度最大值出现在6、7月;对流层O_3柱浓度的高值区分布在长三角中部、北部区域,对流层NO_2柱浓度高值区分布于长三角中部,HCHO总柱浓度高值区相对分散,且四季的分布各不相同。O_3与NO_2和HCHO在时间和空间上呈现一定的相关性。  相似文献   

2.
Photochemical indicators for determination of O3–NOx–ROG sensitivity and their sensitivity to model parameters are studied for a variety of polluted conditions using a comprehensive mixed-phase chemistry box model and the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect the indicators are identified and analyzed. Condensed mixed-phase chemical mechanisms are derived from the sensitivity analysis.Our results show that cloud chemistry has a significant impact on the indicators and their sensitivities, particularly on those involving H2O2, HNO3, HCHO, and NOz. Caution should be taken when applying the established threshold values of indicators in regions with large cloud coverage. Among the commonly used indicators, NOy and O3/NOy are relatively insensitive to most model parameters, whereas indicators involving H2O2, HNO3, HCHO, and NOz are highly sensitive to changes in initial species concentrations, reaction rate constants, equilibrium constants, temperature, relative humidity, cloud droplet size, and cloud water content.  相似文献   

3.
Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×106 to 3.2×106 cm-3. Simultaneously we measured the concentrations of O3, H2O, NO, NO2, CH4, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O3 and NO2. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO x concentrations. It is argued that additional, so far unidentified. HO x loss reactions must be responsible for that discrepancy.  相似文献   

4.
Simultaneous observations for the total column densities of NO2, O3 and H2O were carried on using the porta-ble Spectrometer (438-450 nm and 400-450 nm) and the visible Spectrometer (544.4-628 nm) during premonsoon thunderstorms and embedded hail storm activity at Pune (18o32’N & 73o51’E), India. These observations confirm the fact that there is an increase in O3 and NO2 column densities during thunderstorms. The increase in O3 was observed following onset of thunderstorm, while the increase in NO2 was observed only after the thunder flashes occur. This implies that the production mechanisms for O3 and NO2 in thunderstorm are different. The observed column density of NO2 value (1 to 3 × 1017molecules · cm-2) during thunderstorm activity is 10 to 30 times higher than the value (1 × 1016molecules · cm-2) of a normal day total column density. The spectrometric observations and observations of thunder flashes by electric field meter showed that 6.4 × 1025molecules / flash of NO2 are produced. The increased to-tal column density of ozone during thunderstorm period is 1.2 times higher than normal (clear) day ozone concentra-tion. The multiple scattering in the clouds is estimated from H2O and O2 absorption bands in the visible spectral re-gion. Considering this effect the calculated amount of ozone added in the global atmosphere due to thunderstorm ac-tivity is 0.26 to 0.52 DU, and the annual production of ozone due to thunderstorm activity is of the order of 4.02 × 1037 molecules /year. The annual NO2 production may be of the order of 2.02 × 1035molecules / year.  相似文献   

5.
Measurements of formaldehyde, HCHO, using tunable diode laser abssrption spectroscopy (TDLAS) are reported for four sites in North America. The TDLAS apparatus and its application to these measurements is described. Detection limits of ca. 0.25 ppbv were obtained with a three-minute time resolution. Two distinct types of diurnal behaviour were observed: in the absence of local pollution sources the HCHO diurnal variation was weak and HCHO is not lost during the night. We conclude that the lifetime of HCHO with respect to dry deposition was greater than 50 h at the least-polluted site. At sites downwind of pollution sources, the HCHO peaks near noon and declines in the afternoon. At the least-polluted location, the most probable value for HCHO was 0.25–0.5 ppbv, while hourly averaged values up to 12 ppbv were observed at the other locations.  相似文献   

6.
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   

7.
全球闪电活动与对流层上部NO及O3的相关性分析   总被引：1，自引：1，他引：0       下载免费PDF全文
为了解闪电对对流层上部微量气体的贡献,利用全球水资源和气候中心(GHRC)提供的1995年4月—2006年6月的闪电卫星格点资料,以及高层大气研究卫星(UARS)上的卤素掩星试验(HALOE)1991年10月—2005年11月的观测资料,分析了全球闪电与对流层上部NO和O3体积分数的时空分布特征及其相关性。结果表明:全球闪电12、1、2月集中在南半球,6—8月集中在北半球,全球闪电的季节分布与NO、O3类似;NO体积分数在350 h Pa附近达到最大,该高度的南半球NO体积分数变化范围为7×10-12~11×10-12、北半球为3×10-12~17×10-12;450~300 h Pa,北半球夏季O3体积分数呈明显增加趋势,且同一高度上夏季的值比年平均值大25%左右,南半球夏季O3体积分数高于冬季,但差异并不大。结论进一步证明了闪电与对流层上部NO及O3的密切关系,也为研究全球气候变化提供有力证据。  相似文献   

8.
对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.  相似文献   

9.
We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH2O, an important intermediate of CH4 (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO x -radicals via photodissociation of CH2O in the gas phase. In the droplets, the hydrated form of CH2O, its oxidation product HCO2 –, and H2O2 recycle O2 – radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O3. Further O3 concentrations are reduced as a result of decreased formation of O3 during periods with clouds. Additionally, NO x , which acts as a catalyst in the photochemical formation of O3, is depleted by clouds during the night via scavenging of N2O5. This significantly reduces NO x -concentrations during subsequent daylight hours, so that less NO x is available for O3 production. Clouds thus directly reduce the concentrations of O3, CH2O, NO x , and HO x . Indirectly, this also affects the budgets of other trace gases, such as H2O2, CO, and H2.  相似文献   

10.
Summary Vertical profiles of H2O, CO2, O3, NO and NO2 were measured during the Hartheim Experiment (HartX) to develop and calibrate a multi-layer resistance model to estimate deposition and emission of the cited gaseous species. The meteorological and gas concentration data were obtained with a 30 m high telescopic mast with 7 gas inlets located at 5 m intervals and meteorological sensors at 5, 15 and 30 m above ground; a complete gas profile was obtained every 9 min 20 s. Measured profiles were influenced by several exchange processes, namely evapotranspiration, dewfall, assimilation of CO2 in the tree crowns, soil respiration, deposition of NO2 and O3 to the soil and advection of NOx from the nearby highway. Surprisingly, no decrease in O3 concentration was observed in the crown layer during daytime, probably due to the relatively low density of foliage elements and strong turbulent mixing.The advantage of measuring in-canopy profiles is that turbulent exchange coefficients need not be estimated as a prerequisite to obtaining vertical flux estimates. In recent years, flux-gradient relationships in canopies have been subject to many criticisms. If fluxes are calculated at several heights considering only the transfers between the turbulent air and the interacting surfaces at a certain height, and those fluxes are then integrated vertically in a subsequent step, then exchange estimates (deposition or emission) can be obtained independent of turbulent exchange conditions.Typical estimated deposition velocities calculated for a 3-day period are between 4 and 10 mm/s for NO2 and about 4–9 mm/s for O3 (day and night values respectively). This leads to deposition rates of about 20–40 ng N/m2s for NO2 and about 30–40 mg O3/m2 deposited daily under the conditions encountered during HartX. Sensitivity tests done with the best available and most realistic values for model parametrization have shown that sensitivity is large with respect to the soil and cuticula resistances as well as for gas-phase ozone destruction and that more research is required to describe the effectiveness of cuticula and soil in modifying sink characteristics for NO2 and O3.With 12 Figures  相似文献   

11.
Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl2 or BrCl) increased.  相似文献   

12.
The kinetics of the reaction of nitrous acid (HONO) with nitric acid (HNO3), nitrate radicals (NO3) and dinitrogen pentoxide (N2O5) have been studied using Fourier transform infrared spectroscopy. Experiments were performed at 700 torr total pressure using synthetic air or argon as diluents. From the observed decay of HONO in the presence of HNO3 a rate constant of k<7×10-19 cm3 molecule-1 s-1 was derived for the reaction of HONO with HNO3. From the observed decay of HONO in the presence of mixtures of N2O5 and NO2 we have also derived upper limits for the rate constants of the reactions of HONO with NO3 and N2O5 of 2×10-15 and 7×10-19 cm3 molecule-1 s-1, respectively. These results are discussed with respect to previous studies and to the atmospheric chemistry of HONO.  相似文献   

13.
This paper describes laboratory experiments designed to obtain the infrared spectra of some atmospherically important radical species and related compounds. A Fourier transform spectrometer was used that was capable of yielding resolutions as great as 0.0024 cm-1, and optical paths of up to 512 m were employed. The objective of the experiments was to obtain the spectra for subsequent application to remote sounding measurements in the atmosphere.Radicals were generated by a variety of chemical reactions involving atoms or other highly reactive precursors. Spectra of the 3 band of NO3, at ca. 1500 cm-1, were obtained with up to 0.005 cm-1 resolution using the reaction between NO2 and O3 to produce the radical. The most satisfactory source of ClO was found to be the reaction between Cl and O3, and the (1-0) vibration-rotation band in the region 829–880 cm-1 was recorded at a resolution of 0.02 cm-1. We were unable to observe infrared absorption of HO2 with any of the radical sources that we tested. High-resolution survey spectra were obtained of compounds used as reactants, or formed as side-products in the radical-generating processes. These compounds included N2O5, HNO3, ClONO2, FNO2, Cl2O, HO2NO2, and probably FO2.The ability to monitor concentrations of the NO3 radical in the visible region of the spectrum as well as the concentrations of reactants and other products in the infrared region allowed us to undertake a study of the time-dependent interactions occurring when NO2 reacts with O3. The results indicate the importance of heterogeneous processes, especially when traces of water are present, and lend credence to suggestions that heterogeneous mechanisms in the NO3–N2O5–H2O system might be a viable source of HNO3 in the atmosphere.  相似文献   

14.
It is essential to quantify the background reactivity of smog-chambers, since this might be the major limitation of experiments carried out at low pollutant concentrations typical of the polluted atmosphere. Detailed investigation of three chamber experiments at zero-NO x in the European Photoreactor (EUPHORE) were carried out by means of rate-of-production analysis and two uncertainty analysis tools: local uncertainty analysis and Monte Carlo simulations with Latin hypercube sampling. The chemical mechanism employed was that for methane plus the inorganic subset of the Master Chemical Mechanism (MCMv3.1). Newly installed instruments in EUPHORE allowed the measurement of nitrous acid and formaldehyde at sub-ppb concentrations with high sensitivity. The presence of HONO and HCHO during the experiments could be explained only by processes taking place on the FEP Teflon walls. The HONO production rate can be described by the empirical equation W(HONO)EUPHORE dry = a × j NO 2× exp (− T 0/T) in the low relative humidity region (RH < 2%, a = 7.3×1021 cm−3, T 0 = 8945K), and by the equation W(HONO)EUPHORE humid = W(HONO)EUPHORE dry+ j NO 2× b × RH q in the higher relative humidity region (2% < RH < 15%, b = 5.8×108 cm−3 and q = 0.36, and RH is the relative humidity in percentages). For HCHO the expression W(HCHO)EUPHORE = c × j NO 2exp (− T′0/T) is applicable (c = 3.1×1017 cm−3 and T′0 = 5686 K). In the 0–15% relative humidity range OH production from HONO generated at the wall is about a factor of two higher than that from the photolysis of 100 ppb ozone. Effect of added NO2 was found to be consistent with the dark HONO formation rate coefficient of MCMv3.1.  相似文献   

15.
Rate constants for the gas-phase reactions of OH radicals, NO3 radicals and O3 with the C7-carbonyl compounds 4-methylenehex-5-enal [CH2=CHC(=CH2)CH2CH2CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH2=CHC(CH3)=CHCH2CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm3 molecule–1 s–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10–10, (4.75 ± 0.35) × 10–13 and (1.46 ± 0.12) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10–10, (2.17 ± 0.30) × 10–12, and (4.13 ± 0.81) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10–10, (1.75 ± 0.27) × 10–12, and (5.36 ± 0.28) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10–10, (1.81 ± 0.35) × 10–12, and (6.98 ± 0.40) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO3 radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.  相似文献   

16.
Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO y , called NO z , was neither NO nor NO2. This NO z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO z to NO3 - in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO3 and N2O5 by aerosol of surface area proportional to the NO2 mixing ratio, shows that NO3 and N2O5 may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N2O5 forming NO3 - in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N2O5 was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO2 and the cloud liquid water content were related to each other. Also, indications of conversion of NO x to NO z were found. To explain these observations, scavenging of NO x and HNO2 by cloud droplets and/or aqueous-phase oxidation of NO2 - by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO x or SO2, NO3 - which had entered the cloud as aerosol particles was liberated as HNO3 vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO3 to particulate NO3 -, was observed.  相似文献   

17.
Rain and air of Florence have been collected in a continuous way andanalysed by flow analysis spectrofluorimetric methods for formaldehydeand hydrogen peroxide. Diurnal and seasonal variations were observed;the mean/maximum concentrations of all data (as gm–3) are 3.3/23.4 for HCHO and 0.4/4.93 forH2O2. The effect of external sources and ofphotochemical reactions produces periods of positive and negativecorrelations for these compounds. The mean/maximum rain concentration ofall data are 98/443 g l–1 for HCHO and 84/685 g l–1 for H2O2. Concentrationratios rain/air and discrepancies to Henry's Law equilibrium arediscussed.  相似文献   

18.
An updated version of the Regional Acid Deposition Model(RADM)driven by meteorologicalfields derived from Chinese Regional Climate Model(CRegCM)is used to simulate seasonal variationof tropospheric ozone over the eastern China.The results show that:(1)Peak O_3 concentration moves from south China to north China responding to the changing ofsolar perpendicular incidence point from south to north.When solar perpendicular incidence pointmoves from north to south,so does the peak O_3 concentration.(2)In the eastern China.the highest O_3 month-average concentration appears in July.thelowest in January and the medium in April and October.The pattern mainly depends on the solarradiation,the concentration of O_3 precursors NO_x and NMHC and the ratio of NMHC/NO_x.(3)Daily variations of O_3 over the eastern China are clear.Namely,O_3 concentrations rise withthe sun rising and the maximums appear at noon.then O_3 concentrations decrease.The highest dailyvariation range of O_3 appears in summer(40×10~(-9) in volume fraction)and the lowest in winter(20×10~(-9) in volume fraction).(4)Daily variations of O_3 over the western China are not clear.The daily variation range of O_3 isless than 10×10~(-9) in volume fraction.  相似文献   

19.
Simultaneous measurements of peroxy and nitrate radicals at Schauinsland   总被引：3，自引：0，他引：3  
We present simultaneous field measurements of NO3 and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O3, NO x , NO y , and hydrocarbons, as well as meteorological parameters. NO2, NO3, HO2, and (RO2) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO3 and HO2 were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO3, RO2, and HO2 exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO3 and RO2 radical concentrations at night.The measured trace gas set allows the calculation of NO3 and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO2 concentrations. The chemical budget of both NO3 and RO2 radicals can be understood if emissions of monoterpenes are included. The measured HO2 can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO2 radicals implies the presence of hydroxyl radicals at night in concentrations of up to 105 cm–3.  相似文献   

20.
Generally, it is assumed that UV-light, high temperature or reactive molecules like O3 and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O2-dissociation rates on natural quartz sand at 40˚C and compared these with O2-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O2-molecules the measured rates are in the 10−12–10−4 range. We have also measured dissociation rates of H2 and N2, water-formation from H2 and O2 mixtures, exchange of N between N2, NO x and a breakdown of HNO3, NO2 and CH4 on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H2, NO2 and CH4. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO x or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N2, O2 and H2O.  相似文献   

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