首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 234 毫秒
1.
The role of perturbations of reactive trace gas concentration distributions in turbulent flows in the planetary boundary layer (PBL) is discussed. The paper focuses on disturbances with larger spatial scales. Sequential nesting of a chemical transport model is applied to assess the effect of neglecting subgrid chemical perturbations on the formation and loss of ozone, NO x , peroxyacetyl nitrate (PAN) and HNO3 calculated with a highly complex chemical mechanism. The results point to characteristic differences regarding the process of mixing of chemically reactive species in the PBL and lower troposphere.  相似文献   

2.
The impact of natural and anthropogenicnon-methane hydrocarbons (NMHC) on troposphericchemistry is investigated with the global,three-dimensional chemistry-transport model MOGUNTIA.This meteorologically simplified model allows theinclusion of a rather detailed scheme to describeNMHC oxidation chemistry. Comparing model resultscalculated with and without NMHC oxidation chemistryindicates that NMHC oxidation adds 40–60% to surfacecarbon monoxide (CO) levels over the continents andslightly less over the oceans. Free tropospheric COlevels increase by 30–60%. The overall yield of COfrom the NMHC mixture considered is calculated to beabout 0.4 CO per C atom. Organic nitrate formationduring NMHC oxidation, and their transport anddecomposition affect the global distribution of NO x and thereby O3 production. The impact of theshort-lived NMHC extends over the entire tropospheredue to the formation of longer-lived intermediateslike CO, and various carbonyl and carboxyl compounds.NMHC oxidation almost doubles the net photochemicalproduction of O3 in the troposphere and leads to20–80% higher O3 concentration inNO x -rich boundarylayers, with highest increases over and downwind ofthe industrial and biomass burning regions. Anincrease by 20–30% is calculated for the remotemarine atmosphere. At higher altitudes, smaller, butstill significant increases, in O3 concentrationsbetween 10 and 60% are calculated, maximizing in thetropics. NO from lightning also enhances the netchemical production of O3 by about 30%, leading to asimilar increase in the global mean OH radicalconcentration. NMHC oxidation decreases the OH radicalconcentrations in the continental boundary layer withlarge NMHC emissions by up to 20–60%. In the marineboundary layer (MBL) OH levels can increase in someregions by 10–20% depending on season and NO x levels.However, in most of the MBL OH will decrease by10–20% due to the increase in CO levels by NMHCoxidation chemistry. The large decreases especiallyover the continents strongly reduce the markedcontrasts in OHconcentrations between land and oceanwhich are calculated when only the backgroundchemistry is considered. In the middle troposphere, OHconcentrations are reduced by about 15%, although dueto the growth in CO. The overall effect of thesechanges on the tropospheric lifetime of CH4 is a 15%increase from 6.5 to 7.4 years. Biogenic hydrocarbonsdominate the impact of NMHC on global troposphericchemistry. Convection of hydrocarbon oxidationproducts: hydrogen peroxides and carbonyl compounds,especially acetone, is the main source of HO x in theupper troposphere. Convective transport and additionof NO from lightning are important for the O3 budgetin the free troposphere.  相似文献   

3.
A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 103 cm-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO2) and methyl nitrate (CH3ONO2) were shown to be minor components of the total NO y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO2 to HOCl or Cl2 were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.  相似文献   

4.
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   

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

6.
During 18–23 July 1990, 31 smoke samples were collected from an aircraft flying at low altitudes through the plumes of tropical savanna fires in the Northern Territory, Australia. The excess (above background) mixing ratios of 17 different trace gases including CO2, CO, CH4, several non-methane hydrocarbons (NMHC), CH3CHO, NO x (– NO + NO2), NH3, N2O, HCN and total unspeciated NMHC and sulphur were measured. Emissionratios relative to excess CO2 and CO, and emissionfactors relative to the fuel carbon, nitrogen or sulphur content are determined for each measured species. The emission ratios and factors determined here for carbon-based gases, NO x , and N2O are in good agreement with those reported from other biomass burning studies. The ammonia data represent the first such measurements from savanna fires, and indicate that NH3 emissions are more than half the strength of NO x emissions. The emissions of NO x , NH3, N2O and HCN together represent only 27% of the volatilised fuel N, and are primarily NO x (16%) and NH3 (9%). Similarly, only 56% of the volatilised fuel S is accounted for by our measurements of total unspeciated sulphur.  相似文献   

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

8.
In situ aircraft measurements of O3, CO,HNO3, and aerosol particles are presented,performed over the North Sea region in the summerlower stratosphere during the STREAM II campaign(Stratosphere Troposphere Experiments by AircraftMeasurements) in July 1994. Occasionally, high COconcentrations of 200-300 pbbv were measured in thelowermost stratosphere, together with relatively highHNO3 concentrations up to 1.6 ppbv. The particlenumber concentration (at standard pressure andtemperature) between 0.018-1 m decreased acrossthe tropopause, from >1000 cm-3 in the uppertroposphere to <500 cm-3 in the lowermoststratosphere. Since the CO sources are found in thetroposphere, the elevated CO mixing ratios areattributed to mixing of polluted tropospheric air intothe lowermost extratropical stratosphere. Further wehave used a chemical model to illustrate that nitrogenoxide reservoir species (mainly HNO3) determinethe availability of NOx (=NO + NO2) andtherefore largely control the total net O3production in the lower kilometers of thestratosphere. Model simulations, applying additionalNOx perturbations from aircraft, show that theO3 production efficiency of NOx is smallerthan previously assumed, under conditions withrelatively high HNO3 mixing ratios, as observedduring STREAM II. The model simulations furthersuggest a relatively high O3 productionefficiency from CO oxidation, as a result of therelatively high ambient HNO3 and NOxconcentrations, implying that upward transport of COrich air enhances O3 production in the lowermoststratosphere. Analysis of the measurements and themodel calculations suggest that the lowermoststratosphere is a transition region in which thechemistry deviates from both the upper troposphere andlower stratosphere.  相似文献   

9.
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   

10.
郭凤霞  陈聪 《大气科学》2012,36(4):713-721
为了解闪电对对流层上部NOx的贡献,本文利用美国全球水资源和气候中心（GHRC）提供的1995年4月~2005年12月的闪电卫星格点资料及高层大气研究卫星 (UARS) 上的卤素掩星试验装置 (HALOE) 1991年10 月~2005 年11月的观测资料,分析了中国地区闪电与对流层上部NOx体积混合比的时空分布特征及两者的相关性.结果表明:中国地区闪电和对流层上部的NOx在季节分布、年际分布和空间分布上保持很好的一致性,闪电是对流层上部NOx的重要来源;NO极值高度在350 hPa左右,云闪直接产生的NO是极值产生的主要原因,NO2的极值高度在250 hPa左右,因为闪电产生的NO在传输过程中会被氧化成NO2并通过雷暴的垂直输送作用抬升到更高高度;强对流活动有利于NOx的传输,而人类活动产生的NOx一般较难输送到对流层上部,因此闪电多发区的NOx极值较大,所在的高度也较高.  相似文献   

11.
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   

12.
Lightning is thought to represent an important source of tropospheric reactive nitrogen species NOx (NO + NO2),but estimates of global production of NOx by lightning varyconsiderably. We evaluate the production of NOx by lightning using a global chemical/transport model, satellite lightning observations, and airborne NOx measurements. Various model calculations are conducted toassess the global NOx production rate of lightning by comparing the model calculations with airborne measurements. The results show that the simulated NOx in the tropical middle and upper troposphere are very sensitiveto the amount and altitude of the lightning NOx used in the model. A global lightning NOx production of 7 Tg N yr–1uniformly distributed in convective clouds or 3.5 Tg N yr–1 distributedin the upper cloud regions produces good agreement between calculated and measured NOx concentrations in the tropics.  相似文献   

13.
Field measurement programs in Brazil during the dry seasons in August and September 1979 and 1980 have demonstrated the large importance of the continental tropics in global air chemistry. Many important trace gases are produced in large amounts over the continents. During the dry season, much biomass burning takes place, especially in the cerrado regions, leading to a substantial emission of air pollutants, such as CO, NO x , N2O, CH4 and other hydrocarbons. Ozone concentrations are enhanced due to photochemical reactions. The large biogenic organic emissions from tropical forests play an important role in the photochemistry of the atmosphere and explain why CO is present in such high concentrations in the boundary layer of the tropical forest. Carbon monoxide production may represent more than 3% of the net primary productivity of the tropical forests. Ozone concentrations in the boundary layer of the tropical forests indicate strong removal processes. Due to atmospheric supply of NO x by lightning, there is probably a large production of O3 in the free troposphere over the Amazon tropical forests. This is transported to the marine-free troposphere and to the forest boundary layer.  相似文献   

14.
An improvement of long-range air pollution transport and diffusion model which includes planetary boundary layer (PBL) dynamics and chemistry of SO2 and NOx, the processes of dry and wet deposition has been developed and used in the Southeast Europe. The transport and diffusion process are described on the basis of a combination of the Eulerian and Lagrangian approaches. A similarity theory is used for calculation of the PBL characteristics. A known linear chemistry module which includes 5 nitrogen and 2 sulphate species is incorporated. The model results for the region of Southeast Europe are in good agreement with the Meteorological Synthesizing Center West, Oslo information.  相似文献   

15.
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   

16.
Three online coupled chemical transport model simulations were analyzed for three summer months of 2015 in Poland. One of them was run with default emission inventory, the other two with NOx and VOC emissions reduced by 30%, respectively. Obtained ozone concentrations were evaluated with data from air quality measurement stations and ozone sensitivity to precursor emissions was estimated by ozone concentration differences between simulations and with the use of indicator ratios. They were calculated based on modeled mixing ratios of ozone, total reactive nitrogen and its components, nitric acid and hydrogen peroxide. The results show that the model overestimates ozone concentrations with the largest errors in the morning and evening, which is primarily related to the way vertical mixing is resolved by the model. Better model performance for ozone is achieved in rural than urban environment, as PBL and mixing mechanisms play more significant role in urban areas. Modeled ozone shows mixed sensitivity to precursor concentrations, similarly to other European regions, but indicator ratios have different values than are found in literature, particularly H2O2/HNO3 is larger than in southern Europe. However, indicator ratios often differ between locations and transition values need to be established individually for a given region.  相似文献   

17.
传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O3））前体物的氧化反应,具有一定的不确定性,导致模拟结果产生偏差.针对该问题,本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM）,模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O3和其前体物随时间的变化趋势.对模拟的O3日最大8 h平均浓度的统计分析表明,徐州表现最好（标准平均误差=-0.15,标准平均偏差=0.23）.在长三角地区,居民源对挥发性有机物（VOCs）的贡献最大,占39.08%,其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小,约为2.11%.对活性氧化氮（NOy）的分析表明,其主要组分是NOx（80%）,其次是硝酸（HNO3）（<10%）.O3的空间分布与NOy和NOx非常相似.HCHO等其他氧化产物的分布与NOx相似,这很可能是由于在高NOx条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似,表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.  相似文献   

18.
The objectives of this study were to identify species and levels of volatile organic compounds (VOCs), and determine their oxidation capacity in the rural atmosphere of western Senegal. A field study was conducted to obtain air samples during September 14 and September 15, 2006 for analyses of VOCs. Methanol, acetone, and acetaldehyde were the most abundant detected chemical species and their maximum mixing ratios reached 6 parts per billion on a volume basis (ppbv). Local emission sources such as firewood and charcoal burning strongly influenced VOC concentrations. The VOC concentrations exhibited little temporal variations due to the low reactivity with hydroxyl radicals, with reactivity values ranging from 0.001 to 2.6 s−1. The conditions in this rural site were rather clean. Low ambient NO x levels limited ozone production. Nitrogen oxide (NO x ) levels reached values less than 2 ppbv and maximum VOC/NO x ratios reached 60 ppbvC/ppbv, with an overall average of 2.4 ± 4.5 ppbvC/ppbv. This indicates that the rural western Senegal region is NO x limited in terms of oxidant formation potential. Therefore, during the study period photochemical ozone production became limited due to low ambient NO x levels. The estimated ozone formation reactivity for VOCs was low and ranged between −5.5 mol of ozone/mol of benzaldehyde to 0.6 mol/mol of anthropogenic dienes.  相似文献   

19.
Halogens in the atmosphere chemically destroy ozone. In the troposphere, bromine has higher ozone destruction efficiency than chlorine and is the halogen species with the widest geographical spread of natural sources. We investigate the relative strength of various sources of reactive tropospheric bromine and the influence of bromine on tropospheric chemistry using a 6-year simulation with the global chemistry transport model MOZART4. We consider the following sources: short-lived bromocarbons (CHBr3, CH2BrCl, CHBr2Cl, CHBrCl2, and CH2Br2) and CH3Br, bromine from airborne sea salt particles, and frost flowers and sea salt on or in the snowpack in polar regions. The total bromine emissions in our simulations add up to 31.7 Gmol(Br)/yr: 63 % from polar sources, 24.6 % from short-lived bromocarbons and 12.4 % from airborne sea salt particles. We conclude from our analysis that our global bromine emission is likely to be on the lower end of the range, because of too low emissions from airborne sea salt. Bromine chemistry has an effect on the oxidation capacity of the troposphere, not only due to its direct influence on ozone concentrations, but also by reactions with other key chemical species like HO x and NO x . Globally, the impact of bromine chemistry on tropospheric O3 is comparable to the impact of gas-phase sulfur chemistry, since the inclusion of bromine chemistry in MOZART4 leads to a decrease of the O3 burden in the troposphere by 6 Tg, while we get an increase by 5 Tg if gas-phase sulfur chemistry is switched off in the standard model. With decreased ozone burden, the simulated oxidizing capacity of the atmosphere decreases thus affecting species associated with the oxidation capacity of the atmosphere (CH3OOH, H2O2).  相似文献   

20.
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   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号