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1.
Oxidation reactions of the proposed CFC substitutes HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3) have been studied in the laboratory using long-path Fourier transform infrared spectroscopy. The air oxidation of the HCFCs was initiated by the photolysis of Cl2 forming Cl atoms that abstract H atoms from the HCFC. CF3C(O)Cl was the only carbon containing compound observed in the infrared spectrum of the products of the HCFC-123/Cl2 irradiations and its yield was approximately one. The product data are consistent with formation of CF3C(O)Cl by Cl elimination of the intermediate halogenated alkoxy radical CF3CCl2O. The Cl-initiated oxidation of HCFC-141b led to the formation of CO and C(O)FCl. The product data are consistent with a 1 : 1 relationship between C(O)FCl formed and HCFC-141b reacted. Product data were compatible with both decomposition by cleavage of the C–C bond of the radical CFCl2CH2O leading to the prompt generation of C(O)FCl and reaction of the radical with O2 forming the two carbon halogenated aldehyde CFCl2CH(O), which in the presence of Cl was likely oxidized to C(O)FCl. An approximate method was developed in which the ratio was extracted from analysis of the time evolution of HCFC-141b, C(O)FCl, and CO. The data suggest that the contributions are comparable.  相似文献   

2.
The products of the Cl-atom initiated reactions of a series of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) in air have been investigated at 298 K and one atmosphere (740 Torr total pressure) of air. The products observed and quantified and their yields (%) were as follows: from CHF2Cl (HCFC-22), C(O)F2 (100%); from CHFCl2 (HCFC-21), C(O)FCl (100%); from CH2FCl (HCFC-31), HC(O)F (100%); from CH3F (HFC-41), HC(O)F (100%); from CH3CFCl2 (HCFC-141b), C(O)FCl (100%); from CH3CF2Cl (HCFC-142b), C(O)F2 (100%); from CH3CHF2 (HFC-152a), C(O)F2 (92%); from CHCl2CF3 (HCFC-123), CF3C(O)Cl (98%); from CHFClCF3 (HCFC-124), CF3C(O)F (101%); and from CHF2CF3 (HFC-125), C(O)F2 (100%). The reaction mechanisms are discussed.  相似文献   

3.
A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NOX. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO2 concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO2 is a minor process and that most of the reaction occurs with O2. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO2 concentrations.  相似文献   

4.
The absorption cross-sections of HCFC-123 (CF3–CHCl2), HCFC-141b (CH3–CFCl2) and HCFC-142b (CH3–CF2Cl) are measured between 170 and 250 nm for temperatures ranging from 295 to 210 K with uncertainties between 2 and 4%. They are compared with other available determinations. Temperature effects are discussed and parametrical formulae are proposed to compute the absorption cross-section for wavelengths and temperatures useful in atmospheric modelling calculations. Photodissociation coefficients are presented and their temperature-dependence is discussed.  相似文献   

5.
Lifetimes, scavenging ratios, andbudgets describe the cycling of atmosphericconstituents and are often used in formulating airpollution control strategies. Most previous studiesof sulfur lifetimes, budgets, and scavenging ratioshave been based on limited observational data or datafrom highly simplified models. The Regional AcidDeposition Model (RADM2.61) shows some skill inpredicting atmospheric mixing ratios of acidicmaterials and other related trace constituents andacid deposition patterns in North America, and so,analysis of its established, theoretical, databaseserves as a counterpoint to previous studies of sulfurbudgets, lifetimes, and scavenging ratios. The annualbudget shows that the net transport (outflow minusinflow) of sulfur compounds out of eastern NorthAmerica is equal to the total deposition within thedomain. Of the total deposition, 63% is from wetdeposition and 37% is from dry deposition. Theannual average lifetime of sulfur dioxide (38 hours),estimated by the turnover time, is limited by aqueousconversion, while that for sulfate aerosols (54 hours)is limited by their removal in precipitation. Theannual average lifetime of sulfur in this domain isslightly more than three days. Episodic lifetimes andbudgets, based on particular synoptic situations, showlarge variations around the annual values. Episodicprecipitation scavenging ratios exhibit similarvariability and are used to offer explanations ofseveral potential biases found in the wet sulfurdeposition amounts as predicted by the EMEP sulfurtransport model and other published results.  相似文献   

6.
The reaction mechanisms of products, along with their rates of reaction with hydroxyl radicals and their rates of photolysis, have been used to obtain carbon monoxide, CO, yields from the products of the homogenous atmospheric photooxidation from emissions of hydrocarbons and other volatile organic compounds, VOCs. Seasonally averaged CO yields are estimated for a number of types of VOCs. The annual production of CO is estimated for the contiguous United States from combustion sources of CO and from the atmospheric photooxidation of anthropogenic and biogenic emissions of volatile organic compounds. Limitations on estimates of CO yields and of CO production from various heterogeneous processes are discussed.  相似文献   

7.
The product distributions have been calculated for more abundant alkanes contributing most of the carbon atoms in the alkane fraction of an ambient air hydrocarbon mixture reasonably representative of U.S. emissions. The effects of ambient temperatures on product yields has been calculated for a range of temperatures from 250 to 330 K. The sensitivity of product yields to uncertainties in alkoxy radical process rate constants has been examined with emphasis on uncertainties in decomposition reactions. Chemical lifetimes are estimated at 300 K under summertime conditions for hydrocarbons and for products of alkane photooxidation in the atmosphere. The atmospheric distribution of alkanes and products is evaluated in terms of the extent to which reaction processes are likely to occur in the planetary boundary layer compared to the free troposphere.The calculations predict a substantial effect of temperature on product yields. A large decrease in alkyl nitrate yields and a smaller decrease in ketone yields occur with increasing temperature. The yields of the short-lived, more reactive aldehydes undergo substantial increases with increasing temperature. Lower yields of ketones and higher yields of aldehydes are associated with the use of higher compared to lower decomposition process rate constants. For the type of U.S. hydrocarbon mixture available from measurements, 16 oxygenated products account for more than 60% of the total alkane carbon atoms converted to products, with most of these carbon atoms accounted for by four products. The effects of increased temperature on product reactivity and radical production may also influence O3 production.  相似文献   

8.
城市大气气溶胶细粒子的化学成分及其来源   总被引：11，自引：0，他引：11  
于凤莲 《气象》2002,28(11):3-6
大气气溶胶细颗粒物（PM10、PM2．5）是近年来大气气溶胶研究的热点。细粒子中含有多种化学元素与化合物。细粒子中的化学成分随时空变化而变化。细粒子主要来自车辆尾气、化石、油料及生物质燃料燃烧等人为排放源和二次污染。  相似文献   

9.
The binary water–sulphuric acid nucleation has long been considered an important path for new particle formation in the atmosphere. The formation rate depends nonlinearly on temperature and vapour concentrations. We aim to find out if atmospheric small scale and mesoscale spatial and temporal variability can increase the nucleation rate significantly. Simultaneous and separate effects of variation in temperature, humidity and sulphuric acid concentration on the mean nucleation rate have been modelled. We have assumed that the distributions of variables are Gaussian and compare the mean of simulated nucleation rates with the nucleation rate in mean conditions without variation. According to our studies the atmospheric variability can increase the mean nucleation rate by orders of magnitude but the significant effect is limited to specific conditions. The effect seems to be more important in the lower troposphere than in the upper troposphere, where temperature and sulphuric acid concentrations are lower. In addition, our model simulations indicate that the atmospheric variability can only explain part of the difference between measured and theoretically required sulphuric acid concentrations in conditions where particle formation has been observed. We have parametrised the effect of atmospheric variability as a simple correction factor for the effect of temperature and humidity variation.  相似文献   

10.
《Atmospheric Research》2007,83(3-4):503-513
The binary water–sulphuric acid nucleation has long been considered an important path for new particle formation in the atmosphere. The formation rate depends nonlinearly on temperature and vapour concentrations. We aim to find out if atmospheric small scale and mesoscale spatial and temporal variability can increase the nucleation rate significantly. Simultaneous and separate effects of variation in temperature, humidity and sulphuric acid concentration on the mean nucleation rate have been modelled. We have assumed that the distributions of variables are Gaussian and compare the mean of simulated nucleation rates with the nucleation rate in mean conditions without variation. According to our studies the atmospheric variability can increase the mean nucleation rate by orders of magnitude but the significant effect is limited to specific conditions. The effect seems to be more important in the lower troposphere than in the upper troposphere, where temperature and sulphuric acid concentrations are lower. In addition, our model simulations indicate that the atmospheric variability can only explain part of the difference between measured and theoretically required sulphuric acid concentrations in conditions where particle formation has been observed. We have parametrised the effect of atmospheric variability as a simple correction factor for the effect of temperature and humidity variation.  相似文献   

11.
The gas-phase degradation of NH3 in the atmosphere still has many uncertainties. One of them is the possible isomerisation of NH2O to NHOH, as indicated by kinetic studies. Since NH2O is formed during the gas-phase oxidation of ammonia in the troposphere, this reaction can potentially influence the subsequent production of N2O and NOx. So far, the isomerisation has never been implemented into current chemical schemes describing the atmospheric gas-phase degradation of NH3 and its atmospheric relevance has never been assessed. The N2O yield from NH3 degradation is calculated to be in the range of 10–43 %. It depends on the NO2 and O3 concentrations, but is independent of the NH3 concentration. Compared with the results from recent literature, the N2O yield derived from the new mechanism is 20–80% lower, implying a smaller global N2O source strength of 0.4 Tg yr- 1. The production of NH2SO2 seems to be less important for the atmospheric degradation of NH3. NH3 oxidation is a sink for NOx at NOx mixing ratios of more than about 1 ppb and a source at lower NOx burdens.  相似文献   

12.

Global Climate Models (GCMs) generally exhibit significant biases in the representation of large-scale atmospheric circulation. Even after a sensible bias adjustment these errors remain and are inherited to some extent by the derived downscaling products, impairing the credibility of future regional projections. In this study we perform a process-based evaluation of state-of-the-art GCMs from CMIP5 and CMIP6, with a focus on the simulation of the synoptic climatological patterns having a most prominent effect on the European climate. To this aim, we use the Lamb Weather Type Classification (LWT, Lamb British isles weather types and a register of the daily sequence 736 of circulation patterns 1861-1971. METEOROL OFF, GEOPHYS MEM; 737 GB; DA 1972; NO 116; PP 1-85; BIBL 2P1/2, 1972), a subjective classification of circulation weather types constructed upon historical simulations of daily mean sea level pressure. Observational uncertainty has been taken into account by considering four different reanalysis products of varying characteristics. Our evaluation unveils an overall improvement of salient atmospheric circulation features consistent across observational references, although this is uneven across models and large frequency biases still remain for the main LWTs. Some CMIP6 models attain similar or even worse results than their CMIP5 counterparts, although in most cases consistent improvements have been found, demonstrating the ability of the new models to better capture key synoptic conditions. In light of the large differences found across models, we advocate for a careful selection of driving GCMs in downscaling experiments with a special focus on large-scale atmospheric circulation aspects.

  相似文献   

13.
Ground-based remote sensing systems have been used during the ESCOMPTE campaign, to continuously characterize the boundary-layer behaviour through many atmospheric parameters (wind, extinction and ozone concentration distribution, reflectivity, turbulence). This analysis is focused on the comparison of the atmospheric stratification retrieved from a UV angular ozone lidar, an Ultra High Frequency wind profiler and a sodar, above the area of Marseille, on June 26th 2001 (Intensive Observation Period 2b). The atmospheric stratification is shown to be very complex including two superimposed sea breezes, with an important contribution of advection. The temporal and spatial evolution of the stratification observed by the UV lidar and by the UHF radar are in good agreement although the origin of the echoes of these systems is quite different. The complexity of the dynamic situation has only partially been retrieved by a non-hydrostatic mesoscale model used with a 3 km resolution.  相似文献   

14.
The presence of amino acids in atmospheric precipitation and aerosols has been noted for many years, yet relatively little is known about these or other nitrogen containing organic compounds in the atmosphere. Marine and continental rainwater analyses indicate that atmospheric aerosols, and subsequently atmospheric precipitation, may contain substantial levels of free and combined amino acids. The most likely source of amino N in the remote marine atmosphere appears to be the injection of proteinaceous material through the action of bursting bubbles at the sea-air interface or the long range transport from terrestrial sources. The capacity of these substrates to undergo photooxidation and photodegradation in the atmosphere to simpler species, such as ammonium ions, carboxylic acids, and for the S containing amino acids, oxidized forms of sulfur, has received little attention from atmospheric chemists. The photochemistry of covalently bound amino groups, particularly as found in peptides and amino acids, is discussed here with the purpose of summarizing what is known of their occurrence and their possible importance to atmospheric chemistry.  相似文献   

15.
Summary A three-dimensional non-hydrostatic atmospheric model RAMS, version3b, is used to examine the impact of complex topography on the sea breeze under heterogeneous and degradation land use characteristics. In the study, it is shown that topography plays an important role in the sea-breeze circulation by aligning the sea breeze front to the coastline and locating the convergence zones close to the mountain range. When the sea breeze is coupled with the upslope wind, the sea-breeze circulation is strengthened by the topography.Sensitivity analyses are carried out to determine the influence of vegetation and soil moisture, i.e., land surface modifications, to this thermally driven flow. Land degradation results in an enhanced sea-breeze circulation which is characterized by a stronger onshore flow, a stronger return current, a larger updraft velocity associated with the sea-breeze front and further inland penetration. Other important features are a deeper sea-breeze depth, a larger downdraft velocity behind the sea-breeze front, and a longer offshore extent. The results also show how land changes modify the sea breeze temporal evolution resulting in an earlier onset and later end. The study stresses the convenience of using three-dimensional models with detailed land surface information to model the sea breeze in complex terrain where land use is rapidly modified.Received February 25, 2002; accepted October 7, 2002 Published online April 10, 2003  相似文献   

16.
This paper demonstrates the performance of a new design of atmospheric pressure flow-tube reactor coupled with an ion trap mass spectrometer. The reactor is designed for studying gas-phase reactions with reaction times in the range from 0.2 to 2 s. The system provides a simple, fast and robust method for introducing the reactant mixtures and for identifying the products of gas-phase reactions. As a practical example of application, we used the flow reactor to study the reaction of O3 with 2,3-dimethyl-2-butene. Good agreement was obtained between the flow tube results and previously reported studies for the identification of major products and measurement of their yields. This design has the potential to be used to study the atmospheric ozonolysis reactions of unsaturated species at realistic pressures and temperatures.  相似文献   

17.
A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NOx. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO2 concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.  相似文献   

18.
Difunctional organic nitrates are important products of the atmospheric reaction of NO3 radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH3CH(ONO2)CH2(ONO2); 1,2-butandiol dinitrate, CH3CH2CH(ONO2)CH2(ONO2); 2,3-butandiol dinitrate, CH3CH(ONO2)CH(ONO2)CH3;cis 1,4-dinitrooxy-2-butene, CH2(ONO2)CH=CHCH2(ONO2); 3,4-dinitrooxy-1-butene, CH2(ONO2CH(ONO2)CH=CH2; -nitrooxy acetone, CH3COCH2(ONO2); 1-nitrooxy-2-butanone, CH3CH2COCH2(ONO2); 3-nitrooxy-2-butanone, CH3CH(ONO2)COCH3.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO2 is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO y in the atmosphere, especially during the night, is briefly discussed.  相似文献   

19.
Air masses are characterized by physical (temperature, humidity) and chemical (transported gases and aerosols) properties, being associated their arrival to different meteorological scenarios. The knowledge of the air masses over a region is fundamental as complementary information in several atmospheric studies, being the calculation of back-trajectory the most widely used tool whenever air masses are analyzed. A study of air masses has been carried out in southwestern Iberian Peninsula using 5-day kinematic back trajectories computed by the HYSPLIT model at three heights (500, 1,500 and 3,000 m) from 1997 to 2007. The main aims have been to characterize their vertical behaviour and their thermal and humidity properties. Thirteen trajectory clusters have been defined, showing the northerly and westerly clusters a high coupling degree. Seasonal daily variation of potential temperature and specific humidity has been analyzed, obtaining higher differences among clusters in the cold season.  相似文献   

20.
利用分裂窗算法反演陆地表面温度的研究进展   总被引：25，自引：4，他引：25       下载免费PDF全文
俞宏  石汉青 《气象科学》2002,22(4):494-500
本文以LST反演的分裂窗算法作了回顾和比较，LST反演的分裂窗算法最一般的形式是Ts=T4 A(T4-T5) B,其中Ts是陆地表面温度，T4和T5分别是AVHRR分裂窗通道4和5的亮温度，A和B是由大气、观测角及地表辐射率所决定的系数，不同的算法其系数的确定有很大的不同，地表比辐射率的确定是LST反演中的主要难点，目前也有多种方法来确定地表比辐射率值，最后本文还指出了目前在LST反演中存在的局限性。  相似文献   

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