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1.
Monthly mean total vertical column abundances of acetylene have been determined from series of infrared solar spectra recorded at the Jungfraujoch station, Switzerland, between June 1986 and April 1991. The data have been obtained by nonlinear least-squares fittings of the 5 band R19 transition of C2H2 at 776.0818 cm-1. The average of 22 monthly mean total vertical columns of C2H2 retrieved during that time interval of almost 5 years was found to be equal to (1.81±0.12)×1015 molec/cm2, which corresponds to an average mixing ratio of (0,22±0.013) ppbv (parts per billion by volume) in a troposphere extending from the altitude of the station (3.58 km), up to 10.5 km. Despite the large variability found from year to year, a least-squares sine fit to the data reveals a seasonal variation with an amplitude of about ±40% of the mean; the maximum occurs during mid-winter and the minimum in the summer. The present results are compared critically with similar in-situ data found in the literature. A sinusoidal fit to all such free troposphere measurements made in-situ between 30°N and 60°N indicates good agreement in shape and phase with the seasonal variation derived above the Jungfraujoch, but their average column abundance, 2.3×1015 molec/cm2, is about 30% higher; this difference is explained on the basis of non-upwelling meteorological conditions generally prevailing during ground-based remote solar observations.  相似文献   

2.
A method for the estimation of the reaction probability of the heterogeneous N2O5+H2O 2HNO3 reaction using the deposition profile in a laminar flow tube, in which the walls are coated with the condensed aqueous phase of interest, is presented. The production of gas phase nitric acid on the surface followed by its absorption complicates the deposition profiles and hence the calculation of the reaction probability. An estimation of the branching ratio for this process enables a more appropriate calculation to be carried out. Reaction probabilities of N2O5 on substances including some normally constituting atmospheric aerosols, NaCl, NH4HSO4, as well as Na2CO3 are estimated and found to depend on relative humidity and characteristics of the coating used. These fell within the range (0.04–2.0)×10–2.  相似文献   

3.
A discharge-flow tube coupled with resonance fluorescence and chemiluminescence detection has been used to investigate the reactions IO + HO2 products (1) and IO + O(3P) I + O2(2), at T = 296 ± 1 K and P = 1.7 - 2 Torr. The rate constants k-1 and k2 have been found to be (7.1 ± 1.6) × 10-11 cm3 molecule-1 s-1 and (1.35 ± 0.15) × 10-10 cm3 molecule-1 s-1, respectively.  相似文献   

4.
We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of exp=(6.0±0.8)×10–2 at 298 K and with a total pressure of 38 Torr for SO2, (5.0±1.0)×10–2 at 297 K and total pressure of 52 Torr for HNO3, (1.5±0.6)×10–3 at 298 K and total pressure of 50 Torr for NO2, (2.4±1.0)×10–2 at 290 K and total pressure of 70 Torr for NH3.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10–1 (298 K) for SO2, (1.1±0.1)×10–1 (298 K) for HNO3, (9.7±0.9)×10–2 (290 K) for NH3, (1.5±0.8)×10–3 (298 K) for NO2 but this last value should not be considered as the true value of for NO2 because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.  相似文献   

5.
Infrared absorption features due to ClO in the lower stratosphere have been identified from groundbased solar absorption spectra taken from Aberdeen, U.K. (57° N, 2° W) on 20 January 1995. A vertical column abundance of 3.42 (±0.47)×1015 molec cm-2 has been derived from 13 independent absorption features in the P and R branches of the (0–1) vibration-rotation band of 35ClO, spanning the spectral region 817–855 cm-1. The observed absorption features are consistent with very high levels of ClO (approximately 2.6 parts per billion by volume (ppbv)) in the altitude range 16–22 km. A comparison of this profile with a 3D chemical transport model profile indicates the observation was made inside the polar vortex and shows good qualitative agreement but the model underestimates the concentrations of ClO. Simultaneous measurements of other species were made including HCl, HF and ClONO2. These columns yield a value for HCl+ClONO2+ClO of 7.02±0.65×1015 molec cm-2. This is lower than the total inorganic chlorine (ClO y ) column of 10.7±1.6×1015 molec cm-2 estimated from mean measured (HCl+ClONO2)/HF ratios together with in-vortex HF measurements. The discrepancy is probably due to significant amounts of the ClO dimer (Cl2O2) in the lower part of the stratosphere. The measurements of highly elevated levels of ClO are used to estimate O3 loss rates at the 400, 475 and 550 K levels making assumptions about the probable distribution of ClO and Cl2O2. These are compared with loss rates derived from ozone sonde data.  相似文献   

6.
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   

7.
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   

8.
The absorption cross-sections of water vapor and oxygen were measured, using a low-pressure radio frequency discharge through traces of hydrogen in argon as a light source for Ly() radiation. The cross-sections are H2O = 1.59 × 10–17 cm2 and O2 = 1.13 × 10–20 + 1.72 × 10–23 for water and oxygen, respectively, where P is the oxygen pressure in units of Torr. Ly() lamps, such as used for this work, are important light sources for photochemical laboratory work and find applications for trace-gas detection in the atmosphere. For the latter application, accurate cross-sections of water vapor and oxygen are needed.  相似文献   

9.
Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO3 radicals and O3 have been measured at 296±2 K. The rate constants (cm3 molecule–1 s–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10–11; camphenilone, (5.15±1.44)×10–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10–10; for reaction with the NO3 radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10–11; and for reaction with O3: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.  相似文献   

10.
Accurate values for the rate and temperature dependence of the reaction NO + O3 NO2 + O2 are important in the chemical modelling of photochemical processes in the atmosphere. Previous measurements have been made at low total pressures and/or with very large mixing ratios relative to those observed in the atmosphere. In this study the reaction rate has been measured using a novel approach under tropospheric conditions of temperature and pressure, and at tens of ppb (mixing ratios of 1 in 108) between 263 and 328 K. The resultant Arrhenius expression (k=Ae-Ea/RT) gives a larger activation energy (Ea/R=1670 ± 100) than the recommended literature value (Ea/R=1400 ± 200), and a larger pre-exponential factor (A=5.1 ± 1.6 × 10-12 cf. recommended A=2.0 × 10-12), but the second-order rate constant at 298 K (1.90 × 10-14 molecules cm-3 s-1 ± 10%) is similar to the recommended value. The results confirm a lack of pressure dependence of the reaction, but were made over too small a range in temperature to address the issue of curvature of the simple Arrhenius expression.  相似文献   

11.
Quantitative infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere are reported. The results have been obtained from the analysis of absorption features of the 9 band at 12.2 m, which have been identified in high-resolution ballon-borne and aircraft solar absorption spectra. The ballon-borne spectral data were recorded at sunset with the 0.02 cm-1 resolution University of Denver interferometer system from a float altitude of 33.5 km near Alamogordo, New Mexico, on 23 March 1981. The aircraft spectra were recorded at sunset in July 1978 with a 0.06 cm-1 resolution interferometer aboard a jet aircraft at 12 km altitude, near 35°N, 96°W. The balloon analysis indicates the C2H6 mixing ratio decreased from 3.5 ppbv near 8.8 km to 0.91 ppbv near 12.1 km. The results are consistent with the colum value obtained from the aircraft data.  相似文献   

12.
The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10–11, 5.7×10–11, 8.04×10–12, 4.9×10–13, and 1.0×10–13 cm3 molecule–1 sec–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm3 molecule–1 s–1: PAN, <7×10–15; PPN, (1.14±0.12)×10–12; HCOOH, (2.00±0.25)×10–13; CH3OOH, (5.70±0.23)×10–11; CH3COCH3, (2.37±0.12)×10–12; and CH3COC2H5, (4.13±0.57)×10–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10–12 cm3 molecule–1 sec–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.  相似文献   

13.
Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO2) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm3molecule–1 s–1) were found: kDMS+Br = (4.9 ±1.0) ×10–14, kDMSO + Br < 6 × 10–14,kDMSO 2 + Br 1 × 10–15,kDMSO + BrO = (1.0 ± 0.3) × 10–14 andkDMSO 2 + BrO 3 × 10–15 (allvalues are given with one on the experimental data). DMSO, SO2, COS, CH3SBr andCH3SO2Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO2and CH3SO2Br were the only sulphur containing products thatwere identified. DMSO, DMSO2 and SO2 were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO2 was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO2 with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.  相似文献   

14.
Barnes  I.  Bastian  V.  Becker  K. H.  Fink  E. H.  Nelsen  W. 《Journal of Atmospheric Chemistry》1986,4(4):445-466
The reactions of OH radicals with SO2, H2S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH3ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO2, H2S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10-12, (5.5±0.8)×10-12 and (1.1±0.2)×10-11 cm3 s-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O2 and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H2O2 at wavelengths greater than 260 nm as the OH source in 1 atm N2, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10-11 cm3 s-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.  相似文献   

15.
The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10–12 cm3 s–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10–17 cm3 s–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.  相似文献   

16.
As a component of the Canadian Arctic Haze Study, held coincident with the second Arctic Gas and Aerosol Sampling Program (AGASP II), vertical profiles of aerosol size distribution (0.17 m), light scattering parameters and cloud particle concentrations were obtained with an instrumented aircraft and ground-based lidar system during April 1986 at Alert. Northwest Territories. Average aerosol number concentrations range from about 200 cm–3 over the Arctic ice cap to about 100 cm–3 at 6 km. The aerosol size spectrum is virtually free of giant or coarse aerosol particles, and does not vary significantly with altitude. Most of the aerosol volume is concentrated in the 0.17–0.50 m size range, and the aerosol number concentration is found to be a good surrogate for the SO4 = concentration of the Arctic haze aerosol. Comparison of the aircraft and lidar data show that, when iced crystal scattering is excluded, the aerosol light scattering coefficient and the lidar backscattering coefficient are proportional to the Arctic haze aerosol concentration. Ratios of scattering to backscattering, scattering to aerosol number concentration, and backscattering to aerosol number concentration are 15.3 steradians, 1.1×10–13 m2, and 4.8×10–15 m2 sr–1, respectively. Aerosol scattering coefficients calculated from the measured size distributions using Mie scattering agree well with measured values. The calculations indicate the aerosol absorption optical depth over 6 km to range between 0.011 and 0.018. The presence of small numbers of ice crystals (10–20 crystals 1–1 measured) increased light scattering by over a factor of ten.  相似文献   

17.
The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10–20 cm2 molecule–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH2OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10–11 and (1.1± 0.3)×10–11 cm3 molecule–1 s–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.  相似文献   

18.
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   

19.
Since 1978, a measuring station has been operated at Cape Point (34°21 S, 18°29 E). In this article, results of measurements of CO, CFCl3, CCl4, O3, N2O and CH4 are presented as monthly means and analyzed with respect to long-term trends and seasonal variations. For CO and CH4, very similar seasonal variations have been observed, indicating strong interrelations between these two gases. For CO and O3, no significant changes of the mean annual concentrations can be established for the observation periods of 10 and 5 years, respectively. The measurements yield a growth rate of 9.1 pptv yr-1 for CFCl3 (1980–1987) and 0.6 ppbv yr-1 for N2O (1983–1987). The concentration increases of CH4 (10.3 ppbv yr-1 for 1983–1987) and of CCl4 (2.1 pptv yr-1 for 1980–1988) are analyzed for temporal changes during the last years.Presented at the Second Conference on Baseline Observations in Atmospheric Chemistry (SABOAC II) in Melbourne, Australia, November 1988.  相似文献   

20.
During April 1986, as part of an international arctic air chemistry study (AGASP-2), ground level observations of aerosol trace elements, oxides of sulphur and nitrogen and particle number size distribution were made at Alert Canada (82.5N, 62.3W). Pollution haze was evident as indicated by daily aerosol number (size > 0.15 m diameter) and SO4 = concentrations in the range 125 – 260 cm–3 and 1.6 – 4.5 g m–3, respectively. Haze and associated acidic gases tended to increase throughout the period. SO2 and peroxyacetylnitrate (PAN) mixing ratios were in the range 140 – 480 and 370 – 590 ppt(v), respectively. About 88% of the total end-product nitrogen was in the form of PAN. In air dried to 2% relative humidity by warming to room temperature, the aerosol mass size distribution had a major mode at 0.3 m diameter and a minor one at 2.5 m. Aerosol mass below 1.5 m was well correlated with SO4 =, K+ and PAN. There was a steady increase in the oxidized fraction of total airborne sulphur and nitrogen oxide throughout April as the sun rose above the horizon and remained above. The mean oxidation rate of SO2 between Eurasia and Alert was estimated as 0.25 – 0.5% h–1. The molar ratio of total nitrogen oxide to total sulphur oxide in the arctic atmosphere (0.67±0.17) was comparable to that in European emissions. A remarkably strong inverse correlation of filterable Br and O3 led to the conclusion that O3 destruction and filterable Br production below the Arctic surface radiation inversion is associated with tropospheric photochemical reactions involving naturally occurring gaseous bromine compounds.  相似文献   

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