Tropospheric transformation products of a series of hydrofluorocarbons and hydrochlorofluorocarbons

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.     

Temperature-dependence of ultraviolet absorption cross-sections of alternative chlorofluoroethanes

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.     

Determination of rate constants for reactions of some hydrohaloalkanes with OH radicals and their atmospheric lifetimes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with partly halogenated alkanes using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units 10^–13 cm³ molecule^–1 s^–1): (8.1 _–1.2 ^+1.5 ) exp{–(1516±53)/T} for CHF₂Cl (HCFC-22); (10.3 _–1.5 ^+1.8 ) exp{–(1588±52)/T} for CH₂FCF₃ (HFC-134a); (11.3 _–1.6 ^+2.1 ) exp{–(918±52)/T} for CHCl₂CF₂Cl (HCFC-122); (9.2 _–2.0 ^+2.5 ) exp{–(1281±85)/T} for CHFClCF₂Cl (HCFC-123a).The atmospheric lifetimes for the substances have been estimated to be 12.6, 12.9, 1.05, and 4.8 years, respectively, and the accuracy of the estimates is discussed.     

Atmospheric trace gas analysis using matrix isolation-fourier transform infrared spectroscopy

A novel cryogenic sampling method combining the matrix isolation technique with FTIR spectroscopy has been developed for atmospheric trace gas analysis. It is applicable to a wide range of molecules with detection limits typically in the 10–50 ppt range. The method is described along with some measurements of N₂O, CFCl₃, CF₂Cl₂, OCS, CS₂, SO₂ and PAN from samples collected at ground level and from an aircraft between 9 and 14 km.     

Ultraviolet absorption cross-sections of chloro and chlorofluoro-methanes at stratospheric temperatures

Absorption cross-sections of nine halomethanes (CCl₄, CHCl₃, CH₂Cl₂, CH₃Cl, CFCl₃, CF₂Cl₂, CF₃Cl, CHFCl₂, and CHF₂Cl), measured between 174 and 250 nm for temperatures ranging from 225 to 295 K, are presented with uncertainties ranging from 2 to 4% and compared with previous determinations made for comparable temperature ranges.The largest temperature effect which takes place near the absorption threshold, decreases the absorption cross-section up to 50% for highly chlorinated methanes, but is negligible for molecules highly stabilized by hydrogen and/or fluorine. Extrapolated values for temperatures of aeronomical interest are presented, as well as parametrical formulas which give absorption cross-section values for given wavelength and temperature ranges.     

Tropospheric degradation products of CH2FCF3 (HFC-134a)

Chlorine atom-initiated photooxidations of CH₂FCF₃ (HFC-134a) in O₂-N₂ diluent were carried out to identify the products formed from the \(CF_3 CHF\dot O\) radical reactions and to determine the product yields as a function of temperature, pressure and O₂ concentration. CF₃C(O)F and HC(O)F were the major ‘first-generation’ products observed, along with smaller yields of C(O)F₂ and, as yet, undetermined yields of CF₃OOOCF₃ and CF₃OOC(O)F. The relative importance of the two major \(CF_3 CHF\dot O\) reaction pathways, is expressed by the rate constant ratio $$k_{O_2 } /k_d = 3.2 \times 10^{ - 25} e^{(3510 \pm 470)/T} cm^3 molecule^{ - 1}$$ The decomposition reaction leading to HC(O)F and ?F₃ radical products is predicted to be the dominant pathway at the Earth's surface while mainly CF₃C(O)F formation will occur at the tropopause.     

European sources of halocarbons and nitrous oxide: Update 1986

Semi-continuous measurements of CFCl₃, CF₂Cl₂, CCl₄, CH₃CCl₃ and N₂O were made at Adrigole, Ireland as part of the Atmospheric Lifetime Experiment (ALE). Clean, baseline air from the Atlantic Ocean was measured approximately 70% of the time; pollution events from Europe, for the remainder. The two final years of ALE data from Adrogole give a five-year record from July 1978 to June 1983. This paper extends previous work on the relative enhancements of trace gases during pollution episodes and presents (1) unambiguous identification of elevated levels of N₂O concurrent with halocarbon pollution events, (2) detection of trends in emission of CH₃CCl₃, (3) discovery of seasonal variations in emission of CF₂Cl₂, CCl₄ and CH₃CCl₃, (4) characterization of typical summer and winter pollution episodes, and (5) identification of weather patterns over Europe that are associated with high concentrations of CFCs at Adrigole. Some of these results assume that CFCl₃ represents a uniform, well buffered source from the continent. The latter two results are particularly useful in the testing and calibration of three-dimensional chemical transport models. Observed enhancements are marginally consistent with estimates of halocarbon use by the chemical industry. The source of nitrous oxide correlated with halocarbons is 0.8 Tg(N)/yr from Europe alone and represents approximately 10% of the global stratospheric loss.     

A study of the gas-phase reaction of carbonyl fluoride with water

Ab initio molecular orbital calculations are carried out to determine the mechanism and energetics of the homogeneous reaction of carbonyl fluoride, CF₂O, with water, H₂O. The reaction is found to proceed through two chemically activated intermediates: CF₂(OH)₂ and FC(O)OH. These intermediates in the CF₂O+H₂O reaction are suggested to be transient. The CF₂(OH)₂ dissociates to form FC(O)OH and HF, and the FC(O)OH subsequently dissociates to form CO₂ and HF. The net reaction is CF₂O+H₂O 2HF+CO₂     

Scenarios of possible changes in atmospheric temperatures and ozone concentrations due to man's activities,estimated with a one-dimensional coupled photochemical climate model

A one-dimensional coupled climate and chemistry model has been developed to estimate past and possible future changes in atmospheric temperatures and chemical composition due to human activities. The model takes into account heat flux into the oceans and uses a new tropospheric temperature lapse rate formulation. As found in other studies, we estimate that the combined greenhouse effect of CH₄, O₃, CF₂Cl₂, CFCl₃ and N₂O in the future will be about as large as that of CO₂. Our model calculates an increase in average global surface temperatures by about 0.6°C since the start of the industrial era and predicts for A.D. 2050 a twice as large additional rise. Substantial depletions of ozone in the upper stratosphere by between 25% and 55% are calculated, depending on scenario. Accompanying temperature changes are between 15°C and 25°C. Bromine compounds are found to be important, if no rigid international regulations on CFC emissions are effective. Our model may, however, concivably underestimate possible effects of CFCl₃, CF₂Cl₂, C₂F₃Cl₃ and other CFC and organic bromine emissions on lower stratospheric ozone, because it can not simulate the rapid breakdown of ozone which is now being observed worldwide. An uncertainty study regarding the photochemistry of stratospheric ozone, especially in the region below about 25 km, is included. We propose a reaction, involving excited molecular oxygen formation from ozone photolysis, as a possible solution to the problem of ozone concentrations calculated to be too low above 45 km. We also estimate that tropospheric ozone concentrations have grown strongly in the northern hemisphere since pre-industrial times and that further large increases may take place, especially if global emissions of NO_x from fossil fuel and biomass burning were to continue to increase. Growing NO_x emissions from aircraft may play an important role in ozone concentrations in the upper troposphere and low stratosphere.     

The heterogeneous formation of N2O in air containing NO2, O3 and NH3

In a nighttime system and under relatively dry conditions (about 15 ppm H₂O), the reaction mixture of NO₂, O₃, and NH₃ in purified air turns out to result in the formation of nitrous oxide (N₂O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm.N₂O is thought to arise through the heterogeneous reaction of gaseous N₂O₅ and absorbed NH₃ at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\]In principle, there is competition between this reaction and that of adsorbed H₂O with N₂O₅, resulting in the formation of HNO₃. At high water concentrations (RH>75%), no formation of N₂O was found. Although the rate constant of adsorbed NH₃ with gaseous N₂O₅ is much larger than that of the reaction of adsorbed H₂O with gaseous N₂O₅, the significance of the observed N₂O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H₂O and NH₃ on a surface. A number of NH₃ and H₂O adsorption measurements on several materials are discussed.     

On the temporal variance of stratospheric trace gas concentrations

The relative variances in stratospheric observations of longlived trace gases CH₄, N₂O, CF₂Cl₂, CFCl₃ show large differences. These differences are greatly reduced when the local mean standard deviation is normalized to the local vertical gradient. This ratio, called ‘equivalent displacement height’ exhibits a characteristic vertical profile which is very similar for all the longlived trace gases, as well as for O₃. With the help of this ratio, it is demonstrated that the variances are essentially due to natural causes, i.e., transport. Using the mixing length hypothesis a theoretical expression for the equivalent displacement height is derived. From it the meridional slope of the mixing surfaces and the mixing length can be calculated as function of the altitude. Additional information is obtained on the variance of that slope. The uncertainty of the measured mean trace gas profiles is defined.     

Secular evolution of the vertical column abundances of CHCIF2 (HCFC-22) in the Earth's atmosphere inferred from ground-based IR solar observations at the Jungfraujoch and at Kitt Peak,and comparison with model calculations

Series of high-resolution infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, between 06/1986 and 11/1992, and at Kitt Peak National Observatory, Tucson, Arizona (U.S.A.), from 12/1980 to 04/1992, have been analyzed to provide a comprehensive ensemble of vertical column abundances of CHCIF₂ (HCFC-22; Freon-22) above the European and the North American continents. The columns were derived from nonlinear least-squares curve fittings between synthetic spectra and the observations containing the unresolved 2v ₆ Q-branch absorption of CHCIF₂ at 829.05 cm^–1. The changes versus time observed in these columns were modeled assuming both an exponential and a linear increase with time. The exponential rates of increase at one-sigma uncertainties were found equal to (7.0±0.35)%/yr for the Junfraujoch data and (7.0±0.23)%/yr for the Kitt Peak data. The exponential trend of 7.0%/yr found at both stations widely separated in location can be considered as representative of the global increase of the CHCIF₂ burden in the Earth's atmosphere during the period 1980 to 1992. When assuming two realistic vertical volume mixing ratio profiles for CHCIF₂ in the troposphere, one quasi constant and the other decreasing by about 13% from the ground to the tropopause, the concentrations for mid-1990 were found to lie between 97 and 111 pptv (parts per trillion by volume) at the 3.58 km altitude of the Jungfraujoch and between 97 and 103 pptv at Kitt Peak, 2.09 km above sea level. Corresponding values derived from calculations using a high vertical resolution-2D model and recently compiled HCFC-22 releases to the atmosphere, were equal to 107 and 105 pptv, respectively, in excellent agreement with the measurements. The model calculated lifetime of CHCIF₂ was found equal to 15.6 years. The present results are compared critically with similar data found in the literature. On average, the concentrations found here are lower by 15–20% than those derived from in situ investigations; this difference cannot be explained by the absolute uncertainty of ±11% assigned presently to the infrared remote measurements.     

Reaction of OH Radicals with Acetone: Determination of the Branching Ratio for the Abstraction Pathway at 298 K and 1 Torr

We have determined the 2-oxo-propyl CH₃C(O)CH₂ (sometimes called 1-methylvinoxy or acetonyl) radical yield for the reaction of acetone with OH radical relative to the 2-oxo-propyl yields for the reactions of F- and Cl atoms with acetone using the Discharge Flow technique. The 2-oxo-propyl radical has been monitored by Laser Induced Fluorescence LIF at short reaction times in the systems: OH + acetone (R1), F + acetone (R2), and Cl + acetone (R3). From these measurements we have deduced the branching ratio for the 2-oxo-propyl radical formation in the title reaction to be in the range 0.8 R 1.     

Kinetics of the Reactions of IO with HO2 and O(3P)

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.     

Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

A high-sensitive technique to detect O(¹S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(¹S) production process from the UV photodissociation of O₃, N₂O, and H₂O₂. The quantum yields for O(¹S) formation from O₃ photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10⁻⁴ and (5 ± 3) × 10⁻⁵, respectively. Based on thermochemical considerations, the O(¹S) formation from O₃ photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(¹S)+O₂(X³Σ_g ⁻). Analysis of the Doppler profile of O(¹S) produced from O₃ photolysis at 193 nm also indicates that the O(¹S) atoms are produced from the spin-forbidden process. In the photolysis of N₂O and H₂O₂ at 193 nm, no discernible signal of O(¹S) atoms has been detected. The upper limit values of the quantum yields for O(¹S) production from N₂O and H₂O₂ photolysis at 193 nm are estimated to be 8 × 10⁻⁵ and 3 × 10⁻⁵, respectively. Using the experimental results, the impact of the O(¹S) formation from O₃ photolysis on the atmospheric OH radical formation through the reaction of O(¹S)+H₂O has been estimated. The calculated results show that the contribution of the O(¹S)+H₂O reaction to the OH production rate is ∼2% of that of the O(¹D)+H₂O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(¹S) at 557.7 nm have also been discussed.     

GHOST – A Novel Airborne Gas Chromatograph for In Situ Measurements of Long-Lived Tracers in the Lower Stratosphere: Method and Applications

A novel fully-automated airborne gas chromatograph for in situmeasurements of long-lived stratospheric tracers hasbeen developed, combining the high selectivity of a megabore PLOTcapillary column with recently developed sampling and separationtechniques. The Gas cHromatograph for theObservation of Stratospheric Tracers (GHOST)has been successfully operated during three STREAM campaigns(Stratosphere TRoposphere Experiment byAirborne Measurement) onboard a Cessna Citation IIaircraft in two different modes: Either N₂O andCF₂Cl₂(CFC-12) or CFC-12 and CFCl₃ (CFC-11) have been measuredsimultaneously, with a time resolution of 2 min for both modes.Under flight conditions the instrument precision (1) forthese species is better than 0.9%, and the accuracy(1) is better than 2.0% of the tropospheric values ofall measured compounds. The detection limits (3) arebelow 28 ppb for N₂O, 14 ppt for CFC-12, and 8 ppt forCFC-11, respectively, i.e., well below 10 % of the troposphericvalues of all measured compounds. Post-mission optimization of thechromatographic separation showed a possible enhancement of thetime resolution by up to a factor of 2, associated with acomparable increase in precision and detection limit. As test ofactual performance of GHOST results from an in-flight N₂Ointercomparison with a tunable diode laser absorptionspectrometer (TDLAS) are presented. They yield an excellentagreement between both instruments. Furthermore, on the basis ofthe hitherto most extensive set of upper tropospheric and lowerstratospheric data, the relative stratospheric N₂2O lifetime isre-assessed. When referenced to the WMO reference CFC-11 lifetimeof 45 ± 7 years an N₂O lifetime of 91 ± 15 yearsis derived, a value substantially smaller than the WMO referencelifetime of 120 years. Moreover, this value implies astratospheric N₂O sink strength of 16.3 ± 2.7 Tg (N)yr^–1 which is 30% larger than previous estimates.     

Stratospheric response to chemical perturbations

The paper presents a coupled chemical-radiative one-dimensional model which is used to assess the steady-state and time-dependent composition and temperature changes in relation to the release in the atmosphere of chemicals such as CO₂, N₂O, CH₄, NO _x and chlorofluorocarbons.The model indicates that a doubling in CO₂ leads to an increase in temperature of 12.7 K near the stratopause and to an increase in total ozone of 3.3% with a local enhancement of 17% at 40 km altitude. Additional release of N₂O leads to an ozone reduction in the middle stratosphere. The reduction in the ozone column is predicted to be equal to 8.8% when the amount of N₂O is doubled. The chemical effect of CH₄ on ozone is particularly important in the troposphere. A doubling in the mixing ratio of this gas enhances the O₃ concentration by 11% at 5 km. The predicted increase of the ozone column is equal to 1.4%. A constant emission of CFCl₃ (230 kT/yr) and CF₂Cl₂ (300 kT/yr) leads to a steady-state reduction in the ozone column of 1.9% compared to the present-day situation. The effect of some uncertainties in the chemical scheme as well as the impact of a high chlorine perturbation are briefly discussed.Finally the results of a time dependent calculation assuming a realistic scenario for the emission of chemical species are presented and analyzed.     

厌氧条件下土壤反硝化气体(N2、N2O、NO)和CO2排放——氦环境培养—气体同步直接测定法的应用初探

反硝化过程是维系闭合氮循环所必需的氮素形态转化环节。土壤反硝化过程速率及产物比的直接测定是研究氮循环过程机理的基础,但却是一个难题。为解决此难题,德国卡尔斯鲁厄技术研究所与中国科学院大气物理研究所最近合作新建了一套通过氦环境培养-气体同步直接测定土壤反硝化气体--氮气（N2）、氧化亚氮（N2O）、一氧化氮（NO）和二氧化碳（CO2）排放的系统和与之配套的三阶段培养方法。为检验该新建系统和配套方法测定土壤反硝化过程的准确性和可靠性,以华北地区广泛分布的盐碱地农田土壤（采自山西运城）为研究对象开展实验室培养试验,在初始可溶性有机碳（DOC）供应比较充足约300 mgC kg–1干土（d.s.）的条件下,测试了不同初始土壤硝态氮含量水平（10、100 mgN kg–1d.s.左右,分别表示为10N和100N）的反硝化气体和CO2排放过程。结果显示：100N的反硝化速率（定义为N2、N2O 和NO 排放速率之和）显著高于10N 处理（统计检验显著水平p＜0.01）;两个处理的反硝化产物均以N2为主（质量比分别占77%和75%）,产物的NO/N2O摩尔比分别为1.2和1.5,N2O/N2摩尔比均为0.19;土壤反硝化气体动态排放速率及相关指标的测定结果表明,培养土壤中消失的硝态氮被回收81%～87%,培养前后的氮平衡率达92%～95%。因此,该新建方法测定土壤反硝化速率和产物比的结果具有很好的可靠性,为定量研究土壤反硝化过程提供了有效的直接测定手段。研究中检测到的土壤反硝化产物NO/N2O摩尔比大于1,不同于以往用液体培养基纯培养反硝化细菌得出的NO/N2O摩尔比远小于1的结论。这意味着,不能用NO/N2O摩尔比小于1与否来推断土壤排放的N2O和NO是主要来源于反硝化作用还是硝化作用。     

Traffic aerosols (18 nm particle size 18 μm) source apportionment during the winter period

In November 2004–January 2005, a micro orifice uniform deposit impactor (MOUDI) and a Nanometer (nanometer)-MOUDI were used in the center of Taiwan to measure particle size (18 nm particle size 18 μm) distributions of atmospheric aerosols at a traffic site during the winter period. The average Mass in Media Aerodynamic Diameter (MMAD) of suspended particles is 0.99 μm this study. As for the ultra fine and nanometer (nanometer) particle mode, the composition order for these major ions species was SO₄²⁻ NH₄⁺ NO₃⁻ Mg²⁺ Ca²⁺ Na⁺ K⁺ Cl⁻. An ion Chromatography (DIONEX-100) was used to analyze major anion species, Cl⁻, NO₃⁻, SO₄²⁻ and cation species, NH₄⁺Na⁺, K⁺, Ca²⁺Mg²⁺. Their concentrations were also extracted from various particles size modes (nanometer (nanometer), ultra fine, fine and coarse). The results obtained in this study also indicated that the average portions for the major ionic species (SO₄²⁻, NH₄⁺ and Mg²⁺) in the nanometer (nanometer), ultra fine, fine and coarse particulate modes are about 34%, 37%, 63% and 30%, respectively at this traffic sampling site during the winter period.     

CH4和N2O的辐射强迫与全球增温潜能

CH₄和N₂O作为主要温室气体,自工业革命以来排放量急剧增加,已经被列入《京都议定书》要求控制它们的排放。本文利用高光谱分辨率的辐射传输模式,计算了CH₄、N₂O在晴空大气和有云大气条件下的瞬时辐射效率和平流层调整的辐射效率,以及它们的全球增温潜能(GWP)和全球温变潜能(GTP),并根据模式结果拟合了CH₄和N₂O的辐射强迫的简单计算公式。本文的研究表明:CH₄和N₂O在有云大气下的平流层调整的辐射效率分别为4.142×10-4 W m-2 ppb-1和3.125×10-3 W m-2 ppb-1 (1ppb=10-9),经大气寿命调整后的辐射效率分别为3.732×10-4 W m-2 ppb-1和2.987×10-3 W m-2 ppb-1,与IPCC(2007)的相应结果高度一致。CH₄和N₂O 100年的全球增温潜能GWP分别为16和266;100年的脉冲排放的全球温变潜能GTPP分别为0.24和233;持续排放的全球温变潜能GTPS分别为18和268。它们在未来全球变暖和气候变化中,影响仅次于CO₂,仍然起着非常关键的作用。