OH-initiated degradation of several hydrocarbons in the atmosphere simulation chamber SAPHIR

Degradation of isoprene, m-xylene, n-octane, propene, and methacrolein by hydroxyl radicals has been studied in the simulation chamber SAPHIR under burden of trace gases as they are typical for the moderately polluted planetary boundary layer. Measured time series of the hydrocarbon mixing ratios and the OH concentrations were used to determine the rate constants. The hydrocarbons were measured with gas chromatography and proton transfer reaction mass spectrometry. OH was measured with the Jülich DOAS (differential optical absorption spectroscopy) instrument. In all cases except methacrolein good agreement was found with the reference rate constants taken from the Master Chemical Mechanism (MCM3.1). The data for methacrolein are consistent with the results of Karl et al. (J. Atmos. Chem 55, 2006, doi:) who reported a 12% smaller value. The degradation of hydrocarbons provides an independent method to analyse precision and accuracy of the OH measurements. A precision of better than 4% over a period of nearly 4 months was found. The accuracy is within the limitations given by the light absorption cross section of OH. Both results are consistent with earlier results by Hausmann et al. (J. Geophys. Res. 102:16011–16022, 1997).     

Reactions of Cl Atoms with Selected VOCs: Kinetics, Products and Mechanisms

The reactions of isoprene, MBO (2-methyl-3-buten-2-ol) and toluene with chlorine atoms have been studied at 298 ± 5 K and 740 ± 5 Torr with the use of FTIR spectroscopy. Major products of the isoprene-Cl reaction and of the MBO-Cl reaction have been identified and quantified, and reaction mechanisms have been tentatively proposed in order to explain the products formed. The reaction between isoprene and Cl atoms yields mainly HCl, formyl chloride, formic acid, methylglyoxal (pyruvic aldehyde), CO and CO2, while the MBO-Cl reaction forms acetone, HCl, formyl chloride, formic acid, CO, CO2. As products from the reaction between toluene and Cl we identified and quantified HCl and benzaldehyde. The rate constants for the reactions of isoprene and toluene with Cl atoms have also been determined using a relative rate method. The measured values are: kisoprene = (5.5 ± 1.0) × 10–10 cm3 molecule–1 s–1 and ktoluene = (5.6 ± 1.3) × 10–11 cm3 molecule–1 s–1. Atmospheric lifetimes have been estimated from these values.     

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C₅ isoprene hydroxy carbonylsC₅H₈O₂, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C₅ carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C₅ hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHO_x in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.     

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH

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.     

Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure

Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique.The following rate coefficients (in units of 10^-12 cm³ molecule^-1 s^-1) were obtained: 1,2-propandiol dinitrate, <0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; -nitrooxyacetone, <0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50.The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.     

Laboratory Studies of the Hydrogen Kinetic Isotope Effects (KIES) of the Reaction of Non-Methane Hydrocarbons with the OH Radical in the Gas Phase

The hydrogen kinetic isotope effects (KIEs) of the reactions of 15 non-methane hydrocarbons (NMHCs) with the OH radical were measured at 298 ± 2 K. The measurements were made using NMHCs without artificial isotopic labeling or enrichment. The following average hydrogen KIE values, in per mil (), were obtained: 29.8 ± 2.1 (toluene),51.6 ± 2.1 (n-butane), 97.3± 12.5 (i-butane), 63.2 ± 5.9 (cyclopentane), 10.5 (p-xylene), 26.8 ± 3.5 (ethylbenzene), 65.9± 7.0 (n-pentane), 79.5 ± 9.6 (cyclohexane), 52.8 ± 5.0(n-hexane), 38.9 ± 7.8 (n-heptane), 33.4 ± 3.1 (n-octane), 29.6 ± 1.6(n-nonane), and 29.0 ± 5.3 (n-decane). The KIEs for reactions of two alkenes (cyclohexene and 1-heptene) could not be determined accurately due to interference from reaction with ozone, but nevertheless the results clearly show that the KIEs for reaction of alkenes with OH are significantly lower than those for saturated hydrocarbons. The KIEs for reaction of alkanes are smaller than isotope effects reported in literature for the reactions of NMHCs artificially labeled with deuterium. The main reason for this difference is the reduced probability for reaction at a labeled site for compounds with close to natural deuterium abundance, although some impact of secondary isotope effects cannot be ruled out. Still, the KIEs for NMHCs with natural or close to natural abundance of deuterium are of sufficient magnitude to allow determination of the extent of chemical processing of hydrocarbons in the atmosphere using methods analogous to stable carbon KIE studies. Furthermore, it is shown that combining stable hydrogen and stable carbon isotope ratio data has the potential to also provide valuable information regarding the stable isotope ratios of emissions, and specifically to test one of the key assumptions of the stable isotope hydrocarbon clock, the absence of significant variations of the stable isotope ratio for the emitted NMHCs.     

Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes

The formation yields of nine carbonyl products are reported from the gas-phase OH radical-initiated reactions (in the presence of NO _x ) and the O₃ reactions with seven monoterpenes. The products were identified using GC/MS and GC-FTIR and quantified by GC-FID analyses of samples collected on Tenax solid adsorbent cartridges. The identities of products from camphene, limonene and -pinene were confirmed by comparison with authentic standards. Sufficient quantities of products from the 3-carene, limonene, -pinene, sabinene and terpinolene reactions were isolated to allow structural confirmation by proton NMR spectroscopy. The measured total carbonyl formation yields ranged from non-detectable for the OH radical reaction with camphene and the O₃ reactions with 3-carene and limonene to 0.5 for the OH radical reaction with limonene and the O₃ reaction with sabinene.     

Advances in studies of the middle and upper atmosphere and their coupling with the lower atmosphere

Recent advances in studies of the middle and upper atmosphere and their coupling with the lower atmosphere in China are briefly reviewed. This review emphasizes four aspects: (1) Development of instrumentation for middle and upper atmosphere observation; (2) Analyses and observation of middle and upper atmosphere; (3) Theoretical and modeling studies of planetary wave and gravity wave activities in the middle atmosphere and their relation to lower atmospheric processes; (4) Study on the coupling between the stratosphere and the troposphere.     

Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

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.     

低层垂直风切变和冷池相互作用影响华北地区一次飑线过程发展维持的数值模拟

利用三维数值云模式和雷达资料四维变分同化技术,通过对6部新一代多普勒天气雷达观测资料进行快速更新循环同化和云尺度数值模拟,初步分析了2009年7月23日发生在华北地区的一次飑线过程的低层动力和热动力影响机制。结果表明,这次飑线过程处在低层中等强度切变的环境条件下,低层环境垂直风切变和冷池相互作用是本次飑线过程维持发展和传播的关键机制。在飑线发展的初期,低层垂直风切变较强,但冷池偏弱,冷池传播速度(C)和垂直于飑线的低层切变分量(ΔU)的比值C/ΔU<1,飑线回波前倾。而此时环境热力条件(对流有效位能较高和自由对流高度较低)对飑线的发展加强起到了积极作用,克服了这种低层切变和冷池不平衡所形成的不利条件。在飑线的加强和成熟阶段,由于对流降水使冷空气不断下沉,从而导致冷池快速加强,使低层切变和冷池强度逐渐达到近似平衡状态(C/ΔU≈1),低层大气处于最强的垂直抬升状态,飑线发展最为强盛,飑线回波直立。随着时间的推移,降水累积效应导致冷池强度明显大于低层切变强度(C/ΔU>1),不利的形势导致飑线逐渐趋于消散,飑线回波明显变宽、后倾,回波顶高显著下降。对模拟结果的定性分析和定量计算均表明,影响这次飑线过程发展维持的低层垂直风切变和冷池相互作用机制与Rotunno和Weisman等用来解释飑线发展演变的RKW理论一致。另外,模拟结果显示,低层0—3km风切变对飑线的发展维持最为重要,但是0—6km的中层风切变也有正面作用,特别是在飑线发展旺盛阶段,应该考虑其影响。     

低层垂直风切变和冷池相互作用影响华北地区一次飑线过程发展维持的数值模拟

春夏季我国华南地区水汽充足,飑线可以在短时间尺度迅速增长。为探究水汽含量对飑线升尺度增长过程的影响,利用WRF模式对2020年5月11日华南地区的一次飑线进行数值模拟,分析华南飑线系统升尺度增长机制,并研究不同层次水汽的变化对其强度及结构的影响。分析显示此次飑线发生在“上干下湿”的不稳定层结中,存在高空急流与低层切变相互配合。模拟结果显示,前期广东省西南部的最大对流有效位能(MCAPE)较大,利于不稳定能量在此积累,同时此处的低层垂直风切变较大,飑线线性结构能更好地维持,随后南移与暖区对流合并,尺度进一步增长。水汽试验表明,MCAPE值主要受低层水汽的影响,低层水汽越多,雷暴高压更强,较大的MCAPE值及低层垂直风切变使得对流后向新生尺度增长,维持时间更长。减小中层水汽后地面强降水减少,对流强度减弱且很快分散为对流单体,但当飑线移动到MCAPE值大值区时又一次发展形成线性结构。因此增加低层水汽或减少中层水汽后的环境利于对流新生,但减少中层水汽后中层干空气相对而言使得线性结构难以维持。进一步研究飑线内部结构表明,垂直运动及后向入流也能影响飑线的尺度增长,此次对流系统中较强的后向入流增强了上升运动,同时形成向前的出流,造成地面大风天气。增强低层水汽后,对流后部层状云区范围更大,系统中的上升运动更强,且保持垂直,利于对流长时间维持;减小中层水汽后,对流强度减弱,回波顶高度降低。发展阶段后向入流增强,干冷空气迅速下沉,地面冷池增强,向前的出流形成大风天气。