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1.
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2.
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。  相似文献   

3.
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   

4.
An experimental study involving the Mainz vertical wind tunnel is described where the rate of SO2 removed from the air by freely suspended water drops was measured for SO2 concentrations in the gas phase ranging between 50 and 500 ppb, and for various H2O2 concentrations in the liquid phase. In a first set of experiments, the pH inside the SO2 absorbing drops was monitored by means of colour pH indicators added to the drops. In a second set of experiments, the amount of SO2 scavenged by the drops was determined as sulfate by an ionchromatograph after the drops had been removed from the vertical air stream of the wind tunnel after various times of exposure to SO2. The results of our experimental study were compared with the theoretical gas diffusion model of Walcek and Pruppacher which was reformulated for the case of SO2 concentrations in the ppbv(v) range for which the main resistance to diffusion lies in the gas phase surrounding the drop. Excellent agreement between experiment and theory was obtained. Encouraged by this agreement, the theory was used to investigate the rate of sulfate production inside a drop as a function of pH. The sulfate production rate, which includes transport and oxidation, was compared with the production rate based on bulk equilibrium, as cited in the literature.  相似文献   

5.
Gas exchange experiments were conducted in the tropical Atlantic Ocean during a ship expedition with FS Meteor using a small rubber raft. The temporal change of the mixing ratios of CO, H2, CH4 and N2O in the headspace of a floating glass box and the concentrations of these gases in the water phase were measured to determine their transfer velocities across the ocean-atmosphere interface. The ocean acted as a sink for these gases when the water was undersaturated with respect to the mixing ratio in the headspace. The transfer velocities were different for the individual gases and showed still large differences even when normalized for diffusivity. Applying the laminar film model, film thicknesses of 20 to 70 m were calculated for the observed flux rates of the different gas species. When the water was supersaturated with respect to atmospheric CO, H2, CH4 and N2O, the transfer velocities of the emission process were smaller than those determined for the deposition process. In case of H2 and CH4, emission was even not calculable although, based on the observed gradient, the laminar film model predicted significant fluxes at the air-sea interface. The results are interpreted by destruction processes active within the surface microlayer.  相似文献   

6.
A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO2 was adsorbed as N2O4 approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO2, NO, O2 and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO2, NO and O2 were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO2 was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N2O4. NO was supposed to be a predissociation product from the electronically excited NO2 prepared through the photodissociation of N2O4.  相似文献   

7.
The photochemical oxidation of SO2 in the presence of NO and C3H6 was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO2 concentration were constant, SO4 2- concentration, derived from the total volume of aerosol produced, peaked when [C3H6]/[NO] was approximately 6.0. Another increase im SO4 2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO2 oxidation mechanisms. At low [C3H6]/[NO] ratios, the processes proceed via the HO–SO2 reaction, while at high ratios the O3–C3H6 adduct is assumed to oxidize SO2 to produce SO4 2- aerosols.  相似文献   

8.
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.  相似文献   

9.
The kinetics of the reaction of NO2 with O3 have been investigated at 296 K, using UV absorption spectroscopy to monitor decay of NO2 or O3 and infrared laser absorption spectroscopy to monitor formation of the reaction product N2O5. The results both for the rate coefficient at 296 K (k 1=3.5×10-17 cm3 molecule-1 s-1) and the reaction stoichiometry (NO2/O3=1.85±0.09) are in good agreement with previous studies, confirming that the two step mechanism involving formation of symmetrical NO3 as an intermediate is predominant.% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaaeOmaaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaa% bodaaeqaaOWaa4ajaSqaaaqabOGaayPKHaGaaeOtaiaab+eadaWgaa% WcbaGaae4maaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaabkdaaeqa% aaaa!41D7!\[{\text{NO}}_{\text{2}} + {\text{O}}_{\text{3}} \xrightarrow{{}}{\text{NO}}_{\text{3}} + {\text{O}}_{\text{2}} \]% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaae4maaqabaGccqGHRaWkcaqGobGaae4tamaaBaaa% leaacaqGYaaabeaakiabgUcaRiaab2eadaGdKaWcbaaabeGccaGLsg% cacaqGobWaaSbaaSqaaiaabkdaaeqaaOGaae4tamaaBaaaleaacaqG% 1aaabeaakiabgUcaRiaab2eaaaa!4464!\[{\text{NO}}_{\text{3}} + {\text{NO}}_{\text{2}} + {\text{M}}\xrightarrow{{}}{\text{N}}_{\text{2}} {\text{O}}_{\text{5}} + {\text{M}}\]A possible minor role for the unsymmetrical ONOO species is suggested to account for the lower-than-expected stoichiometry factor. The importance of this reaction in the oxidation of atmospheric NO2 is discussed.  相似文献   

10.
A three-dimensional model of the global ammonia cycle   总被引：16，自引：0，他引：16  
Using a three-dimensional (3-D) transport model of the troposphere, we calculated the global distributions of ammonia (NH3) and ammonium (NH 4 + ), taking into account removal of NH3 on acidic aerosols, in liquid water clouds and by reaction with OH. Our estimated global 10°×10° NH3 emission inventory of 45 Tg N-NH3 yr– provides a reasonable agreement between calculated wet NH 4 + deposition and measurements and of measured and modeled NH 4 + in aerosols, although in Africa and Asia especially discrepancies exist.NH3 emissions from natural continental ecosystems were calculated applying a canopy compensation point and oceanic NH3 emissions were related to those of DMS (dimethylsulfide). In many regions of the earth, the pH found in rain and cloud water can be attributed to acidity derived from NO, SO2 and DMS emissions and alkalinity from NH3. In the remote lower troposphere, sulfate aerosols are calculated to be almost neutralized to ammonium sulfate (NH4)2SO4, whereas in the middle and upper troposphere, according to our calculations, the aerosol should be more acidic, as a result of the oxidation of DMS and SO2 throughout the troposphere and removal of NH3 on acidic aerosols at lower heights. Although the removal of NH3 by reaction with the OH radical is relatively slow, the intermediate NH2 radical can provide a substantial annual N2O source of 0.9 –0.4 +0.9 Tg, thus contributing byca. 5% to estimated global N2O production. The oxidation by OH of NH3 from anthropogenic sources accounts for 10% of the estimated total anthropogenic sources of N2O. This source was not accounted for in previous studies, and is mainly located in the tropics, which have high NH3 and OH concentrations. Biomass burning plumes, containing high NO x and NH3 concentrations provide favourable conditions for gas phase N2O production. This source is probably underestimated in this model study, due to the coarse resolution of the 3-D model, and the rather low biomass burning NH3 and NO x emissions adopted. The estimate depends heavily on poorly known concentrations of NH3 (and NO x ) in the tropics, and uncertainties in the rate constants of the reactions NH2 + NO2 N2O + H2O (R4), and NH2 + O3 NH2O + O2 (R7).  相似文献   

11.
An extention of our previous theory for trace gas absorption into freely-falling cloud and raindrops is presented. This theory describes the convective diffusion of a trace gas through air and into a water drop with internal circulation, the drop falling at its terminal velocity. Using flow fields for the circulating water inside and for the moving air outside the drop, obtained by numerical solutions to the Navier—Stokes equation of motion, we numerically solved the convective diffusion equation to determine the uptake of SO2 by water drops of various sizes, time exposure to the gas phase, and concentration of SO2 in the gas phase. It was found that for drops of radius larger than 1 mm and relatively low gas concentrations (10 ppb (v)), resistance to gas diffusion lies mainly in the gas phase; while for drops of radius less than 500 m and gas concentrations larger than those found in the atmosphere (1% (v)), the resistance to diffusion lies primarily in the liquid phase. With drop sizes and gas concentrations between these limits, the rate of SO2 uptake is controlled by a coupled resistance to diffusion inside and outside the drop. In addition to our general model, a simplified version was formulated which allows considerable savings in computer time for evaluation and improved ease of handling without significant loss of accuracy. A comparison between our simplified model and that of Barrie (1978) shows that the boundary-layer approach of Barrie may be a useful alternate approach to estimating trace gas absorption by water drops, provided appropriate values are chosen for the thickness of the boundary layers involved.  相似文献   

12.
The rate of formation of N2O via the thermochemically favourable reaction of NO3(A2E) with N2, which would represent an additional source of stratospheric N2O and therefore NOx, has been investigated. Mixtures of NO2+O3 in synthetic air were photolysed at 662 nm. No evidence was found for the production of N2O via this pathway, the upper limit for the quantum yield of nitrous oxide formation being % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% GaeqOXdy2aaSbaaSqaamaaBaaameaadaWgaaqaamaaBaaabaGaamOt% amaaBaaabaGaaGOmaiaad+eaaeqaaaqabaaabeaaaeqaaaWcbeaatu% uDJXwAK1uy0HMmaeHbfv3ySLgzG0uy0HgiuD3BaGqbaOGae8hzIqOa% aGimaiaac6cacaaI2aGaaiyjaaaa!4E60!\[\phi _{_{_{_{N_{2O} } } } } \le 0.6\% \]. However, a dark conversion of NOx to N2O was observed and is attributed tentatively to a heterogeneous reaction on the wall of the reaction vessel. This process, although most likely to be insignificant in the atmosphere, needs to be taken into consideration in laboratory investigations or field studies of N2O emission or deposition.  相似文献   

13.
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.  相似文献   

14.
An experimental investigation of the simultaneous absorption of NH3 and SO2 from the ambient atmosphere by freely falling water drops has been carried out in the Mainz vertical wind tunnel. The experimental results were found to be in good agreement with the results derived from computations with the Kronig-Brink convective diffusion model and also with a model which assumes a drop to be well mixed at all times. Encouraged by this agreement, these computation schemes for the uptake of gas by single drops where incorporated in a pollution washout model with realistic SO2, NH3 and CO2 gas profiles. This model allows an entire raindrop size distribution to fall through a gas layer. The results of this plume-model show that the SO2 uptake is strongly dependent on the NH3 concentration in the atmosphere and on the rainrate. We also find that the small drops contribute more towards the washout of these gases. In the case of simultaneous presence of NH3 and SO2, desorption of these gases is negligible.  相似文献   

15.
For the purpose of testing our previously described theory of SO2 scavenging a laboratory investigation was carried out in the UCLA 33 m long rainshaft. Drops with radii between 250 and 2500 m were allowed to come to terminal velocity, after which they passed through a chamber of variable length filled with various SO2 concentrations in air. After falling through a gas separating chamber consisting of a fluorocarbon gas the drops were collected and analyzed for their total S content in order to determine the rate of SO 2 absorption.The SO2 concentration in air studied ranged between 1 and 60% (v). Such relatively large concentrations were necessary due to the short times the drops were exposed to SO2 in the present setup. The present experimental results were therefore not used to simulate atmospheric conditions but rather to test our previously derived theory which is applicable to any laboratory or atmospheric condition. Comparison of our studies with the results from our theory applied to our laboratory conditions led to predicted values for the S concentration in the drops which agreed well with those observed if the drops had radii smaller than 500 m. In order to obtain agreement between predicted and observed S concentrations in larger drops, an empirically derived eddy diffusivity for SO2 in water had to be included in the theory to take into account the effect of turbulent mixing inside such large drops.In a subsequent set of experiments, drops initially saturated with S (IV) were allowed to fall through S-free air to determine the rate of SO 2 desorption. The results of these studies also agreed well with the results of our theoretical model, thus justifying the reversibility assumption made in our theoretical models.In a final set of experiments, the effects of oxidation on SO2 absorption was studied by means of drops containing various amounts of H2O2. For comparable exposure times to SO2, the S concentration in drops with H2O2 was found to be up to 10 times higher than the concentration in drops in which no oxidation occurred.  相似文献   

16.
This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO2 and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO2, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO2 data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO3. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×109 molecs cm-2 s-1. The dominant sourceof BL SO2 was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO2 was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10-5 s-1. In contrast to the DMSand SO2 simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.  相似文献   

17.
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   

18.
采用漂浮通量箱法和扩散模型法同步地观测了模拟内陆水体在不同条件下的CH4和N2O的水-气交换通量,旨在比较两类方法取得结果的异同。结果显示:这两类方法所测得的绝大多数CH4排放通量都与水中溶解氧呈显著线性负相关(显著性系数P0.001)。同时N2O排放通量与表层水温及水中铵态氮、硝态氮、溶解碳和溶解氧的关系可用包含所有上述水环境因素的Arrhenius动力学方程来表达,这些因素可以共同解释86%~90%的N2O通量变化(P0.0001),且不同方法测定的N2O通量的表观活化能和对表层水温的敏感系数分别介于47~59 kJ mol-1和1.92~2.27之间;扩散模型法所获得的CH4和N2O通量分别是箱法测定值的13%~175%和15%~240%,差异程度因模型而异;不同模型取得通量间相差20%~1200%,平均相差2.3倍。上述结果表明:仅用一种模型方法来取得CH4或N2O排放通量易形成较大偏差;不同扩散模型法和箱法测定的通量在反映CH4和N2O排放的内在规律方面具有一致性,但它们对真实气体通量的测量是否都存在不同程度的系统误差,尚需进一步研究。  相似文献   

19.
We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H2O2, NH3 and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H2O2 and NH3 are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H2O2 is driven by co-condensation with water vapour onto ice crystals while NH3 uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH4+ in the ice could explain this result. Finally, it appears that the H2O2–SO2 reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.  相似文献   

20.
Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H2O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO2 (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C9-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH2OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC9-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H2O. The atmospherically important reaction of thestabilised C9-Criegee intermediate with H2Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H2O2(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C9-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.  相似文献   

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