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1.
Three-dimensional excitation–emission matrix (EEM) fluorescence spectra of water-soluble organic compounds (WSOC) from aerosol samples were measured and compared with those reported in the literature for natural dissolved organic matter. The EEM profiles of the WSOC presented three characteristic excitation/emission (Exc/Em) peaks: 240/405 nm, 310/405 nm and 280/340 nm. The fluorescence intensities at Exc/Em240/405 nm and Exc/Em310/405 nm are located at wavelengths shorter than those reported for aquatic humic substances, indicating a smaller content of both aromatic structures and condensed unsaturated bond systems in the WSOC fraction. The EEM profiles of fractions obtained by the isolation procedure of the WSOC by the XAD resins showed that a fractionation has occurred and the XAD-8 eluate is highly representative of the total WSOC of collected aerosol. Synchronous scan spectra were more detailed than conventional fluorescence emission spectra, appearing more suitable for studying multicomponent samples such as the WSOC from atmospheric aerosols.  相似文献   

2.
Significant quenching of fluorescence by Cu in rainwater samples from southeastern North Carolina demonstrates that chromophoric dissolved organic matter (CDOM) is an effective ligand for Cu in rainwater. A strong inverse correlation between the decrease in fluorescence upon Cu addition and CDOM abundance suggests the presence of excess binding sites for Cu in high CDOM samples. Electroanalytical studies indicate that CDOM extracted from C18 cartridges formed Cu complexes with concentrations and conditional stability constants similar to ligands found in ambient rainwater. When authentic rainwater samples were photolyzed with simulated sunlight both photoproduction and photodestruction of ligands were observed, suggesting the photochemical response of Cu-complexing ligands in rainwater is the result of two competing reactions. The rate of CDOM photobleaching was directly related to changes in strong ligands (KCuL ∼ 1015) whereas weaker ligands (KCuL < 1013) were not correlated, suggesting the photolabile CDOM resides in the strong ligand class. A photolysis study comparing filtered and unfiltered rainwater samples indicated that Cu-complexing ligands adsorbed onto or otherwise associated with particles are photodegraded much more rapidly than dissolved ligands. Photolysis with UV radiation appears to be most effective at engendering changes in Cu ligands, however a significant photochemical response was also observed when samples were exposed to photosynthetically active radiation with wavelengths greater than 400 nm. Results from this study demonstrate that complexation of Cu by CDOM has important ramifications for controlling both the speciation of the metal and the reactivity of CDOM in rainwater.  相似文献   

3.
Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH4+ and ~32% NO3– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH4+ and NO3− in rainwater ranged from 1.7–55 μmol L−1 and 0.16–18 μmol L−1, respectively, accounting for ~87% by NH4+ and ~13% by NO3− of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH4+ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH4+ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH3) by marine biological activity from the ocean could become a significant source of NH4+ over the South Pacific. While NO3− was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH4+ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m−2 d−1, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.  相似文献   

4.
Summary This paper presents a study of the sensibility of the Penman-Monteith evapotranspiration model to climatic (available energy and vapour pressure deficit) and parametric (aerodynamic and canopy resistances, r a and r c respectively) factors in a semi-arid climate, for crops in contrasting water status (well irrigated and under water stress) and of different heights. Three experiments were carried out in southern Italy on reference grass (≈ 0.1 m), grain sorghum (≈ 1 m) and sweet sorghum (≈ 3 m). For this analysis the sensitivity coefficients, taken as hourly means, were evaluated during the growth season when the crops completely covered the soil. The relative errors on evapotranspiration were also evaluated for r a and r c . The results showed that, for reference grass, available energy and aerodynamic resistance play a major role. For crops under water stress the most important term to evaluate is canopy resistance. For a tall crop, as sweet sorghum, the role of the vapour pressure deficit is fundamental, both when the crop is in good water status and under water stress. Received July 14, 1997 Revised February 5, 1998  相似文献   

5.
Concentrations of manganese in 56 rain events in Wilmington, NC, USA rainwater from April 1, 2005 to March 31, 2006 were 11 ± 3 nM for dissolved Mn and 1.2 ± 0.4 nM for particulate Mn. Concentrations of both forms of Mn were higher in terrestrial storms relative to marine events. This observation along with the positive correlation of Mn with pollutant indicators suggests anthropogenic inputs to rain at this location, as has been observed at other locations. The ratio of Mnpart/Mndiss was threefold larger in summer relative to winter rain, which matched the increase of particulate to dissolved Fe in rainwater suggesting influence of Saharan dust during the summer. Like Fe in rain, Mn undergoes photoreduction in rainwater, which has also been shown to be important in Mn cycling in seawater. The flux of Mn removed from the atmosphere via wet deposition is 1.5 × 10−5 moles m−2 yr−1 at this location, which is approximately twice the flux reported from two rainwater studies conducted in the early 1980s on Bermuda. Atmospheric input of Mn to the oceans is important because Mn like Fe is an essential and potentially limiting nutrient. Experiments mixing authentic rainwater and seawater demonstrate that rainwater dissolved Mn does not rapidly precipitate in seawater suggesting wet deposition is an important source of soluble, stable Mn to surface seawater.  相似文献   

6.
The uptake of water vapor on MgCl2×6H2O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H2O to salt uptake data were obtained from the kinetics of H2O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H2O on MgCl2×6H2O films: γ 0 (MgCl2) = (6.5 ± 1.0) × 10−6 exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H2O adsorption on NaCl was found to be much lower than on MgCl2×6H2O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10−6 at T = 300 K. The results show that the rate of H2O adsorption to salt surfaces is drastically dependent on the salt sample composition.  相似文献   

7.
Summary ?Above orographically structured terrain considerable differences of the regional wind field may be identified during large-scale extreme wind events. So far, these regional differences could not be resolved by climate models. To determine the relationships between large-scale atmospheric conditions, the influence of orography, and the regional wind field, data measured in the upper Rhine valley within the framework of the REKLIP Regional Climate Project were analyzed and calculations were made using the KAMM mesoscale model. In the area of the upper Rhine valley, ratios of the wind velocity in the Rhine valley at 10 m above ground level, νval, and the large-scale flow velocity, νlar, are between νval/νlar ≈ 0.1 and νval/νlar ≈ 1. The νval/νlar ratio exhibits a strong dependence on thermal stratification, δ, and decreases from νval/νlar ≈ 1 at δ = 0 K m−1 to νval/νlar ≈ 0.2 at δ = 0.0075 K m−1. In areas, where the lateral mountainous border of the Rhine valley is interrupted, the νval/νlar ratio increases again with increasing stability or decreasing Froude number. This is obviously due to flow around the Black Forest under stable stratification. It is demonstrated by model calculations that a complex wind field develops in the Rhine valley at small Froude numbers (Fr < 1) irrespective of the direction of large-scale flow. The νval/νlar ratio is characterized by small values in the direct lee side (νval/νlar ≈ 0.2) and high values on the windward side of the lateral mountainous border of the Rhine valley (νval/νlar ≈ 0.8). Received October 22, 2001; revised June 18, 2002; accepted June 23, 2002  相似文献   

8.
Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10−5 ± 2.8 × 10−5 s−1 and 1.9 × 10−4 ± 1.6 × 10−5 s−1, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH4 +, Cl−, SO4 2−, and NO3 − were found to be higher than those of Na+, K+, and Ca2+ of oceanic and crustal origins. This enrichment implied that gaseous species NH3, HCl, and HNO3 could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.  相似文献   

9.
A Laser Induced Fluorescence (LIF) instrument has been developed to detect iodine monoxide (IO) radicals in the atmosphere. An all solid-state Nd:YAG pumped Ti:Sapphire laser operating at approximately 445 nm was used to excite the (2,0) band of the IO A2Π3/2 ← X2Π3/2 electronic transition, with off-resonance fluorescence in the (2,5) band detected at 521 nm. The sensitivity of the instrument was determined by calibration. IO (between 10 and 150 pptV) was generated following the 184.9 nm photolysis of N2O/CF3I/N2 mixtures with O3 actinometry used to determine the photolysis flux. The detection limit was determined to be 0.3 pptV for a 300 s integration period, with an uncertainty of 23% (1σ). The instrument was deployed in August/September 2006 during the RHaMBLe (Reactive Halogens in the Marine Boundary Layer) campaign in Roscoff, France. Located on a small jetty, a few metres from the water’s edge at high tide, the instrument measured significant levels of IO on 11 days, with a maximum of 27.6 ± 3.2 pptV observed on one day (averaged over 10 s) representing the highest IO mixing ratio recorded in the marine boundary layer to date. IO displayed a clear diurnal profile with a maximum at low tide during the daytime. These results represent the first point measurements of IO in the atmosphere by LIF.  相似文献   

10.
Palaeoclimates across Europe for 6000 y BP were estimated from pollen data using the modern pollen analogue technique constrained with lake-level data. The constraint consists of restricting the set of modern pollen samples considered as analogues of the fossil samples to those locations where the implied change in annual precipitation minus evapotranspiration (P–E) is consistent with the regional change in moisture balance as indicated by lakes. An artificial neural network was used for the spatial interpolation of lake-level changes to the pollen sites, and for mapping palaeoclimate anomalies. The climate variables reconstructed were mean temperature of the coldest month (T c ), growing degree days above 5  °C (GDD), moisture availability expressed as the ratio of actual to equilibrium evapotranspiration (α), and P–E. The constraint improved the spatial coherency of the reconstructed palaeoclimate anomalies, especially for P–E. The reconstructions indicate clear spatial and seasonal patterns of Holocene climate change, which can provide a quantitative benchmark for the evaluation of palaeoclimate model simulations. Winter temperatures (T c ) were 1–3 K greater than present in the far N and NE of Europe, but 2–4 K less than present in the Mediterranean region. Summer warmth (GDD) was greater than present in NW Europe (by 400–800 K day at the highest elevations) and in the Alps, but >400 K day less than present at lower elevations in S Europe. P–E was 50–250 mm less than present in NW Europe and the Alps, but α was 10–15% greater than present in S Europe and P–E was 50–200 mm greater than present in S and E Europe. Received: 3 January 1996 / Accepted: 15 July 1996  相似文献   

11.
The fractions of local traffic (LT), urban background (UBG) and regional background (RBG) of the particle pollution at a traffic-influenced kerbside in Dresden, Germany, were determined by measurements of size-segregated mass concentration, chemical composition and particle size distributions in a network of five measurement stations partly existing and partly set up for this study. Besides the kerbside station, one urban background site and three rural sites were included in the study. Using data from these different sites, the LT, UBG, and RBG contributions were calculated, following the approach of Lenschow et al. (2001). At the kerbside site, 19% of the total number concentration (DpSt = 10–600 nm) could be attributed to the RBG, 15% to the UBG, and 66% to the LT immediately nearby. Particle mass concentrations up to Dpaer = 420 nm RBG amounts to 68%, UBG to 21%, and LT only to 11%. Highest mass concentrations were observed at all stations in autumn and winter during easterly inflow directions. The local traffic fraction of PM10 mass at the kerbside station was found to be 30% for westerly inflow, but only 7% for southeasterly inflow due to the dominating transport fraction from up to 80% of the particle mass at this inflow direction. Size-resolved investigation showed the main fractions in both the particle size ranges of Dpaer = 0.42 to 1.2 and 0.14 to 0.42 μm at all stations. The main components sulphate, ammonium and total carbon showed higher concentrations at south-eastern/eastern inflow in autumn at all stations, while nitrate at the kerbside and urban background site was higher during westerly inflow in winter. The chemical composition at the regional background site at westerly inflow (12% nitrate, 8% sulphate, 11% total carbon) was significantly different from that at easterly inflow (3% nitrate, 15% sulphate, 22% total carbon). The prevailing part of the ionic mass was always found in the fine particle range of Dpaer = 0.14 to 1.2 μm at all stations. For all inflow directions highest total carbon concentrations were observed at the kerbside station, especially in the ultra-fine size range of Dpaer = 0.05 to 0.14 μm with up to 30% of the whole carbon. PAH concentrations were always higher at south-eastern/eastern inflow especially during wintertime. Trace metal components and silicon were found mainly in the coarse mode fraction at the kerbside resulting from abrasion or resuspension.  相似文献   

12.
Ambient respirable particles (PM10; aerodynamic diameter ≤10 μm) collected in a tropical urban environment (Delhi, India) during December 2008-November 2009 were characterized with respect to 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) and 8 major and trace metals (Fe, Mn, Cd, Cu, Ni, Pb, Zn and Cr). Concentrations of Σ16PAHs (annual mean: 74.7 ± 50.7 ng m−3, range 22.1–258.4 ng m−3) and most metallic species were at least an order of magnitude greater than values reported from similar locations worldwide. Seasonal variations in Σ16PAHs were significant (p < 0.001) with highest levels in winter while crustal and anthropogenic metals showed significant but mutually opposite seasonal dependence. Statistically significant associations were observed between chemical species and various meteorological parameters. The PAH profile was dominated by combustion-derived large-ring species (~85%) that were essentially local in origin. Principal component analysis–multiple linear regression (PCA-MLR) apportioned four sources: crustal dust (73%), vehicular emission (21%), coal combustion (4%) and industrial emission (2%) that was further validated by hierarchical cluster analysis (HCA). Temporal trend analysis showed that crustal sources were predominant in summer (p < 0.05) while the remaining sources were most active in winter. Summertime intrusions of Saharan dust were identified with the help of aerosol maps and air parcel backward trajectories. Inhalation cancer risk assessment showed that up to 3,907 excess cancer cases (357 for PAHs, 122 for Cd, 2040 for Cr (VI) and 1387 for Ni) are likely in Delhi considering lifetime inhalation exposure to these chemicals at their current concentrations.  相似文献   

13.
We use a reduced complexity climate model with a three-dimensional ocean component and realistic topography to investigate the effect of stratification-dependent mixing on the sensitivity of the North Atlantic subpolar gyre (SPG), and the Atlantic meridional overturning circulation (AMOC), to idealized CO2 increase and peaking scenarios. The vertical diffusivity of the ocean interior is parameterized as κ ∼ N −α, where N is the local buoyancy frequency. For all parameter values 0 ≤ α ≤ 3, we find the SPG, and subsequently the AMOC, to weaken in response to increasing CO2 concentrations. The weakening is significantly stronger for α ≥ αcr ≈ 1.5. Depending on the value of α, two separate model states develop. These states remain different after the CO2 concentration is stabilized, and in some cases even after the CO2 concentration has been decreased again to the pre-industrial level. This behaviour is explained by a positive feedback between stratification and mixing anomalies in the Nordic Seas, causing a persistent weakening of the SPG.  相似文献   

14.
In stably stratified flows vertical movement of eddies is limited by the fact that kinetic energy is converted into potential energy, leading to a buoyancy displacement scale z B . Our new mixing-length concept for turbulent transport in the stable boundary layer follows a rigid-wall analogy, in the sense that we assume that the buoyancy length scale is similar to neutral length scaling. This implies that the buoyancy length scale is: ℓ B  = κ B z B , with κ B ≈ κ, the von Karman constant. With this concept it is shown that the physical relevance of the local scaling parameter z/Λ naturally appears, and that the α coefficient of the log-linear similarity functions is equal to c/κ 2, where c is a constant close to unity. The predicted value α ≈ 1/κ 2 = 6.25 lies within the range found in observational studies. Finally, it is shown that the traditionally used inverse linear interpolation between the mixing length in the neutral and buoyancy limits is inconsistent with the classical log-linear stability functions. As an alternative, a log-linear consistent interpolation method is proposed.  相似文献   

15.
The kinetics of heterogeneous reactions of NO2 with 17 polycyclic aromatic hydrocarbons (PAHs) adsorbed on laboratory generated kerosene soot surface was studied over the temperature range (255–330) K in a low pressure flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption due to their desorption and reaction with NO2 were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of reaction time, NO2 concentrations in the gas phase being analyzed by mass spectrometer. No measurable decay of PAHs due to the reaction with NO2 was observed under experimental conditions of the study (maximum NO2 concentration of 5.5 × 1014 molecule cm−3 and reaction time of 45 min), which allowed to determine the upper limits of the first-order rate constants for the heterogeneous reactions of 17 soot-bound PAHs with NO2: k < 5.0 × 10−5 s−1 (for most PAHs studied). Comparison of these results to previous studies carried on different carbonaceous substrates, showed that heterogeneous reactivity of PAHs towards NO2 is, probably, dependent on the substrate nature even for resembling, although different carbonaceous materials. Results show that particulate PAHs degradation by NO2 alone is of minor importance in the atmosphere  相似文献   

16.
Aerodynamic Parameters of Urban Building Arrays with Random Geometries   总被引：5，自引：5，他引：0  
It is difficult to describe the flow characteristics within and above urban canopies using only geometrical parameters such as plan area index (λ p ) and frontal area index (λ f ) because urban surfaces comprise buildings with random layouts, shapes, and heights. Furthermore, two types of ‘randomness’ are associated with the geometry of building arrays: the randomness of element heights (vertical) and that of the rotation angles of each block (horizontal). In this study, wind-tunnel experiments were conducted on seven types of urban building arrays with various roughness packing densities to measure the bulk drag coefficient (C d ) and mean wind profile; aerodynamic parameters such as roughness length (z o ) and displacement height (d) were also estimated. The results are compared with previous results from regular arrays having neither ‘vertical’ nor ‘horizontal’ randomness. In vertical random arrays, the plot of C d and z o versus λ f exhibited a monotonic increase, and z o increased by a factor of almost two for λ f = 48–70%. C d was strongly influenced by the standard deviation of the height of blocks (σ) when λ p ≥ 17%, whereas C d was independent of σ when λ p = 7%. In the case of horizontal random arrays, the plot of the estimated C d against λ f showed a peak. The effect of both vertical and horizontal randomness of the layout on aerodynamic parameters can be explained by the structure of the vortices around the blocks; the aspect ratio of the block is an appropriate index for the estimation of such features.  相似文献   

17.
High-resolution water vapour measurements made by the Atmospheric Radiation Measurement (ARM) Raman lidar operated at the Southern Great Plains Climate Research Facility site near Lamont, Oklahoma, U.S.A. are presented. Using a 2-h measurement period for the convective boundary layer (CBL) on 13 September 2005, with temporal and spatial resolutions of 10 s and 75 m, respectively, spectral and autocovariance analyses of water vapour mixing ratio time series are performed. It is demonstrated that the major part of the inertial subrange was detected and that the integral scale was significantly larger than the time resolution. Consequently, the major part of the turbulent fluctuations was resolved. Different methods to retrieve noise error profiles yield consistent results and compare well with noise profiles estimated using Poisson statistics of the Raman lidar signals. Integral scale, mixing-ratio variance, skewness, and kurtosis profiles were determined including error bars with respect to statistical and sampling errors. The integral scale ranges between 70 and 130 s at the top of the CBL. Within the CBL, up to the third order, noise errors are significantly smaller than sampling errors and the absolute values of turbulent variables, respectively. The mixing-ratio variance profile rises monotonically from ≈0.07 to ≈3.7 g2 kg−2 in the entrainment zone. The skewness is nearly zero up to 0.6 z/z i , becomes −1 around 0.7–0.8 z/z i , crosses zero at about 0.95 z/z i , and reaches about 1.7 at 1.1 z/z i (here, z is the height and z i is the CBL depth). The noise errors are too large to derive fourth-order moments with sufficient accuracy. Consequently, to the best of our knowledge, the ARM Raman lidar is the first water vapour Raman lidar with demonstrated capability to retrieve profiles of turbulent variables up to the third order during daytime throughout the atmospheric CBL.  相似文献   

18.
Recently, several attempts have been made to model the wind velocity in an urban canopy in order to accurately predict the mixing and transport of momentum, heat, and pollutants within and above the canopy on an urban scale. For this purpose, unverified assumptions made by Macdonald (Boundary-Layer Meteorol 97:25–45, 2000) to develop a model for the profile of the mean wind velocity within an urban canopy have been used. In the present study, in order to provide foundations for improving the urban canopy models, the properties of the spatially-averaged mean quantities used to make these assumptions have been investigated by performing large-eddy simulations (LES) of the airflow around square and staggered arrays of cubical blocks with the following plan area densities: λ p = 0.05, 0.11, 0.16, 0.20, 0.25, and 0.33. The LES results confirm that the discrepancy between the spatial average of wind velocity and Macdonald’s five-point average of wind velocity can be large in both types of arrays for large λ p . It is also confirmed that Prandtl’s mixing length varies significantly with height within the canopy, contrary to Macdonald’s assumption for both types of arrays and for both small and large λ p . On the other hand, in accordance with Macdonald’s assumption, the sectional drag coefficient is found to be almost constant with height except in the case of staggered arrays with high λ p .  相似文献   

19.
We report on field observations in January 2009 (austral summer) of atmospheric dust devils in the northern part of the Atacama Desert in South America (≈20◦S). An extremely high level of dust-devil activity over the study site has been observed, dependent on local meteorological conditions. We found a high correlation between the dust-devil frequency of occurrence and the Obukhov length scale, L, calculated from meteorological gradient measurements, with a clear tendency for this frequency to increase with decreasing −L. The upper threshold values of −L ≈ 20–30 m, and the 2-m mean wind speed, V 2 ≈ 8m s−1, for dust-devil occurrence have been found, but the minimal V 2 threshold was not observed. Parallel routine meteorological measurements enabled us to calculate the main constituents of the surface energy balance, to obtain direct estimates of the surface albedo (α ≈ 0.21 at the solar noon) and to summarize the local conditions.  相似文献   

20.
The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k 12/k 13, are greater than unity or normal KIEs. The KIEs, reported in per mil according to Cl ɛ = (k 12/k 13−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10−10 cm3 molecule−1 s−1. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.  相似文献   

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