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1.
With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of103 mol/l/atm. The removal increases to 50% forH = 104 mol/l/atm, and to 90% for H =105 mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H2O2 and the strong acids (H2SO4,HNO3, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO4, HNO2 at pH 5,CH2O, the organic acids at pH 6,CH3SOCH3, HOCl, HOBr, and HOI. NH3 islargely removed by liquid phase scavenging at pH 7 and SO2 atpH 7. At pH less thanabout 6, upward transport of SO2 should largelydepend on the efficiency of oxidation processes in thewater droplets by O3 and H2O2.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O3, CO,the hydrocarbons, NO, NO2, HCN, CH3CN,CH3SCH3, CH3O2H, CH3CHOandhigher aldehydes, CH3OH and higher alcohols,peroxyacetylnitrate (PAN), CH3COCH3 andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.  相似文献   

2.
The wind stress in the marine surface layer under unstable conditions and low wind speed has been studied using a Synthetic Aperture Radar (SAR) image of the sea surface and time series of the horizontal and vertical wind velocities and of the wind stress recorded on board the C.N.R. research platform, in the northern Adriatic Sea, during a SAR overflight.A conditional sampling technique has been used on the wind stress time series and on the SAR image to detect downward (sweep) and upward (ejection) bursts of the momentum flux, as well as the two-dimensional structure of the radar backscatter.From the ensemble average of both the wind stress and the backscatter structures, it has been possible to estimate the mean duration of the upward (11 s) and the downward (15 s) wind stress bursts and the mean size of the bright patches of the SAR image (120 m). The front of the mean backscatter structure, associated with the downward wind stress bursts, has been related to the time length of the mean sweep stress structure to get, after accounting for a threshold of the wind stress for the generation of the sea surface wavelets, the translation velocity Ut of the mean wind stress of sweep, very close to the mean wind speed. The vertical coherence of the wind stress structures has permited to refer the translation velocity to a level very close to the sea surface, but above the viscous sublayer. The variability of Ut with height has been studied through comparison with the mean wind speed at different heights z calculated by a boundary-layer model. Accounting for the results reported in the literature, there is an indication that Ut is constant with height in the range 0.5 m z 15 m.The two-dimensional pattern of the wind stress structures has been derived from the SAR image. The structures appear elongated crosswind, as with microfronts, with an average cross- to down-wind ratio of 4. The area covered by the downward wind stress structures represents 13% of the total area.  相似文献   

3.
Tropospheric photodissociation rate coefficients (J values) were calculated for NO2, O3, HNO2, CH2O, and CH3CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO2, less than 2% for HNO2, +6.5% to -16% for CH2O, -6.9% to +24% for CH3CHO, and -24% to +110% for O3. The errors for CH2O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O3, and to a lesser extent for CH3CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.  相似文献   

4.
A statistically relevant correlation between the reaction rate coefficient, k OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E i,v, reveals two classes of compounds: aromatics where –log(k OH/cm3s-1)3/2E i,v(eV)–2 and aliphatics where –log(k OH/cm3s-1)4/5E i,v(eV)+3. The prediction of the rate coefficient, k OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×105 cm3, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.  相似文献   

5.
The ozonolysis of propene has been investigated in a temperature controlled reaction chamber at 295, 260, and 230 K. Experiments were performed using a total zero air pressure of 760 Torr (STP) and propene/ozone reactant mixing ratios ranging from 2.3 to 23 ppmv. An analysis of FTIR spectra collected at the conclusion of each reaction revealed that methane was formed with a yield of 0.14 ± 0.03 (precision) for all the temperatures investigated.In addition, the yield of HCHO decreased from 0.67 ± 0.04 to 0.43± 0.03 upon cooling from 295 to 230 K, whereas the yield of HCOOH increased from 0.11 ± 0.02 to 0.53 ± 0.04. Experiments were also performedusing an excess of cyclohexane (to scavenge OH) and it was found that the formaldehyde yield was 0.79 ± 0.05 and 0.61 ± 0.04 at 295 and260 K, respectively. Finally, to more fully understand the reaction energies involved in product formation, we have performed molecular orbital calculations of heats of formation of reactants, stable intermediates, and products. Three conclusions can be made of this work. First, the reaction CH2OO + Aldehyde Secondary Ozonide HCOOH + Aldehyde is not an important mechanism in formic acid production. Second, the decomposition of the primary ozonide products (e.g., C2 radical species) appears to occur, in part, by a thermal mechanism (e.g., thermalized to chamber temperature). Third, ab initio resultscombined with experiment reveal no correlation between reaction exothermicity and products formed (e.g., kinetically dictated product formation occurs). The abinitio database is provided nevertheless as a starting point for transition state calculations to be performed in the future. Finally, since formaldehyde yield decreases by at most 35% with decreasing temperature and formic acid is relatively unreactive in the atmosphere, our results suggest that temperature-dependent HCHO yield will constitute only a minor perturbation to HOx formation in the middle troposphere.  相似文献   

6.
Naphthalene (C10H8), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q 1(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10-20 cm2/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q 1(2) and Q 1(3) OH lines.  相似文献   

7.
Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO2) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm3molecule–1 s–1) were found: kDMS+Br = (4.9 ±1.0) ×10–14, kDMSO + Br < 6 × 10–14,kDMSO 2 + Br 1 × 10–15,kDMSO + BrO = (1.0 ± 0.3) × 10–14 andkDMSO 2 + BrO 3 × 10–15 (allvalues are given with one on the experimental data). DMSO, SO2, COS, CH3SBr andCH3SO2Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO2and CH3SO2Br were the only sulphur containing products thatwere identified. DMSO, DMSO2 and SO2 were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO2 was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO2 with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.  相似文献   

8.
Two large-aperture infrared scintillometers were positioned at heights (z) of 10 and 1.5 m with beams propagated horizontally over pasture for distances of 3.1 km and 141 m, respectively. From each scintillometer a half-hourly average value of the path-averaged, temperature-structure parameter (CT2) was obtained in unstable atmospheric conditions. The result suggested CT2 to scale with height as z-2/3. Using the CT2-profile method a path-averaged measure of the Obukhov length (L0) was calculated for each half-hour period, whence L0 was used to determine the friction velocity, u* and the surface-layer temperature scaling parameter, T*. The scintillometer-based sensible heat flux density Hsc was then calculated from Hsc = Cpu*T*. A time series of half-hourly averaged Hsc compared to Hec obtained by the eddy covariance method agreed to within 10%, with R2 = 0.67, for a range of unstable conditions (- 0.2 z/L0 - 0.01).  相似文献   

9.
A general relation between the Kolmogorov (1) and von Kármán (k) constants appropriate to flows in the surface boundary layer is obtained by including stability and divergence dependent terms in the development. The result is used to show that the author's earlier inference of the valuek = 0.36 drawn from the observed value ,k 4/3=0.141 cannot have been underestimated due to the neglect of stability or divergence effects. It is concluded that if k is to be 0.4, then 1 must be 0.5.Work performed under the auspices of the U.S. Energy Research and Development Administration.  相似文献   

10.
Airborne measurements made during August 1985 over Greenland and its environs show that both accumulation-mode (0.1 m D2.0 m) and giant (D2 m) particles were present in relatively high concentrations in arctic haze layers and that the accumulation-mode particles dominated light scattering. Particles with diameters (D) between 1 and 4 m consisted predominately of mixed materials, small and dense inclusions, and probably organic compounds containing sulfur. Many of the particles from 0.1 to 1 m in diameter were also of mixed composition, with sulfuric acid, ammonium sulfate and organics probably the dominant constituents.  相似文献   

11.
Plume dispersion in the convective boundary layer (CBL) is investigated experimentally in a laboratory convection tank. The focusis on highly-buoyant plumes that loft near or become trapped in the CBL capping inversion and resistdownward mixing. Such plumes are defined by dimensionless buoyancy fluxes F* 0.1, where F* = Fb/(U w* 2 zi), Fb is the stack buoyancy flux,U is the mean wind speed, w* is the convective velocity scale, and zi is the CBL depth. The aim is to obtain statistically-reliable mean (C) and root-mean-square (rms, c) concentration fields as a function of F* and the dimensionless distance X = w*x/(U zi), where x is the distance downstream of the source.The experiments reveal the following mainresults: (1) For 3 X 4and F* 0.1, the crosswind-integrated concentration (CWIC) fields exhibit distinctly uniform profiles below zi with a CWIC maximum aloft, in contrast to the nonuniform profiles obtained earlier by Willis and Deardorff. (2) The lateral dispersion (y) variation with X is consistent with Taylor's theory for * 0.1 and a buoyancy-enhanced dispersion, y/zi F* 1/3X2/3, forF* = 0.2 and 0.4. (3) The entrapment, the plume fraction above zi, has a mean (E) that follows a systematic variationwith X and F*, and a variability (e/E) that is broad ( 0.3 to 2) near the source but subsides to 0.25 far downstream. (4) Vertical profiles of the concentration fluctuation intensity (c/C) are uniform for z < zi and X > 1.5, but exhibit significant increases: (a) at the surface and close to the source (X 1.5), and(b) in the entrainment zone. (5) The cumulative distribution functions (CDFs) of the scaled concentration fluctuations (c/c) separate into mixed-layer and entrainment-layer CDFs for X 2, with the mixed-layer group collapsing to a single distribution independent of z.These are the first experiments to obtain all components of the lateral and vertical dispersion parameters (rms meander, relative dispersion, total dispersion) for continuous buoyant releases in a convection tank. They also are the first tank experiments to demonstrate agreement with field observations of: (1) the scaled ground-level concentration along the plume centreline, and (2) the dimensionless lateral dispersion _y/z_i of buoyant plumes.  相似文献   

12.
Carbonyl products have been identified and their formation yields measured in the gas phase reaction of ozone with unsaturated oxygenates in experiments carried out at ambient T, p = 1 atm. of purified humid air (RH = 50%) and with sufficient cyclohexane added to scavenge the hydroxyl radical. The compounds studied are the esters methyl acrylate, vinyl acetate and cis-3-hexenyl acetate, the carbonyl crotonaldehyde, the hydroxy-substituted diene linalool, the ether ethylvinyl ether and the keto-ether trans-4-methoxy-3-buten-2-one. The alkene 1-pentene was included for comparison. The nature and formation yields of the carbonyl products from this study and those measured in earlier work under the same conditions are compared to those of alkenes and are supportive of a reaction mechanism that is similar to that for the reaction of ozone with alkenes, i.e. O3 + R1R2C=CR3X (R1COR2 + R3XCOO) + (1 – )(R3COX + R1R2COO), where Ri are the alkyl substituents, X is the oxygen-containing substituent (–CHO for aldehydes; –C(O)R for ketones; –C(O)OR and –OC(O)R for esters; –OH and hydroxyalkyl for alcohols; and –OR for ethers), R1COR2 is the primary carbonyl, R3COX is the other primary product and R1R2COO and R3XCOO are the carbonyl oxide biradicals. The biradicals lead to carbonyls in reactions that are also analogous to those involved in carbonyl formation from biradicals in the ozone-alkene reaction. These features make it possible to predict the nature and formation yields of the major carbonyl products of the reaction of ozone with unsaturated oxygenates that may be components of biogenic emissions.  相似文献   

13.
Aeolian transport of sedimentary particles is a well-recognized phenomenon in cold regions, but the effect of low temperature (T) and specific humidity (q) upon particle entrainment has not previously been investigated. This study reports on wind-tunnel experiments (-12 °C T 32 °C, and 1 g kg-1 q 10 g kg-1) that suggest the aerodynamic drag required to entrain sand sized particles can be 30% lower in cold or high latitude settings, as compared to hot deserts. For any given regional wind velocity, this effect will increase the wind strength index and thereby the proportion of time a surface is active at low temperature.The influence of air temperature and humidity upon the threshold for particle motion is determined by three physical processes: (1) The effect of air viscosity and density on the fluid drag force acting to dislodge sedimentary particles; (2) the effect of viscosity on the turbulent wake shed from these particles, and the frequency and magnitude of burst-sweep events; and (3) the development of inter-particle cohesion via adsorbed water. This study considers the relative importance of each of these processes. The threshold friction velocity model of Shao and Lu is revised to incorporate the inter-particle force associated with hygroscopic water. It is found to perform well when tested against the experimental data obtained for this study.  相似文献   

14.
Convective Profile Constants Revisited   总被引：2，自引：2，他引：0  
This paper examines the interpolation betweenBusinger–Dyer (Kansas-type) formulae,u = (1 -1 6 )-1/4 andt = (1 - 16 )-1/2, and free convection forms. Based on matching constraints, the constants, au and at, in the convective flux-gradient relations, u = (1 - au )-1/3 and t = (1 - at )-1/3, are determined. It isshown that au and at cannot be completely independent if convective forms are blended with theKansas formulae. In other words, these relationships already carryinformation about au and at. This follows because the Kansas relations cover a wide stability range (up to = - 2), which includes a lower part of the convective sublayer (about 0.1 < - < 2). Thus, there is a subrange where both Kansas and convective formulae are valid. Matching Kansas formulae and free convection relations within thesubrange 0.1 < - < 2 and independently smoothing ofthe blending function are used to determine au and at. The values au = 10 for velocity and at = 34for scalars (temperature and humidity) give a good fit. This new approacheliminates the need for additional independent model constants and yields a`smooth' blending between Kansas and free-convection profileforms in the COARE bulk algorithm.  相似文献   

15.
The effect of changes in zonal and meridional atmospheric moisture transports on Atlantic overturning is investigated. Zonal transports are considered in terms of net moisture export from the Atlantic sector. Meridional transports are related to the vigour of the global hydrological cycle. The equilibrium thermohaline circulation (THC) simulated with an efficient climate model is strongly dependent on two key parameters that control these transports: an anomaly in the specified Atlantic–Pacific moisture flux (Fa) and atmospheric moisture diffusivity (Kq). In a large ensemble of spinup experiments, the values of Fa and Kq are varied by small increments across wide ranges, to identify sharp transitions of equilibrium THC strength in a 2-parameter space (between Conveyor On and Off states). Final states from this ensemble of simulations are then used as the initial states for further such ensembles. Large differences in THC strength between ensembles, for identical combinations of Fa and Kq, reveal the co-existence of two stable THC states (Conveyor On and Off)—i.e. a bistable regime. In further sensitivity experiments, the model is forced with small, temporary freshwater perturbations to the mid-latitude North Atlantic, to establish the minimum perturbation necessary for irreversible THC collapse in this bistable regime. A threshold is identified in terms of the forcing duration required. The model THC, in a Conveyor On state, irreversibly collapses to a Conveyor Off state under additional freshwater forcing of just 0.1 Sv applied for around 100 years. The irreversible collapse is primarily due to a positive feedback associated with suppressed convection and reduced surface heat loss in the sinking region. Increased atmosphere-to-ocean freshwater flux, under a collapsed Conveyor, plays a secondary role.  相似文献   

16.
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.  相似文献   

17.
Zusammenfassung In der vorliegenden Arbeit werden neue Klassifikationsprinzipien für Großwetterlagen entwickelt. Bisher wurde bei Wetterlagenklassifikationen das Druckfeld zugrunde gelegt, wobei quasistationären Druckzentren eine nicht berechtigte Vorrangstellung eingeräumt wurde. In der hier versuchten Klassifikation wird vom Strömungsfeld ausgegangen, das in elementare Formen zerlegt wird. Eine zu diesem Zweck durchgeführte statistische Untersuchung ergab, daß alle im Strömungsfeld auftretenden Zirkulationstypen auf drei Grundformen zurückgeführt werden können. Diese Grundformen sind:Driften, Wellen undWirbel.Die Untersuchung ergab im einzelnen, daß in mittleren Breiten der nördlichen Hemisphäre bei 49% aller untersuchten Fälle Driften, bei 23% Wellen und bei 28% Wirbel auftraten.In der hier durchgeführten Klassifikation wird das Druckfeld durch das Strömungsfeld und der Begriff Großwetterlage durch den umfassenderen Begriff des Zirkulationstyps ersetzt. Damit wird der unberechtigte Vorrang der Druckformen bei der Wetterlagenklassifikation aufgegeben. Die Klassifizierung der Zirkulationstypen ergibt sich schließlich durch Kombination der drei Zirkulationselemente: Drift, Welle und Wirbel.
Summary New principles of classification for large-scale weather situations are outlined in this paper. Hitherto the pressure-field has been taken as a basis for such classifications by conceding a precedence of an unjustified position to semi-permanent centres of pressure. The new classification starts from the field of large-scale motions, which is dissected in elementary models. A statistical test yielded the possibility to reduce all types of atmospheric circulations in the following three elementary models:drifts, waves andeddies.In detail it was found out, that drifts occur in 49%, waves in 23% and eddies in 28% of all cases investigated.In the new classification the term pressure-field is substituted by field of motion and the expression large-scale weather situation by the more comprehensive conception type of circulation. By that the unjustified priority of pressure-centers in classifying weather situations is abolished. At last the classification of the types of circulation follows from a combination of the three elementary models: drift, wave and eddy.
résumé La présente étude développe de nouveaux principes de classification des situations météorologiques. Alors que jusqu'ici on s'est fondé sur le champ de pression ce qui conduisait à attribuer aux centres d'action quasi stationnaires un rôle trop important, l'auteur part ici du champ de mouvement décomposé en formes élémentaires. Un examen statistique lui a montré que tous les types de circulation peuvent se ramener à trois formes fondamentales:courants, ondulations ettourbillons.Aux latitudes moyennes de l'hémisphère Nord les courants représentent le 49%, les ondulations le 23% et les tourbillons le 28%.Au champ de pression se substitue donc le champ de courant, et les situations météorologiques se groupent en types de circulation ce qui supprime le rôle prépondérant des formes isobariques. Le classement final des types de circulation résulte de la combinaison des trois types mentionnés:courants, ondulations ettourbillons.

Mit 15 Textabbildungen  相似文献   

18.
Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons   总被引：15，自引：0，他引：15  
Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO3 reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.  相似文献   

19.
Recent studies suggest that the destruction of methane by Cl in the marine boundary layer could be accounted for as another major sink besides the methane destruction by OH. High level ab initio molecular orbital calculations have been carried out to study the CH4+Cl reaction, the carbon Kinetic Isotope Effect (KIE) is calculated using Conventional Transition-State Theory (CTST) plus Wigner and Eckart semiclassical tunneling corrections. The calculated KIE is around 1.026 at 300 K and has a small temperature variation. This is by far the largest KIE among different processes involving atmospheric methane destruction (e.g., OH, soil). A calculated mass balance of atmospheric methane including the KIE for the CH4+Cl reaction is found to favor those methane budgets with enhanced biological methane sources, which have relatively lighter carbon isotope composition.  相似文献   

20.
The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O2 partial pressure at 760 Torr (N2 + O2) and 298±2 K. The major sulfur containing compounds detected were SO2 and CH3SO3H (methane sulfonic acid, MSA) and the major carbon containing compounds were CO, HCHO, CH3OH and CH3OOH (methyl hydroperoxide). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH3OOH has been observed for the first time in such a photooxidation system. Its observation provides evidence for the formation of CH3 radicals by the further oxidation of the CH3S radicals formed in the primary photolysis step.From the behavior of the DMDS photolysis products as a function of the O2 partial pressure, O3 concentration and added OH radical source it is postulated that the further reactions of CH3SOH (methyl sulfenic acid), formed in the reaction OH + CH3SCCH3 CH3SOH + CH3S, are the main source of MSA in the 254 nm photolysis of DMDS.Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.  相似文献   

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