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1.
An experimental and theoretical study has been carried out to investigate the rate of desorption of SO2 from water drops falling at terminal velocity in air. The experiments were carried out in the Mainz vertical wind tunnel in which water drops of various sizes containing S(IV) in various concentrations were freely suspended in the vertical airstream of the tunnel. The results of these experiments were compared with the predictions of three theoretical models, and with the experiments of Walceket al. This comparison shows that the predictions of the diffusion model of Kronig and Brink in the formulation given by Walcek and Pruppacher agree well with the experimental results for all relevant large and small rain-drop sizes, and for all considered concentrations of S(IV) inside the drops. In contrast, the predictions of the diffusion model which assumes complete internal mixing inside a drop agrees with the experimental results only if the concentration of S(IV) inside the drop is less than that equivalent of an equilibrium SO2 concentration of 15 ppbv. At larger concentrations, the theoretical predictions of the model for complete internal mixing progressively deviate from the experimental results. It is further shown that Barrie's double film model can be used to interpret the resistance to diffusion inside a drop in terms of a diffusion boundary layer inside the drop which increases in thickness with decreasing concentration of S(IV). Applying our results to the desorption of SO2 from small and large rain drops falling below an assumed cloud base, shows that for typical contents of S(IV) inside the drops substantial amounts of SO2 will desorb from these drops unless H2O2 is present in the surrounding air.  相似文献   

2.
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   

3.
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   

4.
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   

5.
An experimental study has been carried out in the Mainz vertical wind tunnel to determine the rate at which NH3 in the presence of CO2 is absorbed by freely suspended water drops. The experimental uptake rates were found to be in good agreement with the rates predicted by the Kronig-Brink convective diffusion model and, for gas concentrations in the ppbv range also by the model in which it is assumed that the absorbed gas is well mixed inside the drop (henceforth called well mixed model). The same conclusion was shown to apply also to the desorption of NH3 from a drop previously exposed to NH3. The latter result is in contrast to the desorption of SO2 which must be described by a model which accounts for the diffusion of the species inside the drop. Comparison of our experimental results with theory show further that the uptake of NH3 in presence of CO2 is significantly overestimated if the slow reaction CO2(aq)+H2OHCO 3 – +H+ is neglected in the theoretical computation.  相似文献   

6.
Our previously described absorption model for the scavenging of trace gases by individual cloud and rain drops was applied to an ensemble of drops of given size distribution as found in typical atmospheric rainfalls. This study allowed: (1) determination of the redistribution which a pollution plume suffers as rain falls through it, and (2) determination of the amount of pollutant contained in. the fallen rain. For the present application it was assumed that the pollution plume consisted of SO2, only, and that its concentration varied vertically as a Gaussian distribution centered 200 m above the ground. Rain of various intensities and corresponding drop size distributions was allowed to pass through this pollution layer. The results of our study show that the average height and concentration of the plume decrease in proportion to the total amount of rain which had passed through the pollution layer. The fractional plume washout rate (in % per mm of rain) was found to be inversely proportional to the SO2 gas concentration, the plume height, and the plume thickness. By including the effects of oxidation inside the falling raindrops, it was noted that the removal of SO2 became enhanced by a factor of up to 10 times. For significant oxidation the rate with which SO2 was washed out was found to be inversely proportional to the rainfall rate. For the case of light drizzle (2 mm h-1) and large oxidation rate constants (100 s-1), as much as 40% of the sulfur load could be removed by 1 mm of rain. For the case of a heavier rainfall (25 mm h-1) composed of correspondingly larger drops, the washout rate varied between 2 and 10$ mm-1 over a wide range of oxidation rates.  相似文献   

7.
Laboratory experiments have been carried out to investigate the uptake of sulfur dioxide by water drops containing heavy metal ions where the metal ions serve as catalysts to oxidise the taken up S(IV) into S(VI). During the gas uptake the drops were freely suspended at their terminal velocity in the airstream of the Mainz vertical wind tunnel. Two series of experiments were carried out, one with large millimeter size water drops containing manganese or iron ions, and the other with small water drops containing manganese ions and having radii in hundreds of micron size range. The experimental results were compared against model computations using the Kronig–Brink model and the fully mixed model, modified for the case that heavy metal ions present in the liquid phase act as catalysts for the oxidising process. The results of the model calculations show that there are only small differences between the predicted gas uptake according to the two models. In addition it was found that the experimental obtained results from the uptake of SO2 by water drops containing heavy metal ions for both, large and small water drops did agree with the model results.  相似文献   

8.
In view of the uncertainty of the origin of the secular increase of N2O, we studied heterogeneous processes that contribute to formation of N2O in an environment that comes as close as possible to exhaust conditions containing NO and SO2, among other constituents. The N2O formation was followed using electron capture gas chromatography (ECD-GC). The other reactants and intermediates (SO2, NO, NO2 and HONO) were monitored using gas phase UV-VIS absorption spectroscopy. Experiments were conducted at 298 and 368 K as well as at dry and high humidity (approaching 100% rh) conditions. There is a significant heterogeneous rate of N 2 O formation at conditions that mimic an exhaust plume from combustion processes.The simultaneous presence of NO, SO2, O2 in the gas phase and condensed phase water, either in the bulk liquid or adsorbed state has been confirmed to be necessary for the production of significant levels of N2O. The stoichiometry of the overall reaction is: 2 NO+SO2+H2O N2O+H2SO4. The maximum rate of N2O formation occurred at the beginning of the reaction and scales with the surface area of the condensed phase and is independent of its volume. A significant rate of N2O formation at 368 K at 100% rh was also observed in the absence of a bulk substrate. The diffusion of both gas and liquid phase reactants is not rate limiting as the reaction kenetics is dominated by the rate ofN2O formation under the experimental conditions used in this work. The simultaneous presence of high humidity (90–100% rh at 368 K) and bulk condensed phase results in the maximum rate and final yield of N2O approaching 60% and 100% conversion after one hour in the presence of amorphous carbon and fly-ash, respectively.Work performed in partial fulfillment of the requirements of Dr ès Sciences at EPFL.  相似文献   

9.
A model with spectral microphysics was developed to describe the scavenging of nitrate aerosol particles and HNO3 gas. This model was incorporated into the dynamic framework of an entraining air parcel model with which we computed the uptake of nitrate by cloud drops whose size distribution changes with time because of condensation, collision-coalescence and break-up. Significant differences were found between the scavenging behavior of nitrate and our former results on the scavenging behavior of sulfate. These reflect the following chemical and microphysical differences between the two systems:
  1. nitrate particles occur in a larger size range than sulfate particles.
  2. HNO3 has a much greater solubility than SO2 and is taken up irreversibly inside the drops in contrast to SO2.
  3. nitric acid in the cloud water is formed directly on uptake of HNO3 gas whereas on uptake of SO2 sulfuric acid is formed only after the reaction with oxidizing agents such as e.g., H2O2 or O3.
  4. nitrate resulting from uptake of HNO3 is confined mainly to small drops, whereas sulfate resulting from uptake of SO2 is most concentrated in the largest, oldest drops, which have had the greatest time for reaction.
Sensitivity studies showed that the nitrate concentration of small drops is significantly affected by the mass accommodation coefficient.  相似文献   

10.
The boundary-layer resistance, r d , for water vapour transfer from single drops on a wheat leaf was derived from field measurements of the evaporation rate, drop temperature and air humidity. Parameters are estimated in an equation to calculate r d from drop diameter and wind speed. The relationship between resistance and wind speed is compared with that from other sources, and possible systematic errors in temperature measurements are examined using a model of the drop energy balance.On secondment from Department of Agricultural Sciences, University of Bristol, IACR, Long Ashton Research Station, Long Ashton, Bristol BS18 9AF, U.K.  相似文献   

11.
The pH and the concentrations of sulfate, nitrate, ammonia, and calcium in rainwater were measured for two periods of a single midwest rainstorm which occurred over a mesometeorological network in central Illinois on 24–25 July 1979. Regression analysis was used to compare ion concentrations with rainfall amount, and ion balance was used to compare cation and anion concentrations at individual sites. Only the ions SO4 2- and NO3 - show any significant relationship to rainfall amount, decreasing as rainwater amounts increase (r=–0.57 and –0.60, respectively). During the first period of the rainstorm, a sequential sampler measurements allowed the calculation of detailed temporal variations in SO4 2-, pH, and rain rate. SO4 2- decreased, and pH increased as the rate increased and the opposite temporal pattern occurred as the rain decreased at the end of the period. Reasons for these variations are discussed.Research done while a visiting scientist at the Illinois State Water Survey, Champaign, Illinois, U.S.A.  相似文献   

12.
Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO2) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO2 diurnalcycles, consistent with the photochemical production of SO2 from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO2 from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO2 yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO2 yield is lower in the range of 20–40%.  相似文献   

13.
Henry's law constants KH (mol kg–1 atm–1) for the reaction HOCl(g)=HOCl(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H2SO4 (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg–1 atm–1] of HOCl in aqueous H2SO4 are given by: ln(H*)=6.4946–mH2SO4(–0.04107+54.56/T)–5862 (1/To–1/T) where T(K) is temperature and To=298.15K. The activity coefficient of HOCl in aqueous H2SO4 has a simple Setchenow-type dependence upon H2SO4 molality.  相似文献   

14.
A one-dimensional, time-dependent model of the physics and chemistry of a warm stratiform cloud is used to study the possible impact of chemical inhomogeneity among cloud and raindrops on the oxidation of SO2 in clouds. The effects of chemical inhomogeneity are examined using two contrasting models: In Model 1 a bulk-solution parameterization is adopted which effectively treats all cloud and raindrops as if they are chemically homogeneous; in Model 2 we allow the cloud and raindrops to have a dichotomous distribution. The dichotomous distribution in Model 2 is simulated by assuming that the two groups of cloud droplets nucleate from two chemically distinct populations of condensation nuclei; one being acidic and the other being alkaline. While the two models yield essentially identical results when the ambient levels of H2O2 are greater than the ambient levels of SO2, the rate of conversion of SO2 to sulfuric acid and the amount of sulfate removed in the precipitation can be significantly enhanced in Model 2 over that of Model 1 under conditions of oxidant limitation (i.e., H2O2 < SO2). This enhancement is critically dependent upon the fraction of alkaline nuclei assumed to be present in Model 2 and arises from the rapid increase in the aqueous-phase reaction between O3+SIV at high pH. Our results suggest that cloud models which adopt a bulk-solution parameterization for cloud droplet chemistry, may underestimate the amount of in-cloud SO2 oxidation under oxidant-limited conditions.  相似文献   

15.
Dimethyl sulfide (DMS) and sulfur dioxide (SO2) mixing ratios were measured in the boundary layer on Oahu, Hawaii in April and May 2000. Average DMS and SO2 levels were 22 ± 7 (n = 488) pmol/mol and 23 ± 7 (n = 471) pmol/mol respectively. Anti-correlated DMS and SO2 diurnal cycles, consistent with DMS + OH oxidation were observed on most days. Photochemical box model simulations suggest that the yield of SO2 and total SO2 sink are ∼85% and ∼2 × 104 molec cm− 3 s− 1 respectively. On several days the rate of decrease in DMS and increase in SO2 levels in the early morning were larger that predicted by the model. Dynamical and chemical causes for the anomalous early morning data are explored.  相似文献   

16.
The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO x termination mechanism for the HO—SO2 reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO2 radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO2 production from the HO—SO2 reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.  相似文献   

17.
The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO2 (0–860 ppb), H2O2 (0–150 ppb) and sometimes NH3 (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH4)2SO4 and Na2SO4 droplets. For (NH4)2SO4 droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH3 was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO2 by H2O2, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH3 evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.  相似文献   

18.
The pK 1 * and pK 2 * of H2SO3 have been determined in NaCl solutions as a function of ionic strength (0.1 to 6 m) and temperature (5 and 25 °C). The extrapolated values in water were found to be in good agreement with literature data. The experimental results have been used to determine the Pitzer interaction parameters for SO2, HSO 3 - and SO 3 - in NaCl solutions. The resultant parameters for NaHSO3 and Na2SO3 were found to be in reasonable agreement with the values for NaHSO4 and Na2SO4. It, thus, seems reasonable to assume that the interactions of Mg2+ and Ca2+ with HSO 3 - and SO 3 - can be estimated from the values with HSO 4 - and SO 4 - until experimental values are available. Measurements of pK 1 * and pK 2 * in artificial seawater were found to be in good agreement with the calculated values using the derived Pitzer parameters. It is, thus, possible to make reasonable estimates of the activity coefficients of HSO 3 - and SO 3 - ions and pK 1 * and pK 2 * for the ionization of H2SO3 in marine aerosols.  相似文献   

19.
The chemical removal of SO2 in the presence of different aerosol systems has been investigated in laboratory experiments using a dynamic flow reactor. The aerosols consisted of wetted particles containing one of the following substances: MnCl2, Mn(NO3)2, MnSO4, CuCl2, Cu(NO3)2, CuSO4, FeCl3, NaCl. The SO2 removal rate R was measured as a function of the SO2 gas phase concentration (SO2)g, the spatial metal concentration CMe, and the relative humidity rH in the reactor. A first-order dependence with regard to (SO2)g was observed for each type of aerosol. For the Mn(II) and Cu(II) aerosols R was found to be a non-linear function of CMe except for MnSO4 and Cu(NO3)2 particles. The removal rate showed a significant increase with the relative humidity particularly when rH was close to the deliquescence point of the wetted particles. Among the Mn(II) and Cu(II) aerosols investigated Mn(NO3)2 was found to be most efficient for the chemical removal of SO2 at atmospheric background conditions, especially in haze and fog droplets. The results further indicate that the catalytic oxidation of S(IV) in such aerosol systems may be as efficient as its oxidation by H2O2 in cloud water.  相似文献   

20.
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   

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