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1.
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   

2.
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   

3.
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   

4.
A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO3 (0.01), N2O5 (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.  相似文献   

5.
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   

6.
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   

7.
A new, biogeochemical model of ice age cycles is developed and applied which explains major features of climate variations in the late Quaternary —rapid ice age terminations, large glacial-interglacial amplitudes and 100-kyr cycles — in a way consistent with the paleorecord. Existing models which invoke non-linear, ice-sheet-earth-crust dynamics to explain ice age cycles are not consistent with simultaneous terminations in both hemispheres and other phase relationships implied by the paleorecord. The present model relates climate change to oscillations of oceanic primary (new) production controlled by the availability of inorganic nitrogen. Large oscillations follow shelf erosion events triggered by small sea-level drops. These drops are due to glacial buildup associated with a minimum in Northern Hemisphere insolation. Rapid global warming at terminations is initiated by open ocean denitrification events leading to new production crashes and rapid modification of atmospheric trace gas concentrations (CO2, DMS, N2O). Other feedbacks of the land-ice-atmosphere-ocean system control the rest of the climate cycle. 100-kyr cycles derive from orbital pacemaking of the strong, low-frequency model response. Results suggest that the climate regime transition near 800 kyr B.P. may be related to changes in the continental shelf slope, that existing chronologies based on orbital tuning may need to be revised and that temporary increases in atmospheric N2O concentrations at terminations, due to the denitrification events, may have caused significant greenhouse warming. A spike of elevated N2O concentration at terminations may be recorded in polar ice.  相似文献   

8.
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   

9.
Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl–, NO3 –,SO4 2–, non-sea saltSO4 2– (NSSS),CH3SO3 – (MSA) andNH4 +, and gas phase dimethylsulphide (DMS), HCl,HNO3, SO2, CH3COOH, HCOOH andNH3. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10–4 gm–3 s–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10–4 and2.40 × 10–4 g m–3s–1, respectively. The corresponding rates for MSA were6.23 × 10–6, 8.49 × 10–6and 6.95 × 10–6 g m–3s–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH4 +), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.  相似文献   

10.
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   

11.
To determine if Cu mediated reactions on atmospheric particles are important to HO2 chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO2 to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO2 to form H2O2 indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO2 and H2O2 in the troposphere.  相似文献   

12.
Our previously developed theoretical models for describing the rate at which water-soluble atmospheric trace gases are scavenged by cloud and rindrops were evaluated for the case of acetaldehyde being absorbed and desorbed by water drops of radii between 250 to 2500 m radius. The experimental verification of our theoretical predictions was carried out in the UCLA 33 m high precipitation shaft in which falling water drops were allowed to come to terminal velocity before passing through a chamber of variable lengths filled with air containing acetaldehyde at various partial pressures. For all drop sizes studied, the experimental results and the theoretical predictions were in reasonable agreement.  相似文献   

13.
The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O3 and OH/NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O3/air, and the daytime oxidation of a mixture of -pinene + -pinene with NOx air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O3 and NOx system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.  相似文献   

14.
Summary The importance of representative and long-term recordings of the trace gases SO2, NO x , and NO is explained. Recordings taken under different background conditions and, moreover, simultaneously at neighboring mountain stations, together with other meteorological parameters, are of special interest.The recording stations for the determination of the mentioned gases (a valley station at 740 m a.s.l., a nearby mountain station at 1780 m a.s.l.), the measuring methods, calibration procedures, and zero-air supply are described.The main part deals with the representation of consistent data of trace gases obtained at the two stations (NO only in the valley floor). Special attention was given not only to longterm trends but also to the seasonal and diurnal variations, and to the dependence of the gas concentrations on meteorological parameters. Only on the basis of such a parameterization, the time variations become understandable and the causes can be explained as well as possible. Finally, correlations between the concentrations of the different gas components are shown.With 15 Figures  相似文献   

15.
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   

16.
An experimental study of the scavenging of dichloromethane vapor by water drops falling at terminal velocity, has been carried out in the UCLA precipitation shaft, in order to test the predictions of theoretical washout models. Whereas good agreement between theory and experiment was found for drops of radius 0.332 mm, computed gas uptake rates for 1.253 and 2.21 mm radius drops were much slower than those measured, just as reported previously for the washout of both sulfur dioxide and acetaldehyde. An analysis shows that theory can be reconciled with all of the experimental data by replacing the compound specific aqueous phase Fickian molecular diffusion coefficient used in the theory, by an effective diffusivity, having a constant value, (3×10-4 cm2 s-1), independent of the physical and chemical nature of the absorbed species, for all drops of equivalent radii greater than 0.9 mm.  相似文献   

17.
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   

18.
Concentration differences between small (r < 8.5 m) and large droplets(r > 8.5 m) were observed for formic acid, acetic acid and formaldehyde in fog droplets collected in California's Central Valley. The concentration ratios (large/small droplets) of these compounds were investigated by a stepwise model approach. Assuming thermodynamic equilibrium (KH eff) results in an overestimate of the concentration ratios. Considering the time dependence of gas phase diffusion and interfacial mass transport, it appears that the lifetime of fog droplets might be sufficiently long to enable phase equilibrium for formaldehyde and acetic acid, but not for formic acid (at pH 7). Oxidation by the OH radical has no effect on formaldehyde concentrations but reduces formic acid concentrations uniformly in all drop size classes. The corresponding reaction for acetic acid is less efficient so that only in large droplets, where replenishment is slowed because the uptake rate of acid from the gas phase is slower, is the acid concentration reduced leading to a smaller concentration ratio. Formaldehyde concentrations in fog can be higher than predicted by Henry's Law due to the formation of hydroxymethanesulfonate. Its formation is dependent on the sulfur(IV) concentration. At high pH values the uptake rate for sulfur(IV) is drop-size dependent. However, the observed concentration ratios for formaldehyde cannot be fully explained by the adduct formation. Finally, it is estimated that mixing effects, i.e., the combination of individual droplets into a bulk sample, have a minor influence (<15%) on the measured heterogeneities.  相似文献   

19.
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   

20.
During April 1986, as part of an international arctic air chemistry study (AGASP-2), ground level observations of aerosol trace elements, oxides of sulphur and nitrogen and particle number size distribution were made at Alert Canada (82.5N, 62.3W). Pollution haze was evident as indicated by daily aerosol number (size > 0.15 m diameter) and SO4 = concentrations in the range 125 – 260 cm–3 and 1.6 – 4.5 g m–3, respectively. Haze and associated acidic gases tended to increase throughout the period. SO2 and peroxyacetylnitrate (PAN) mixing ratios were in the range 140 – 480 and 370 – 590 ppt(v), respectively. About 88% of the total end-product nitrogen was in the form of PAN. In air dried to 2% relative humidity by warming to room temperature, the aerosol mass size distribution had a major mode at 0.3 m diameter and a minor one at 2.5 m. Aerosol mass below 1.5 m was well correlated with SO4 =, K+ and PAN. There was a steady increase in the oxidized fraction of total airborne sulphur and nitrogen oxide throughout April as the sun rose above the horizon and remained above. The mean oxidation rate of SO2 between Eurasia and Alert was estimated as 0.25 – 0.5% h–1. The molar ratio of total nitrogen oxide to total sulphur oxide in the arctic atmosphere (0.67±0.17) was comparable to that in European emissions. A remarkably strong inverse correlation of filterable Br and O3 led to the conclusion that O3 destruction and filterable Br production below the Arctic surface radiation inversion is associated with tropospheric photochemical reactions involving naturally occurring gaseous bromine compounds.  相似文献   

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