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1.
Ion-induced binary H2SO4–H2O nucleation is an important mechanism of aerosol formation in the atmosphere. Ions are created in the atmosphere mainly by galactic cosmic rays. The importance of ion-induced nucleation is recognized in some of the observed nucleation events in the background atmosphere. However, the predictions of current ion–aerosol models are highly uncertain mostly due to the lack of detailed experimental information concerning the thermodynamics and kinetics of ion clustering reactions. Here we continue the report of results of our laboratory experiments on the formation and growth of positive and negative cluster ions in H2SO4–H2O vapours in the flow reactor started in Wilhelm et al. [2004. Ion-induced aerosol formation: new insights from laboratory measurements of mixed cluster ions HSO4(H2SO4)a(H2O)w and H+ (H2SO4)a(H2O)w. Atmospheric Environment 38, 1735–1744] and Sorokin et al. [2006. Formation and growth of sulphuric acid–water cluster ions: experiments, modelling, and implications for ion-induced aerosol formation. Atmospheric Environment 40, 2030–2045]. The main attention is given to the definition of the concentration of gaseous sulphuric acid in experiment and also to some aspects of the kinetics of small cluster ions formation. The performed analysis has indicated a threshold concentration of gaseous sulphuric acid for binary homogeneous nucleation of at least about 1010 cm−3 at room temperature and low relative humidity.  相似文献   

2.
The aging processes of two representative natural aerosol, sea-salt and mineral aerosol, are investigated by using a box model equipped with a thermodynamic module (SCAPE). The model is shown to successfully describe the aging processes between the gas-phase anthropogenic pollutants (SO2, NOx, and NH3) and primary aerosol particles, including self-neutralization process/chlorine depletion in the sea-salt aerosol; formation/dissipation of carbonate and bicarbonate ions in the mineral aerosol; irreversible dynamic deposition of SO2 and H2SO4; and reversible thermodynamic distribution of inorganic volatile species. It is found that SO2 and H2SO4 tend to deposit onto the mode with the largest surface area, and that ammonia deposition is controlled by preceding SO2/H2SO4 deposition. During the SO2/H2SO4 deposition, chloride and carbonate are continuously released from the sea-salt and mineral dust particles, respectively. The findings by the model predictions are consistent with field and observational studies.  相似文献   

3.
Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m3, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m3, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m3 of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H2SO4 or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H2SO4 plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H2SO4, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.  相似文献   

4.
ABSTRACT

We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.  相似文献   

5.
ABSTRACT

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult.

We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply).

Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).  相似文献   

6.
Vehicle particle emissions are studied extensively because of their health effects, contribution to ambient PM levels and possible impact on climate. The aim of this work was to obtain a better understanding of secondary particle formation and growth in a diluting vehicle exhaust plume using 3-d information of simulations together with measurements. Detailed coupled computational fluid dynamics (CFD) and aerosol dynamics simulations have been conducted for H2SO4–H2O and soot particles based on measurements within a vehicle exhaust plume under real conditions on public roads.Turbulent diffusion of soot and nucleation particles is responsible for the measured decrease of number concentrations within the diesel car exhaust plume and decreases coagulation rates. Particle size distribution measurements at 0.45 and 0.9 m distance to the tailpipe indicate a consistent soot mode (particle diameter Dp∼50 nm) at variable operating conditions. Soot mode number concentrations reached up to 1013 m−3 depending on operating conditions and mixing.For nucleation particles the simulations showed a strong sensitivity to the spatial dilution pattern, related cooling and exhaust H2SO4(g). The highest simulated nucleation rates were about 0.05–0.1 m from the axis of the plume. The simulated particle number concentration pattern is in approximate accordance with measured concentrations, along the jet centreline and 0.45 and 0.9 m from the tailpipe. Although the test car was run with ultralow sulphur fuel, high nucleation particle (Dp⩽15 nm) concentrations (>1013 m−3) were measured under driving conditions of strong acceleration or the combination of high vehicle speed (>140 km h−1) and high engine rotational speed (>3800 revolutions per minute (rpm)).Strong mixing and cooling caused rapid nucleation immediately behind the tailpipe, so that the highest particle number concentrations were recorded at a distance, x=0.45 m behind the tailpipe. The simulated growth of H2SO4–H2O nucleation particles was unrealistically low compared with measurements. The possible role of low and semi-volatile organic components on the growth processes is discussed. Simulations for simplified H2SO4–H2O–octane–gasoil aerosol resulted in sufficient growth of nucleation particles.  相似文献   

7.
A self-consistent expression for the kinetics of ternary nucleation is developed based on the nucleation flux theory derived by Langer, 1969, Annals of Physics 54, 258–275. The method for obtaining the ternary nucleation flux is based on the solution of a Fokker–Planck equation for the concentration of clusters where both number and cluster energy fluctuations are included. The theory is applied to a nonideal solution of water–sulphuric acid that is nonideally mixed with ammonia. The nucleation rates predicted for this ternary system studied show a considerable increase on the nucleation rate compared to the binary water–sulphuric acid system for gaseous concentrations of ammonia which are likely to occur in the atmosphere. The results of the present study are in qualitative agreement with current laboratory and theoretical studies where a considerable enhancement in the nucleation rate is observed with the addition of tens of parts per trillion by volume of NH3 in the binary H2SO4–H2O system.  相似文献   

8.
The threshold concentrations of gaseous methane sulfonic acid (MSA) required for homogeneous and heterogeneous nucleation of MSA solution droplets in the MSA-water system have been calculated as a function of environmental relative humidity. The MSA concentration required to supersaturate the atmosphere (with respect to aqueous MSA solutions) at 80% r.h. is of the order of 10−12 atm (1 pptv), whereas the concentration required for spontaneous production of new MSA aerosol is of the order of 10−8 atm (10 ppbv). The calculations also show a strong dependence of the saturation curve on relative humidity. At 80 % r.h., 1 pptv MSA vapor supersaturates the atmosphere, whereas at 10 % r.h. about 5 ppbv is required to supersaturate the environment. The role which the conversion of dimethylsulfide (DMS) to MSA and H2SO4 might play in the formation and growth of sub-μm particles in remote oceanic regions is discussed.  相似文献   

9.
Binary nucleation theory is applied to the formation of aqueous sulfuric acid and aqueous methanesulfonic acid particles and the relative rates of aerosol formation in humid atmospheres are compared. An integral model is presented which describes nucleation of solution particles, aerosol growth, and condensable vapor source and depletion rates. To extend this model, the water activities of the ternary solution, sulfuric acid-methanesulfonic acid-water, are estimated, and growth of the nucleated aerosol by incorporation of both types of acid is considered. Predictions of both forms of the model are compared with the experimental results of Hatakeyama et al. [Atmospheric Environment19, 135–141 (1985)] for the photooxidation of dimethylsulfide in humid air.  相似文献   

10.
The influence of soluble compounds leached from real atmospheric aerosol particles (size range Dae: 0.17–1.6 μm) and dissolved NO2 on S(IV) oxidation in aqueous solution is presented. Experiments were conducted with aerosol particles of two different origins (i.e., urban and industrial) and at concentrations of trace gases in the gas mixtures (SO2/air and SO2/NO2/air) typical for a polluted atmosphere. During the introduction of SO2/air into the aqueous aerosol suspensions under dark conditions at pH 4, the formation of SO42− was very slow with a long induction period. However, in the presence of NO2 the oxidation rate of dissolved SO2 in suspensions of aerosols from both origins increased substantially (about 10 times). The results suggest that soluble compounds eluted from atmospheric aerosols have not only a catalytic (e.g. Fe, Mn), but also a pronounced inhibiting effect (e.g., oxalate, formate, acetate, glycolate) on S(IV) autoxidation. When NO2 was also introduced into the aerosol suspensions, the inhibition was not so highly expressed. An explanation for this is that the radical chain mechanism is mainly initiated by the interaction of dissolved NO2 and HSO3. Therefore, at conditions typical for a polluted atmosphere dissolved NO2 can have a significant influence on the secondary formation of SO42−.  相似文献   

11.
Many nonferrous metals are produced from sulfur-bearing minerals. When pyrometallurgical processes are used, sulfur dioxide gas is formed as a byproduct. In many cases, a small but significant portion of the SO2 is oxidized further to SO3 within the pyrometallurgical reactor system. Upon cooling of the gases, as would occur when such gases contact the atmosphere, SO3 will absorb moisture and condense as a sulfuric acid aerosol, typically referred to as acid mist.  相似文献   

12.
Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO2, aerosol SO42−, H2O2 and O3 appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H2O2, O3 and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO42− levels and relative levels of SO2 vs H2O2. Higher aerosol SO42− levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO2 exceeds H2O2. Winter simulations show more nonlinearity than summer simulations.  相似文献   

13.
Electron microscopy-energy dispersive spectroscopy (EM/EDS) can be used to determine the elemental composition of individual particles. However, the accuracy with which atmospheric particle compositions can be quantitatively determined is not well understood. In this work we explore sources of sampling and analytical bias and methods of reducing bias. Sulfuric acid [H2SO4] and ammonium sulfate [(NH4)2SO4] particles were collected on beryllium, silicon, and carbon substrates with similar deposition densities. While [(NH4)2SO4] particles were observed on all substrates, [H2SO4] and ammonia-treated [H2SO4] particles could not be found on beryllium substrates. Interactions between the substrate and sulfuric acid particles are implicated. When measured with EM/EDS, [H2SO4] particles exposed to ammonia overnight were found having lower beam damage rates (0.000 ± 0.002 fraction s−1) than those without any treatment (0.023 ± 0.006 fraction s−1) For laboratory-generated [C10H6(SO3Na)2] particles, the composition determined using the experimental k-factors evaluated from independent particle standards of similar composition and size shows an error less than 20% for all constituents, while greater than 78% errors were found when k-factors were calculated from the theory. This study suggests (1) that sulfate beam damage can be reduced by exposure of atmospheric particle samples to ammonia before analysis, (2) that beryllium is not a suitable substrate for atmospheric particle analysis, and (3) calibration (k-factor determination) using particle standards of similar size and composition to particles present in the atmosphere shows promise as a way of improving the accuracy of quantitative EM analysis.  相似文献   

14.
We propose a source of aerosols in the lower atmosphere associated with the creation, growth, and recombination of ubiquitous cosmogenically generated ions. This particle source should be favorable in the relatively clean, stable marine boundary layer, providing a uniform, continuous fine particle generator in the presence of dimethylsulfide emissions. Through this mechanism, new sulfate aerosols can be formed at sulfuric acid vapor partial pressures well below the supersaturations required for homogeneous binary nucleation of sulfuric acid/water solutions, which is consistent with numerous observations of new particle formation under sub-saturated conditions. The evolving aerosols in turn control the acid vapor concentration and thus modulate the sizes of the precursor ions and the rate of new particle formation. A simple model representing this nonlinear coupled system predicts that the physical and chemical processes connecting ions, vapors, and aerosols effectively constrain the particle population to a relatively narrow range of values. This self-limiting behavior may explain in part the apparent stability of the marine sulfate aerosol, with mean concentrations of the order of several hundred per cubic centimeter.  相似文献   

15.
In order to investigate the effects of humidity on the gas-phase oxidation of SO2 in polluted air and on the subsequent aerosol formation process, photoirradiation experiments were carried out by means of a 4-m3 chamber, in which mixtures containing SO2, NO and C3H6 with concentrations in the ppm range were exposed to simulated solar radiation in different relative humidity (r.h.) conditions. The total amount of oxidized SO2 was quantified from the SO42− yield determined by the chemical analysis of the aerosol product, and a part due to the oxidation by the OH radical was evaluated by estimating the OH concentration from the decay rate of C3H6. The remaining part was assigned to the oxidation by the Criegee intermediate, as it had a good correlation with the progress of the O3 + C3H6 reaction. The contributions of the two oxidizing species to the total conversion and the oxidation rate of SO2 were measured as functions of r.h. As a result, experimental evidence was obtained for the prediction of Calvert and Stockwell's (1983, Envir. Sci. Technol. 17, 428A–443A) simulation that the oxidation due to the Criegee intermediate was retarded by the increase in humidity. The OH contribution, on the other hand, was almost independent of r.h. It was observed consequently that the total oxidized amount of SO2 considerably decreased as r.h. was higher.The humidity effect on the aerosol formation process was found to be more complicated than the effect on the gas-phase chemistry. The maximum rate of increase in the particle number concentration rose linearly with increasing r.h., but the number concentration itself measured at its maximum or at the end of the irradiation reached a ceiling value around r.h. = 30% and went down for higher r.h. The average panicle size in the final stage of the reaction showed a minimum around the same r.h. at which the number concentration was maximum. The H2SO4 concentration in the mist particles, however, decreased monotonically as r.h. got higher. It was suggested that these different responses against the increase in humidity resulted from the cooperation of several processes such as the H2SO4 monomer formation, the H2O condensation, the particle coagulation, etc., which had different dependences on r.h.  相似文献   

16.
The plume opacity and droplet diameters of a monodisperse sulfuric acid aerosol were calculated as a function of the initial H2SO4 concentration, initial H2O concentration and final gas temperature after cooling from an original stack gas temperature of 300°C. Calculation assumptions include heterogeneous heteromolecular condensation of H2SO4 and H2O onto monodisperse nuclei of 0.05 μm dia., three aerosol particle nuclei concentrations of 106, 107 and 108 cm−3 (at 300°C and 760 mm Hg); and a stack or plume diameter of 6 m. The calculated results show that for the conditions considered and with the stack temperatures in excess of 125°C, initial H2SO4 stack gas concentrations of 10ppm or less will result in calculated opacities of less than 20 % for a plume diameter of 6 m. The results show that the calculated opacity is significantly affected by the initial H2SO4 and initial H2O concentrations and the final gas temperature. The increases in the calculated opacities upon cooling of the stack gases are similar in general to the increases in the measured opacities between instack and outstack reported by Nader and Conner (1978) for an oil-fired boiler.  相似文献   

17.
To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO42−) and methanesulfonate (MSx used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS levels. The modelling results indicate that about 80% of the production of MS can be attributed to heterogeneous reactions.Observed submicron nss-SO42− levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO2) to sulfuric acid (H2SO4), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO42− can be explained by condensation of gas-phase H2SO4, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO2 and H2SO4) in good agreement with earlier estimates for the area.  相似文献   

18.
Atmospheric aerosols in subarctic central Alaska were studied for two winter seasons. Both optical absorptivity and excess (non-marine) sulfate undergo seasonal variation similar to that reported in Arctic locations (maximum in late spring and minimum in summer), but the magnitudes are a factor of two smaller than in the Arctic. The meridional variation in aerosol blackness and sulfur content (cleaner air to the south) is contrary to the trend in the Scandinavian Arctic and is interpreted to indicate the existence of pollution sources generally north and west, outside of Alaska's borders.Aerosol size varies with air temperature. Submicrometer aerosol mass and geometric mean diameter (GMD) increase as temperature decreases. Aerosols in all air masses studied were rich in volatile particles. The volatility suggests the presence of aqueous solutions of H2SO4. On the basis of (a) the relativity high aerosol volatility, and (b) the opposite trends between mean diameters and air temperature, it is conjectured that condensation of H2SO4 vapor may be an important mechanism for aerosol evolution in the winter (dark) polar troposphere.  相似文献   

19.
The formation of PM2.5 (aerosol particulate matter less than 2.5 µm in aerodynamic diameter) in association with SO2 emission during sintering process has been studied by dividing the whole sintering process into six typical sampling stages. A low-pressure cascade impactor was used to collect PM2.5 by automatically segregating particulates into six sizes. It was found that strong correlation existed between the emission properties of PM2.5 and SO2. Wet mixture layer (overwetted layer and raw mixture layer) had the function to simultaneously capture SO2 and PM2.5 during the early sintering stages, and released them back into flue gas mainly in the flue gas temperature-rising period. CaSO4 crystals constituted the main SO2-related PM2.5 during the disappearing process of overwetted layer, which was able to form perfect individual crystals or to form particles with complex chemical compositions. Besides the existence of individual CaSO4 crystals, mixed crystals of K2SO4-CaSO4 in PM2.5 were also found during the first half of the temperature-rising period of flue gas. The interaction between fine-grained Ca-based fluxes, potassium vapors, and SO2 was the potential source of SO2-related PM2.5.

Implications: The emission property of PM2.5 and SO2 throughout the sintering process exhibited well similarity. This phenomenon tightened the relationship between the formation of PM2.5 and the emission of SO2. Through revealing the properties of SO2-related PM2.5 during sintering process, the potential interaction between fine-grained Ca-based fluxes, potassium vapors, and SO2 was found to be the source of SO2-related PM2.5. This information can serve as the guidance to develop efficient techniques to control the formation and emission of PM2.5 in practical sintering plants.  相似文献   


20.
A set of atmospheric measurements was carried out at Trombay, Bombay to study the correlation between the concentration variation of freshly formed atmospheric aerosols and the variations in the ambient concentrations of some of the atmospheric trace gases. Daily values of the aerosol concentration both in filtered and unfiltered air together with the concentrations of SO2, NO, O3 and α-activity were measured during a period of 11 months. Statistical analysis of the data shows that variation of particle concentration in the filtered air is a function of not only SO2 variation but also O3 and α-activity variations. The various parameters that are likely to be involved in the formation and the variations of small particle concentration in the atmosphere have been identified.  相似文献   

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