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1.
The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.  相似文献   

2.
Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O2-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–rS(IV) = k · [S(IV)] · [Fe(III))] · e -b·[Ox]  相似文献   

3.
The effect of UV-visible light and natural sunlight on the Fe(III)-catalyzed oxidation of dissolved sulfur dioxide has been studied under the conditions representative for those of acidified atmospheric liquids. The experimental results have shown that both sunlight and UV-visible light enhance the rate of Fe(III)-catalyzed oxidation of aqueous sulfite with wavelength ranging from 300 to 575 nm. The light enhanced oxidation is mainly due to photochemical formation of OH radicals from Fe(OH)2+ complexes in the wavelength region below 420 nm and SO3•− free radicals from Fe(III) sulfite complexes above 420 nm in the absence of organic ligands. Like the Fe(III)-catalyzed thermal chemical oxidation, the Fe(III)-catalyzed photochemical oxidation is also first order with respect to sulfite ion concentration. The sunlight irradiation can increase the Fe(III)-catalyzed oxidation of S(IV) over 45%. The presence of organic complex ligands, such as oxalate, can completely inhibit the Fe-catalyzed oxidation of S(IV) in the dark. However, the photolysis of Fe(III)-oxalato complexes generates oxalate free radicals, leading to the formation of H2O2 and OH radicals and the oxidation of S(IV). The rate of Fe(III)-catalyzed oxidation of S(IV) species is found to increase with increasing light intensity. The effects of sunlight on the Fe(III)-catalyzed oxidation of S(IV) should be taken into account when predicting the daytime rates of sulfuric acid formation in atmospheric water droplets.  相似文献   

4.
The kinetics of the S(IV) oxidation by oxygen in the presence of Mn(II) ions and acetic acid has been studied. Experiments were carried out at 25°C, 3.5?≤?pH?≤?5.0, [S(IV)]≈1?×?10?3 mol/dm3, 1?×?10?6 mol/dm3?≤?[Mn(II)]?≤?1?×?10?5 mol/dm3, 1?×?10?6 mol/dm3?≤?[CH3COOH]?≤?1?×?10?4 mol/dm3. Based on the experimental results, rate constants and orders of the reactions were determined. Depending on the reaction conditions, the observed rate constants for the Mn(II)-catalysed S(IV) oxidation ranged between 3.91?×?10?8 and 8.89?×?10?7 (mol/dm3) s?1, and in the presence of acetic acid they ranged between 2.95?×?10?8 and 7.45?×?10?7 (mol/dm3) s?1. The reaction order in S(IV) was zero for both reactions. The effect of Mn(II) ion and acetic acid concentrations as well as an initial pH of the solution on the S(IV) oxidation rate was discussed. It was found that the rate of the S(IV) oxidation depends on the initial pH of the solution but it is independent of the pH change during the reaction. Acetic acid has a weak inhibiting effect on the Mn(II)-catalysed S(IV) oxidation. Under the experimental conditions the S(IV) oxidation rate decreased no more than twice.  相似文献   

5.
The reaction kinetics of S(IV) autoxidation catalyzed by single metal ions of Mn(II) and Fe(II) or Fe(III) and by a mixture of Mn(II) and Fe(II) under the conditions representative for acidified atmospheric liquid water was investigated. A simple power law kinetic model based on the stability constants for metal-sulfito complexes formed during the first step of a radical chain mechanism predicts well the kinetics for the reactions catalyzed by single metal ions. The calculated stability constants for iron (5.7×103 dm3 mol–1) and manganese (10×104 dm3 mol–1) sulfito complexes are close to those reported in the literature. The catalytic synergism between Mn(II) and Fe(II) was confirmed. For this system the following power law rate equation was suggested:rtot = SFe · rFe + SMn · rMn ,where rFe and rMn are the reaction rates in the presence of Fe(II) and Mn(II), respectively. SFe and SMn are proportional factors, which account for the synergistic effect. The proposed power law rate equation predicts the reaction kinetics very well. The values of SFe (1.35) and SMn (15) indicate that the influence of Fe(II)/Fe(III) on Mn(II)/Mn(III) cycling is larger than, vice versa, agreeing with the reaction mechanism proposed for the S(IV) autoxidation catalyzed by mixed metal ions.  相似文献   

6.
Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 109 M–1 s–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 108 M–1 s–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO– 4 adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10–5 m3 m–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO2 in the atmosphere.  相似文献   

7.
Precipitation samples collected at Erdemli, Turkey, during February 1996–June 1997 were analysed to determine iron content and speciation. The purpose of the measurements was to examine the atmospheric abundance of iron and to quantify its solubility in the region. Spectrophotometric analyses of Fe(II) and reducible Fe(III) in precipitation samples, along with measurements of pH, conductivity, filterable iron (Fefilt), particulate aluminium (Alpar) and particulateiron (Fepar) were performed to determine iron solubility, which principally affects its bioavailability. Backward trajectories corresponding to the sampling dates were analysed to determine the sources of atmospheric constituents arriving at the site. Among these, the mineral dust transported from the Great Sahara to the region is considered to be a rich source of iron. The concentration of Fe(II) varied from below detection limit (0.02 M) up to 0.42 M,while the maximum concentration of total reactive Fe (referred as Fe(II) + reducible Fe(III) = Fereac) was found to be 1.0 M in precipitation. A strong correlation was found between particulate Fe and Al fractions, both of crustal origin. No correlation was observed between the soluble and insoluble fractions of iron. The soluble iron fraction, Fe(II) concentration varied independently from the concentrations of reducible Fe(III), Fefilt, Fepar, and from the pH of the precipitation. The Fefilt fraction (size < 0.45 m), measuredby Atomic Absorption Spectrophotometer, and frequently interpreted to be the soluble iron fraction in the literature, was found to be significantly higher than the corresponding Fereac fraction inprecipitation samples, most likely due to the colloidal iron content of the Fefilt fraction passing through the 0.45 m pore size filter. The volume weighted mean Fefilt concentration of the precipitation samples collected during the episodic `red rain' events was found to be relatively higher. The geometric mean ratios of soluble Fe(II) and of Fereac to Total Fe (Fefilt + Fepar), werefound to be 1.6% and 2.1%, respectively, while the mean ratioof Fefilt to Total Fe was 9.6%. The flux of bioavailable iron (Fereac)fraction in most atmospheric wet deposition events was found to be sufficient for supporting the maximum primary production rates that are typical for the Eastern Mediterranean Sea.  相似文献   

8.
Iron occurs in rain as particulateand dissolved Fe and includes both Fe(II) and Fe(III)species. Model calculations and correlation analysisindicate Fe(II)(aq) occurs almost exclusively as thefree ion whereas Fe(III)(aq) occurs as both ironoxalate and Fe(OH)2 +(aq) with largevariations over the pH range from 4.0 to 5.0. Complexation with humic-like compounds may also beimportant for Fe(III)(aq); however, the concentrationand structural characteristics of these compounds haveyet to be determined. 112 rain samples were collectedfor iron analysis in Wilmington, North Carolina,between 1 July 1997, and 30 June 1999. Total iron,particulate iron and Fe(III)(aq) were higher inconcentration in summer and spring rain relative towinter and autumn rain. Fe(II)(aq) concentrations, incontrast, did not vary seasonally. Particulate iron,which was approximately half the total rainwater iron,was highest between noon and 6 p.m. (EST), probably dueto more intense regional convection including land-seabreezes during that time. The ratio ofFe(II)(aq)/Fe(III)(aq) was also highest in rainreceived between noon and 6 p.m., which most likelyreflects photochemical reduction of Fe(III)(aq)complexes to form Fe(II)(aq). A conceptual modeldepicting the interplay between iron species, lightintensity and organic ligands in rainwater ispresented.  相似文献   

9.
Iron is the most abundant transition metal in the atmosphere and can play a significant role in cloudwater chemistry where its reactivity is closely related to the partitioning between Fe(II) and Fe(III). The objective of this work is to determine the total iron content and the iron speciation in a free tropospheric site, and to understand which factors influence these parameters. We collected 147 samples of cloudwater during 34 cloud events over a period of four years at the puy de Dôme summit. Besides iron we measured other chemical compounds, solar radiation, physico-chemical and meteorological parameters potentially connected with iron reactivity. The total iron concentrations ranged from 0.1 to 9.1 μM with the major frequency occurring at low levels. The pH and presence of organic complexants seem to be the most significant factors connected with total dissolved iron; while the iron oxidation state seems to be an independent factor. Light intensity, presence of complexants or oxidants (H2O2) do not influence the Fe(II)/Fe(Total) ratio, that was quite constant at about 0.75. This could be due to the potential redox that forces the Fe(II)-Fe(III) couple to the reduced form or, more probably to the complexation by Natural Organic Matter, that can stabilize iron in its reduced form and prevent further oxidation. Our field measurements did not show the diurnal cycle observed in surface water and predicted by models of atmospheric chemistry. This result prompts a more careful review of the role of iron and, by analogy, all the transition metals in atmospheric liquid phase, often over-estimated in the literature.  相似文献   

10.
An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] T (2.5–5.0×10–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K 7 andK 8 can be interpreted as intrinsic constants for the coordination of HSO 3 – by FeOH2+ and Fe3+, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×106 M–1 s–1 which is comparable to rate of reaction of FeOH2+ with SO 4 2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.  相似文献   

11.
To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO3.1/2 H2O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe2(SO4)3 or CoSO4, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)108 M–1s–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.  相似文献   

12.
  相似文献   

13.
Differences in total iron and manganese concentrations between large (d > 23 m) and small (4 < d < 23 m) cloud and fog drops were investigated at four locations in the United States. The study examined coastal stratus and stratocumulus clouds in southern California and northern Oregon, frontal and orographic clouds at Mt. Mitchell, North Carolina, and radiation fogs in California's San Joaquin Valley. The speciation of iron as a function of drop size was also examined in some fog samples from the San Joaquin Valley. Total iron and manganese concentrations were generally higher in large drops than in small drops in clouds sampled at Mt. Mitchell and along the southern California coast. These species were typically enriched in small drops at the Oregon coast and San Joaquin Valley sites. Ratios of dissolved Fe(III) to total dissolved Fe ranged from 0.88 to 0.93 in small fog drops. Non-uniform distributions of iron and manganese across the drop size spectrum can influence rates of metal catalyzed S(IV) autooxidation. Approximately 50% of the sampled clouds were calculated to experience autooxidation rate enhancements greater than 30% due to variations in drop acidity and catalyst concentrations with drop size.  相似文献   

14.
The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO 3 − up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation
the concentration of complex is calculated from the stability constant K and concentrations of reactants at a specific reaction time. This rate equation adequately predicts the reaction kinetics in the pH range 3–5, in the concentration ranges 0.1 ≤ [HSO 3 − ] ≤ 0.4 mM and 2 ≤ [Mn(II)] ≤ 14.6 μM. For the temperature range 15–35 °C, the estimated value for activation energy is 92.0 ± 0.1 kJ mol−1 and the Gibbs free energy of formation of the manganese-sulfito complex is −20.4 ± 0.3 kJ mol−1. Furthermore, the kinetics for catalytic reactions with pH maintained constant during the reaction course as well as with initial pH adjusted only at the start of the reaction, is described satisfactorily by the present model.  相似文献   

15.
In this study, the results of four different field experiments concerning the speciation of iron and the concentrations of some other chemical compounds in cloudwater samples are compared to one-another. Hydrogen peroxide concentrations were higher during campaigns, conducted at sites not much influenced by anthropogenic emissions as compared to those conducted at more polluted areas. In contrast, percentages of S(IV) in the cloudwater were lowest at the rural sites and highest at the sites polluted by human activities, indicating a consumption of hydrogen peroxide in the oxidation reaction with S(IV). The concentration of dissolved iron was observed to correlate with the percentage of S(IV), which may be an essential point for the reductive dissolution of oxidic iron compounds of the aerosol particles. As far as the speciation of the dissolved iron is concerned, it became obvious that the percentage of Fe(III) is anticorrelated to the concentration of dissolved iron. This clearly shows the important effect of the chemical and/or photo reductive ways of dissolving the iron(III)-compounds from the aerosol particles. However, a correlation between the pH-value and hydrogen peroxide was observed.  相似文献   

16.
Since 1978, a measuring station has been operated at Cape Point (34°21 S, 18°29 E). In this article, results of measurements of CO, CFCl3, CCl4, O3, N2O and CH4 are presented as monthly means and analyzed with respect to long-term trends and seasonal variations. For CO and CH4, very similar seasonal variations have been observed, indicating strong interrelations between these two gases. For CO and O3, no significant changes of the mean annual concentrations can be established for the observation periods of 10 and 5 years, respectively. The measurements yield a growth rate of 9.1 pptv yr-1 for CFCl3 (1980–1987) and 0.6 ppbv yr-1 for N2O (1983–1987). The concentration increases of CH4 (10.3 ppbv yr-1 for 1983–1987) and of CCl4 (2.1 pptv yr-1 for 1980–1988) are analyzed for temporal changes during the last years.Presented at the Second Conference on Baseline Observations in Atmospheric Chemistry (SABOAC II) in Melbourne, Australia, November 1988.  相似文献   

17.
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   

18.
Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex (Fe(Ⅲ)-Ox). The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(Ⅲ)-Ox under solar irradiation. Although the photolysis mechanisms of Fe(Ⅲ)-Ox have been investigated extensively, information about the oxidation of volatile organic compounds (VOC), specifically the potential for Secondary Organic Aerosol (SOA) formation in the Fe(Ⅲ)-Ox system, is lacking. In this study, a ubiquitous VOC methacrolein (MACR) is chosen as a model VOC, and the oxidation of MACR with Fe(Ⅲ)-Ox is investigated under typical atmospheric water conditions. The effects of oxalate concentration, Fe(Ⅲ) concentration, MACR concentration, and pH on the oxidation of MACR are studied in detail. Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(Ⅲ). The oxidation rate of MACR also accelerates with increasing concentration of oxalate. The effect of Fe(Ⅲ) is found to be more complicated. The oxidation rate of MACR first increases and then decreases with increasing Fe(Ⅲ) concentration. The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration. The production of ferrous and hydrogen peroxide, pH, and aqueous absorbance are monitored throughout the reaction process. The quenching experiments verify that ·OH and (O-·2) are both responsible for the oxidation of MACR. MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight, which contributes to the yield of SOA. These results suggest that Fe(Ⅲ)-Ox plays an important role in atmospheric oxidation.  相似文献   

19.
Measurements of Hg (total gas-phase, precipitation-phase andparticulate-phase), aerosol mass, particulate 210Pb and7Be and precipitation 210Pb were made at an atmosphericcollection station located in a near remote area of northcentral Wisconsin,U.S.A. (46°10N, 89°50W) during the summers of 1993, 1994and 1995. Total Hg and 210Pb were observed to correlate strongly(slope = 0.06 ± 0.03 ng mBq-1; r 2 =0.72) in rainwater. Mercury to 210Pb ratios in particulate matter(0.03 ± 0.02 ng mBq-1; r 2 = 0.06) wereconsistent with the ratio in rain. Enrichment of the Hg/mass ratio (approx.5–50×) relative to soil and primary pollutant aerosols indicatedthat gas-to-particle conversion had taken place during transport. Comparisonof these results with models for the incorporation of Hg into precipitationindicates that atmospheric particles deliver more Hg to precipitation than canbe explained by the presence of soot. A lack of correlation between totalgas-phase Hg (TGM) and a 7Be/210Pb function suggests novertical concentration gradient within the troposphere, and allows an estimateof TGM residence time of 1.5 ± 0.6 yr be made based on surface airsamples.  相似文献   

20.
Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO2), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO4 2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10–12; 24 ppt=1 nmol m–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m–2 d–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO2 concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO2 in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO2. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO2 by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO2 and one-third to MSA. On the other hand, MSA/nss-SO4 2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO4 2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO2, nss-SO4 2- values decreased significantly in the middle FT. NH4 +/nss-SO4 2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.  相似文献   

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