Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds

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.     

Effects of Monochromatic UV-Visible Light and Sunlight on Fe(III)-Catalyzed Oxidation of Dissolved Sulfur Dioxide

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.     

The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

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:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

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.     

On the scavenging of SO2 by large and small rain drops: V. A wind tunnel and theoretical study of the desorption of SO2 from water drops containing S(IV)

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.     

On the scavenging of SO2 by cloud and raindrops: II. An experimental study of SO2 absorption and desorption for water drops in air

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.     

Study of metal aerosol systems as a sink for atmospheric SO2

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 C_Me, 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 C_Me 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.     

A sensitive method for measuring atmospheric concentrations of sulfur dioxide

A new sensitive method for measuring atmospheric concentrations of sulfur dioxide is presented. Samples are obtained using the mist chamber, which collects highly water-soluble gases with high efficiency, and concentrates them in a small volume of water. Particles are removed from the sampled air stream with a teflon filter, before it enters the mist chamber. After collection, the pH of the water is raised above pH 10 using sodium carbonate, then hydrogen peroxide (H₂O₂) is added to oxidize sulfur that may be present in the sulfur (IV) oxidation state, to sulfate. After a reaction time of at least 16 hours, the sulfate concentration is measured by ion chromatography. From the sulfate concentration, the water volume used in the mist chamber, and the volume of air sampled, the atmospheric concentration of SO₂ is computed. The method is not sensitive to other atmospheric sulfur gases such as DMS, SC₂, H₂S, COS, or MSH. The estimated overall precision of the method is 10%. The detection limit at the present stage of technique development is approximately 20 ppt (parts per trillion, or 10^-12 mol · mol^-1) for a 45 minute sampling time, with lower concentrations being detectable with lower precision.     

Kinetics of ammonia and ammonium ion inhibition of the atmospheric oxidation of aqueous sulfur dioxide by oxygen

This is the first study, which shows both NH₃ and NH₄⁺ to inhibit the autoxidation of aqueous SO₂ in the pH range 7.0–8.5. The rate of the autoxidation, R _aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law:

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.     

A Simple Kinetic Model for Autoxidation of S(IV) Oxides Catalyzed by Iron and/or Manganese Ions

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:r_tot = S_Fe · r_Fe + S_Mn · r_Mn ,where r_Fe and r_Mn are the reaction rates in the presence of Fe(II) and Mn(II), respectively. S_Fe and S_Mn are proportional factors, which account for the synergistic effect. The proposed power law rate equation predicts the reaction kinetics very well. The values of S_Fe (1.35) and S_Mn (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.     

Dimethylsulfide oxidation and the ratio of methanesulfonate to non sea-salt sulfate in the marine aerosol

A box model of DMS oxidation in the clean, low-NO _x marine atmospheric boundary layer has been used to predict the latitude dependence of the aerosol methanesulfonate to non sea-salt sulfate ratio. The observed latitude dependence of this ratio in the Southern Hemisphere can be reproduced reasonably well if the full suite of reactions proposed by Yin et al. (1990a) is employed, and a strong temperature dependence is specified in the rates of decomposition of CH₃SO₂ and CH₃SO₃ radicals.     

Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres

A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO₂ + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H₂SO₄ in reaction with SO₂ and detection of H₂SO₄ using an ion molecule reaction with NO₃^─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO₃^─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 10⁵ molecule cm^-3 for OH and 30% and 1 × 10⁵ molecule cm^-3 for HO₂ at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 10⁵ molecules cm^-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO₂.     

Numerical simulation on the rainout-removal of sulfur dioxide and acidification of precipitation from stratiform clouds

The rainout-removal of SO₂ and the acidification of precipitation from stratiform clouds are simulated using a one-dimensional, time-dependent model, parameterized microphysically in which dissolution and dissociation of gaseous SO₂ and H₂O₂, and oxidation reaction in aqueous phase are taken into account. The effects of dynamic factors, including updraft flow and turbulent transport, and the concentration of gaseous SO₂ and H₂O₂ being transported into the clouds on pH value of the precipitation, the conversion rateS(IV)-S(VI) and the wet deposition rate of SO₂ are discussed. This work was supported by fund from the National Scientific Foundation of China.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

Carboxylic Acids: Seasonal Variation and Relation to Chemical and Meteorological Parameters

Formic and acetic acid measured as daily averages in 1993–1994show equal and highly correlated concentrations up to 3 ppb in the summer(May–August). In the winter (October–March) the formicacid/acetic acid ratio was 0.6 and the formic acid concentrations wereusually below 1 ppb. In winter the carboxylic acids correlate withO_x, NO_y, SO₂ and particulatesulphur. The main sources are suggested to be ozonolysis of anthropogenicalkenes and reactions between peroxyacetyl radicals and RO₂radicals. In spring–summer the carboxylic acids correlate withO₃, O_x, HNO₃, PAN,NO_y, SO₂, particulate sulphur and temperature.In addition to the sources of the winter a contribution from ozonolysis ofbiogenic alkenes is likely. Quite similar formic acid/acetic acid ratios forall wind directions suggest that the source(s) are atmospheric oxidationprocesses distributed over large areas. The highest concentrations occurringfor winds from east to south and the correlation with e.g., particulatesulphur indicate chemical production in polluted air masses during longrange transport.     

Hierarchical factor analysis applied for interpreting chemical elements deposited with atmospheric precipitation in Karelia

The data on deposition density of Ag, Al, As, B, Ba, Be, Bi, Br, Ca, Cd, Co, Cr, Cs, Cu, Fe, I, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Se, Si, Sn, Sr, Th, Tl, U, V, Zn, Cl^?, F^?, NO ₃ ^? , and SO ₄ ^2? in atmospheric precipitation were derived at six stations in the Republic of Karelia. The structure and space-time distribution of five sets (factors) of chemical components of the first order and two factors of the second order are revealed with the help of hierarchical factor analysis. Factor analysis of the second order demonstrated that atmospheric precipitation chemistry at all stations considered differs greatly in the winter and summer, forming two independent sets of components. The first-order factors revealed chemical indicators characterizing specific features of the atmospheric precipitation chemistry in the Karelian regions studied.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Analysis of summertime atmospheric transport of fine particulate matter in Northeast Asia

In Northeast Asia, the effect of long-range transport of air pollutants is generally pronounced in spring and winter, but can be important even in summer. This study analyzed summer-time atmospheric transport of elemental carbon (EC) and sulfate (SO₄ ^2?) with the Community Multiscale Air Quality (CMAQ) model driven by the Weather Research and Forecasting (WRF) model. The WRF/CMAQ modeling system was applied to regions ranging from Northeast Asia to the Greater Tokyo Area in Japan in summer 2007. In terms of EC, while the model simulated well the effect of long-range transport, the simulation results indicated that domestic emissions in Japan dominantly contributed (85%) to EC concentrations in the Greater Tokyo. In terms of SO₄ ^2?, the simulation results indicated that both domestic emissions (62%) and long-range transport from the other countries (38%) substantially contributed to SO₄ ^2? concentrations in the Greater Tokyo. Distinctive transport processes of SO₄ ^2? were associated with typical summer-time meteorological conditions in the study region. When a Pacific high-pressure system covered the main island of Japan, domestic emissions, including volcanic emission, dominantly contributed to SO₄ ^2? concentrations in the Greater Tokyo. When a high-pressure system prevailed over the East China Sea and low-pressure systems passed north of Japan, synoptic westerly winds associated with this pressure pattern transported a large amount of SO₄ ^2? from the continent to Japan. In addition, although heavy precipitation and strong wind decreased SO₄ ^2? concentrations near the center of a typhoon, peripheral typhoon winds occasionally played an important role in long-range transport of SO₄ ^2?.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.