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]     

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

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.     

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.     

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

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.     

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.     

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.     

Field Experimental Investigations on the Fe(II)- and Fe(III)-Content in Cloudwater Samples

The Fe(II)/Fe(III)-partition in cloudwater samples collected during two field campaigns is evaluated. It turned out that the simultaneous occurrence of complexing and reducing substances in the atmosphere and the cloud processing increase the solubility of iron compounds present in aerosol particles. A correlation between the concentration of iron(II) in the liquid phase and the intensity of the solar irradiation was observed for most of the cloudwater samples. This could be due to the fact that both the photochemical reduction of the iron(III) complexes and the photochemical reductive dissolution of iron(III)(hydr)oxides are depending on the pH-value. Iron(II) seems to be oxidised back to iron(III) preferably by hydrogen peroxide during the night. Positive correlations were received e.g. between the concentration of dissolved iron and the concentration of oxalate and between the percentage of iron(III) and the concentration of hydrogen peroxide. A negative correlation was found e.g. between the concentration of dissolved iron and the pH-value. The uncertainty of the whole process of sampling and analysis was investigated and the conformity of the results was satisfying considering the sometimes difficult conditions during a field campaign.     

Temporal Variability of Iron Speciation in Coastal Rainwater

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.     

Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

The influence of some low weight mono- and di-carboxylic acids, which were selected on the basis of analysis of the water-soluble fraction of size segregated marine and urban aerosols collected in Slovenia, on the kinetics of S(IV) oxidation catalyzed by Mn(II) under conditions representative of tropospheric liquid water, was investigated. Mono-carboxylic acids inhibit the oxidation, with the strongest influence found for formic acid. Inhibition by glycolic and lactic acid was found to be very similar, while the lowest inhibition was caused by acetic acid. Our results are in agreement with the proposed mechanism, i.e. scavenging of sulfate radicals, since the inhibiting effect of the individual acid increases with higher dissociation constant. An exception is formic acid, where the additional inhibiting steps should be responsible for the induction period and thus for higher inhibition. Malic and malonic acids have practically no influence, while oxalic acid slows down the oxidation, although to a lesser extent than mono-carboxylic acids. An extended version of a previously derived generalized simple kinetic model was also derived and applied for predicting the reaction kinetics in the presence of all examined carboxylic acids at pH 3.5 and 4.5.     

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 oxidation of S(IV) during riming by cloud droplets

Experiments have been performed to investigate whether the process of freezing during riming in clouds may induce oxidation of dissolved SO₂ to SO ₄ ^2– . The experiments were conducted in a cold room at varying temperatures between –6 and –15 °C. Solutions containing dissolved SO₂ and NH₄OH in various proportions, in the range of concentrations between 3×10^–5 and 10^–3 M, were sprayed. Rime was collected on a rotating cylinder and analyzed. Absorption of oxygen from laboratory air was prevented, except in the spray, to avoid spurious oxidation. Blank experiments were made at +3 to +6 °C. The results indicate clearly that, as the dominant cation becomes NH ₄ ⁺ rather than H⁺, substantial oxidation of S(IV) occurs during riming. This is consistent with redox reactions taking place as a result of charge separation at the ice-water interface during freezing.     

Aqueous Oxidation of Sulfur(IV) Catalyzed by Manganese(II): A Generalized Simple Kinetic Model

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

Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

The Role of Multiphase Chemistry in the Oxidation of Dimethylsulphide (DMS). A Latitude Dependent Analysis

A kinetic model for the OH-initiated homogeneous gas phase oxidation of dimethylsulfide (DMS) in the atmosphere (Saltelli and Hjorth, 1995), has been extended here to include the liquid phase chemistry. The updated model has then been employed to predict the temperature dependency of the MSA/nss-SO42- ratio. Model predictions have been compared with observational data reported in Bates et al. (1992). Sensitivity and uncertainty analysis has been performed in a Monte Carlo fashion to identify which are the important uncertainties on the input parameters and which are the possible combinations of parameter values that could explain the field observations. Results of the analysis have indicated that the temperature dependencies of the interactions between gas phase and liquid phase chemistry may to a large extent explain the observed T-dependence of the MSA/nss- SO42- ratio. The potential role of multi-phase atmospheric chemistry, not only in the case of SO2 but also of other oxidation products of DMS and, particularly, of DMS itself, has been highlighted.     

The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater

Elevated concentrations of S(IV) and formaldehyde were observed in fog- and cloudwater at sites in California. The highest concentrations (up to 3 mM S(IV) and 0.7 mM CH₂O) were measured at Bakersfield, during a prolonged period of repeated fog. In Bakersfield [S(IV)] generally exceeded [CH₂O], while in the Los Angeles area the reverse was observed. The lowest concentrations of both species were observed at marine and high altitude sites away from local emissions. Equilibrium computations indicate that high concentrations of S(IV) cannot be achieved without the formation of S(IV)-RCHO adducts.     

雅安市近地面空气负(氧)离子状况初探

本文基于2010~2011年雅安市气象局进行的“雅安市空气负(氧)离子观测研究”资料,对雅安市近地面空气负(氧)离子状况进行了初步分析。主要结论为:(1)雅安市具有优异的空气负(氧)离子生态资源,城区空气负(氧)离子浓度等级大多数情况都在6级(负离子浓度≥2100个/cm³)以上,近郊的负(氧)离子浓度大多数情况都超过6级,较高时可接近60000个/cm³,风景区的负(氧)离子浓度大多数情况都远远超过6级,较高时≥60000个/cm³,是名符其实的“天府之肺”、“中国的绿色宝石”和“中国生态气候城市”。(2)雅安市境内,空气负(氧)离子浓度的日变化规律通常为7时左右最大,15时左右最低;空气负(氧)离子浓度和天气、相对湿度有较密切的关系,通常的规律为:降雨后的清晨、雷雨后,空气负(氧)离子浓度明显增加;空气负(氧)离子浓度和相对湿度成正相关。(3)和国内已有研究资料的地区比较,雅安市空气负(氧)离子浓度水平在国内为最高地区之一。     

热带西太平洋定点海域降水的化学特征研究

对热带西太平洋定点（４°Ｓ，１５６°Ｅ）海域长达４个月的降水化学调查，研究了降水中化学成分的变化特征、连续性与断续性降水过程和西风暴发事件（ＷＷＢＥ）及大风暴降雨过程中降水的化学成分。结果表明：定点海域（４°Ｓ，１５６°Ｅ）纯“海洋性”降水的ｐＨ为５．５５，其Ｍｎ／Ｆｅ比值为０．５４，Ｃｌ－与ＳＯ２－４是降水中最大量的离子；连续性降水ｐＨ呈“∨”型分布，Ｅｈ呈“∧”分布，总－２价硫的浓度Ｓ（－Ⅱ）呈降低分布，且最后趋于稳定，ＳＯ２－４，ＮＨ＋４，ＰＯ３－４等在降雨开始后一段时间出现最大值，呈现与其它组分相反的行为；断续性降水ｐＨ，Ｅｈ趋于升高。西风暴发事件（ＷＷＢＥ）期间，绝大多数组分在降水中浓度高于ＷＷＢＥ发生前、后的浓度，而ＮＨ＋４低于ＷＷＢＥ发生前、后的浓度，ＰＯ３－４，ＳｉＯ２－３则是低于ＷＷＢＥ发生前的浓度，而高于发生后的浓度，大风暴降雨Ｃｌ－，ＳＯ２－４的浓度比正常降雨时可高达数倍，说明海上大风暴使大量海水滴被卷入空中，又随降雨落下，这时的降水ｐＨ也有显著增高。     

典型南涝(旱)北旱(涝)梅雨大气环流特征差异及动力诊断分析

利用NCEP逐日再分析资料,采用合成分析和动力诊断方法比较研究了典型南涝(旱)北旱(涝)梅雨大气环流特征差异,逐一考察了近20种物理量对其主雨带位置的诊断识别能力.结果表明:典型南涝(旱)北旱(涝)梅雨极涡偏强(弱),亚欧中高纬槽脊振幅较大(小),中纬度110°E～150°E地区位势高度明显偏低(高),冷空气势力偏强(...     

Sub-seasonal to Seasonal Hindcasts of Stratospheric Sudden Warming by BCC_CSM1.1(m):A Comparison with ECMWF

This study focuses on model predictive skill with respect to stratospheric sudden warming(SSW) events by comparing the hindcast results of BCC_CSM1.1(m) with those of the ECMWF's model under the sub-seasonal to seasonal prediction project of the World Weather Research Program and World Climate Research Program. When the hindcasts are initiated less than two weeks before SSW onset, BCC_CSM and ECMWF show comparable predictive skill in terms of the temporal evolution of the stratospheric circumpolar westerlies and polar temperature up to 30 days after SSW onset. However, with earlier hindcast initialization, the predictive skill of BCC_CSM gradually decreases, and the reproduced maximum circulation anomalies in the hindcasts initiated four weeks before SSW onset replicate only 10% of the circulation anomaly intensities in observations. The earliest successful prediction of the breakdown of the stratospheric polar vortex accompanying SSW onset for BCC_CSM(ECMWF) is the hindcast initiated two(three) weeks earlier. The predictive skills of both models during SSW winters are always higher than that during non-SSW winters, in relation to the successfully captured tropospheric precursors and the associated upward propagation of planetary waves by the model initializations. To narrow the gap in SSW predictive skill between BCC_CSM and ECMWF, ensemble forecasts and error corrections are performed with BCC_CSM. The SSW predictive skill in the ensemble hindcasts and the error corrections are improved compared with the previous control forecasts.