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.     

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.     

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.     

Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch

In this study the chemical nature of the bulk of water soluble organic compounds in fine atmospheric aerosol collected during summer 1998 at the Jungfraujoch, Switzerland (3580 m asl) is characterised. The mass concentration of water soluble organic substances was similar to those of major inorganic ions, and the water soluble organic matter was found to be composed of two main fractions: (i) highly polyconjugated, acidic compounds with a varying degree of hydrophobicity and (ii) slightly polyconjugated, neutral and very hydrophilic compounds. The contribution of both fractions to the total water soluble organic carbon was about 50%. Separation into individual components was impossible either by HPLC or capillary electrophoresis which indicates the presence of a high number of chemically similar but not identical species. Results obtained by ultrafiltration and HPLC-MS have shown that the molecular weights are of the order of several hundreds. Most of the protonation constants for the acidic compounds determined by capillary electrophoresis were in the range 10⁴–10⁷.     

Application of Non-Ionic Solid Sorbents (XAD Resins) for the Isolation and Fractionation of Water-Soluble Organic Compounds from Atmospheric Aerosols

A detailed procedure using non-ionic macropourous XAD-8 and XAD-4 resins is presented for the isolation and fractionation of aerosol water-soluble organic compounds (WSOC) from aerosol samples. The procedure entails adsorption of WSOC fraction onto XAD-8 and XAD-4 resins, desalting of the adsorbed organic material with ultra-pure water, elution of the retained organic matter with 40% MeOH solution and freeze-drying. Due to resin’s different properties and to certain hydrophobic/hydrophilic interactions between the resin polymers and the organic matter, two major fractions were obtained; namely the XAD-8 and the XAD-4 eluates. The XAD-8 eluate, which accounts for 55–60% of total aerosol WSOC, is represented by partially acidic compounds with significant hydrophobic moieties. The XAD-4 fraction holds few conjugated systems and a higher content of hydrophilic structures with low molecular size, and accounts for 9% of total WSOC. The isolated WSOC sub-fractions were nearly free from inorganic species, and successful recoveries of organic matter from the resins were accomplished. With this procedure the XAD-8 eluate yields a mixture representative of those WSOC that are highly conjugated compounds in atmospheric aerosols. It also allows a successful characterisation of the organic material by advanced analytical techniques without the interference of inorganic species present in the original sample of atmospheric particles.     

Synchronous Scan and Excitation-Emission Matrix Fluorescence Spectroscopy of Water-Soluble Organic Compounds in Atmospheric Aerosols

Three-dimensional excitation–emission matrix (EEM) fluorescence spectra of water-soluble organic compounds (WSOC) from aerosol samples were measured and compared with those reported in the literature for natural dissolved organic matter. The EEM profiles of the WSOC presented three characteristic excitation/emission (_Exc/_Em) peaks: 240/405 nm, 310/405 nm and 280/340 nm. The fluorescence intensities at _Exc/_Em240/405 nm and _Exc/_Em310/405 nm are located at wavelengths shorter than those reported for aquatic humic substances, indicating a smaller content of both aromatic structures and condensed unsaturated bond systems in the WSOC fraction. The EEM profiles of fractions obtained by the isolation procedure of the WSOC by the XAD resins showed that a fractionation has occurred and the XAD-8 eluate is highly representative of the total WSOC of collected aerosol. Synchronous scan spectra were more detailed than conventional fluorescence emission spectra, appearing more suitable for studying multicomponent samples such as the WSOC from atmospheric aerosols.     

Theoretical Modeling of the Size-Dependent Influence of Surface Tension on the Absorptive Partitioning of Semi-Volatile Organic Compounds

The influence of surface tension on the formation of secondary organic aerosol (SOA) is investigated in this study using a size-dependent absorptive partitioning model. A theoretical framework is offered to estimate the surface tension of multi-component aerosols consisting of organic compounds and water. The size-dependent influence of surface tension on the absorptive partitioning of semi-volatile organic compounds is examined via numerical simulations of systems of representative pre-existing aerosol (PA) components and semi-volatile organic compounds that have been observed to constitute SOA. Results indicate that if nonpolar organic species constitute a significant fraction of the PA, the Kelvin effect on SOA formation may be negligible. However, if PA is dominated by polar organic compounds, the Kelvin effect on SOA formation is significant when the PA initial diameter is smaller than approximately 200 nm. If the PA is an aqueous aerosol, the Kelvin effect on SOA formation is most important. A simplified computational scheme for estimation of the Kelvin effect is developed in this study and feasibly could be coupled into three-dimensional air quality models that simulate SOA formation. Available observations also suggest that future modeling and analysis of SOA formation may need to consider the Kelvin effect. Concrete testing of the purely theoretical model presented here requires carefully designed observations that examine the phase distribution of secondary organic compounds between the gas phase and aerosol particles small enough to be affected by surface tension.     

Aerosol Indirect Effects on Warm Clouds in the Grid-Point Atmospheric Model of IAP LASG (GAMIL)

Aerosol indirect effects on warm clouds are estimated in the Grid-point Atmospheric Model of the State Key Laboratory of Numerical Modeling for Atmospheric Sciences and Geophysical Fluid Dynamics,Institute of Atmospheric Physics(IAP LASG)(GAMIL) with a new two-moment cloud microphysics scheme using two different physically-based aerosol activation parameterizations:Abdul-Razzak and Ghan,and Nenes and Seinfeld.The annual global mean changes in shortwave cloud forcing from preindustrial times to present day(a measure of the aerosol indirect effects) estimated from these two parameterizations are remarkably similar:0.76 W m?2 with the Abdul-Razzak and Ghan parameterization,and 0.78 W m?2 with the Nenes and Seinfeld parameterization.Physically-based parameterizations can provide robust representations of aerosol effects on droplet nucleation,meaning that aerosol activation is no longer the most uncertain factor in modeling aerosol indirect effects.     

SEM-EDX Characterisation of Tropospheric Aerosols in the Negev Desert (Israel)

Individual aerosol particles collected in the Negev desert in Israel during a summer and winter campaign in 1996–1997 were analysed by scanning electron microscopy with energy-dispersive X-ray analysis. Hierarchical cluster analysis was performed to interpret the data on the basis of particle diameter and composition. Eleven particle classes (groups) provided clues on sources and/or particle formation. The summer samples were enriched in sulphates and mineral dusts; the winter samples contained more sea salts, aged sea salts, and industrial particles. The fine size fraction below 1 m diameter was enriched in secondary particles and showed evidence of atmospheric processing. The secondary sulphate particles were mainly attributed to long-range transport. A regional conversion from calcite to calcium sulphate occurred during summer. Industrial particles originating from local pollution appeared during winter.     

The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.     

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(...     

青藏高原大气低频振荡与低涡群发性的研究

本文指出，夏半年青藏高原低涡具有群发性，即低涡集中在某些时段连续不断地发生，而在另一些时段又不发生的特征。高原低涡的群发时段与高原大气低频振荡位相转换和垂直结构以及高原大气高频扰动的强弱有联系。这种联系，可能是高原大气扰动——高频部分与低频部分之间的相互作用。     

Exchange of Short-Chain Oxygenated Volatile Organic Compounds (VOCs) between Plants and the Atmosphere: A Compilation of Field and Laboratory Studies

Field and laboratory investigations of the exchange of the short-chain organic acids – formic acid and acetic acid – as well as their homologous aldehydes are discussed. Both acids are substantially released from several plant species. Emission measurements under field conditions are compiled to give an overview of three years of measurements. Emission rates from several tree species were found in the range between zero and 60 nmoles m^–2 min^–1 for acetic acid and between zero and 90 nmoles m^–2 min^–1 for formic acid though also a deposition has been observed to orange trees. Investigations under laboratory conditions showed an order of magnitude lower emission rates with significant differences under light and dark conditions, and a deposition was observed under certain conditions. Hence, low emission rates or even a bi-directional exchange, emission as well as deposition have to be taken into account. Further differences between field and laboratory studies are discussed considering age of trees, stress effects and a potential production of acids by photochemical conversion of precursors inside enclosures during sampling. Field data on the exchange of form- and acetaldehyde show a complex behavior. We found emission as well as uptake. The bi-directional exchange is significantly triggered by the ambient mixing ratios of both aldehyde species and exhibits a compensation point. Further studies are needed for generalization of the exchange of these and potentially also for other compounds.     

Emission of Biogenic Volatile Organic Compounds: An Overview of Field, Laboratory and Modelling Studies Performed during the `Tropospheric Research Program' (TFS) 1997–2000

The present paper summarises results on the emission of biogenicvolatile organic compounds (BVOC) achieved within the frame of thenational `German Tropospheric Research Programme' (TFS) between 1997 and2000. Field measurements were carried out at the meteorologicalmonitoring station `Hartheimer Wald' located in the vicinity of Freiburg(upper Rhine valley), Germany, within a pine plantation dominated byScots pine (Pinus sylvestris L.). The measured BVOC emissionrates were used to determine the daily and seasonal variation of BVOCemission and its dependence on important meteorological and plantphysiological parameters. In parallel, laboratory experiments usingyoung trees of pine (P. sylvestris), poplar (Populustremula ×P. alba) and pedunculate oak (Quercusrobur L.) were performed, and the influence of abiotic (e.g.,light, temperature, seasonality, flooding) factors on the biosynthesisand emission of BVOC was quantified. Based on these data, emissionalgorithms were evaluated and a process-oriented numerical model for thesimulation of the isoprene emission by plants was developed. Inaddition, newly calculated land use and tree species distributions wereused for the calculation of an actual BVOC emission inventory ofGermany.     

Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

A high-sensitive technique to detect O(¹S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(¹S) production process from the UV photodissociation of O₃, N₂O, and H₂O₂. The quantum yields for O(¹S) formation from O₃ photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10⁻⁴ and (5 ± 3) × 10⁻⁵, respectively. Based on thermochemical considerations, the O(¹S) formation from O₃ photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(¹S)+O₂(X³Σ_g ⁻). Analysis of the Doppler profile of O(¹S) produced from O₃ photolysis at 193 nm also indicates that the O(¹S) atoms are produced from the spin-forbidden process. In the photolysis of N₂O and H₂O₂ at 193 nm, no discernible signal of O(¹S) atoms has been detected. The upper limit values of the quantum yields for O(¹S) production from N₂O and H₂O₂ photolysis at 193 nm are estimated to be 8 × 10⁻⁵ and 3 × 10⁻⁵, respectively. Using the experimental results, the impact of the O(¹S) formation from O₃ photolysis on the atmospheric OH radical formation through the reaction of O(¹S)+H₂O has been estimated. The calculated results show that the contribution of the O(¹S)+H₂O reaction to the OH production rate is ∼2% of that of the O(¹D)+H₂O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(¹S) at 557.7 nm have also been discussed.     

餐饮源挥发性有机物(VOCs)排放特征及对臭氧生成的影响

餐饮排放是城市地区挥发性有机物（VOCs）重要的无组织来源,由于其排放特征复杂,是大气环境研究和管理的薄弱环节.本研究采用了现场和实验模拟两种采样方式,利用2,4-二硝基苯肼（DNPH）采样柱和不锈钢罐分别采集羰基化合物和全空气样品,然后利用高效液相色谱（HPLC）和气相色谱-质谱联用仪（GC-MS/FID）对116种组分进行定性定量分析.在此基础上,分析了餐饮源VOCs的排放特征及其影响因素.总体来看,含氧有机物（OVOCs）和烷烃是VOCs浓度的主要贡献者,但不同餐饮源的源谱特征差异较大.另外,通过比较发现食用油的种类、油的使用次数、加热方式、烹饪方式和调味料等因素会对餐饮源VOCs排放特征造成显著影响.进一步分析了不同菜系所排放VOCs的臭氧生成潜势（OFP）,关键组分主要是甲醛、乙醛、丁烯醛、乙烯和丙烯等.本研究成果能够补充我国餐饮源VOCs控制所需的基础数据.