Tropospheric Aqueous Phase Research Articles

Temperature- and pH- Dependent OH Radical Reaction Kinetics of Tartaric and Mucic Acids in the Aqueous Phase.

Tartaric acid and mucic acid are dicarboxylic acids (DCAs), a substance class often found in atmospheric aerosols and cloud droplets. The hydroxyl radical (•OH)-induced oxidation in the aqueous phase is known to be an important loss process of organic compounds such as DCAs. However, the study of •OH kinetics of DCAs in the aqueous phase is still incomplete. In the present study, the rate constants of the •OH reactions of tartaric acid and mucic acid in the aqueous phase were determined by the thiocyanate competition kinetics method as a function of temperature and pH. The following T-dependent Arrhenius expressions (in units of L mol-1 s-1) were first derived for the •OH reactions with tartaric acid─k(T, H2A) = (3.3 ± 0.1) × 1010 exp[(-1350 ± 110 K)/T], k(T, HA-) = (3.6 ± 0.1) × 1010 exp[(-580 ± 110 K)/T], and k(T, A2-) = (3.3 ± 0.1) × 1010 exp[(-1190 ± 170 K)/T]─as well as mucic acid─k(T, H2A) = (2.2 ± 0.1) × 1010 exp[(-1140 ± 150 K)/T], k(T, HA-) = (4.8 ± 0.1) × 1010 exp[(-1280 ± 170 K)/T], and k(T, A2-) = (2.1 ± 0.1) × 1010 exp[(-970 ± 70 K)/T]. A general trend of the •OH rate constant is found as > > . The pH- and temperature-dependent rate constants of the OH radical reactions allow an accurate description of the source and sink processes in the tropospheric aqueous phase.

Reaction Kinetics of Green Leaf Volatiles with Sulfate, Hydroxyl, and Nitrate Radicals in Tropospheric Aqueous Phase.

Green plants exposed to abiotic or biotic stress release C-5 and C-6 unsaturated oxygenated hydrocarbons called Green Leaf Volatiles (GLVs). GLVs partition into tropospheric waters and react to form secondary organic aerosol (SOA). We explored the kinetics of aqueous-phase reactions of 1-penten-3-ol (PENTOL), (Z)-2-hexen-1-ol (HEXOL), and (E)-2-hexen-1-al (HEXAL) with SO4•–, •OH, and NO3•. At 298 K, the rate constants for reactions of PENTOL, HEXOL, and HEXAL with SO4•– were, respectively, (9.4 ± 1.0) × 108 L mol–1 s–1, (2.5 ± 0.3) × 109 L mol–1 s–1, and (4.8 ± 0.2) × 108 L mol–1 s–1; with •OH – (6.3 ± 0.1) × 109 L mol–1 s–1, (6.7 ± 0.3) × 109 L mol–1 s–1, and (4.8 ± 0.3) × 109 L mol–1 s–1; and with NO3• – (1.5 ± 0.15) × 108 L mol–1 s–1, (8.4 ± 2.3) × 108 L mol–1 s–1, and (3.0 ± 0.7) × 107 L mol–1 s–1. The rate constants increased weakly with temperatures ranging from 278 to 318 K. The diffusional limitations of the rate constants appeared significant only for the GLV–•OH reactions. The aqueous-phase reactions appeared negligible in deliquescent aerosol and haze water but not in clouds and rains. The atmospheric lifetimes of GLVs decreased from many days to hours with increasing liquid water content and radicals’ concentration.

Aromatic Carbonyl and Nitro Compounds as Photosensitizers and Their Photophysical Properties in the Tropospheric Aqueous Phase.

Secondary organic aerosol formation in the atmospheric aqueous/particulate phase by photosensitized reactions is currently subject to uncertainties. To understand the impact of photosensitized reactions, photophysical and -chemical properties of photosensitizers, kinetic data, and reaction mechanisms of these processes are required. The photophysical properties of acetophenones, benzaldehydes, benzophenones, and naphthalenes were investigated in aqueous solution using laser flash excitation. Quantum yields of excited photosensitizers were determined giving values between 0.06-0.80 at 298 K and pH = 5. Molar absorption coefficients (εmax(3PS*) = (0.8-13) × 104 L mol-1 cm-1), decay rate constants in water (k1st = (9.4 ± 0.5) × 102 to (2.2 ± 0.1) × 105 s-1), and quenching rate constants with oxygen (kq(O2) = (1.7 ± 0.1-4.4 ± 0.4) × 109 L mol-1 s-1) of the excited triplet states were determined at 298 K and pH = 5. Photosensitized reactions of carboxylic acids and alkenes show second-order rate constants in the range of (37 ± 7.0-0.55 ± 0.1) × 104 and (27 ± 5.0-0.04 ± 0.01) × 108 L mol-1 s-1. The results show that different compound classes act differently as a photosensitizer and can be a sink for certain organic compounds in the atmospheric aqueous phase.

Five-Membered Heterocycles as Potential Photosensitizers in the Tropospheric Aqueous Phase: Photophysical Properties of Imidazole-2-carboxaldehyde, 2-Furaldehyde, and 2-Acetylfuran.

Photosensitized reactions of organic compounds in the atmospheric aqueous and particle phase might be potential sources for secondary organic aerosol (SOA) formation, addressed as aqueous SOA. However, data regarding the photophysical properties of photosensitizers, their kinetics, as well as reaction mechanisms of such processes in the aqueous/particle phase are scarce. The present study investigates the determination of the photophysical properties of imidazole-2-carboxaldehyde, 2-furaldehyde, and 2-acetylfuran as potential photosensitizers using laser flash excitation in aqueous solution. Quantum yields of the formation of the excited photosensitizers were obtained by a scavenging method with thiocyanate, resulting in values between 0.86 and 0.96 at 298 K and pH = 5. The time-resolved absorbance spectra of the excited photosensitizers were measured, and their molar attenuation coefficients were determined ranging between (0.30 and 1.4) × 104 L mol-1 cm-1 at their absorbance maxima (λmax = 335-440 nm). Additionally, the excited photosensitizers are quenched by water and molecular oxygen, resulting in quenching rate constants of k1st = (1.0 ± 0.2-1.8 ± 0.2) × 105 s-1 and kq(O2) = (2.1 ± 0.2-2.7 ± 0.2) × 109 L mol-1 s-1, respectively.

PH- and Temperature-Dependent Kinetics of the Oxidation Reactions of OH with Succinic and Pimelic Acid in Aqueous Solution

Rate constants for the aqueous-phase reactions of the hydroxyl radical with the dicarboxylic acids, succinic acid and pimelic acid were determined using the relative rate technique over the temperature range 287 K ≤ T ≤ 318 K and at pH = 2.0, 4.6 or 4.9 and 8.0. OH radicals were generated by H2O2 laser flash photolysis while thiocyanate was used as a competitor. The pH values were adjusted to obtain the different speciation of the dicarboxylic acids. The following Arrhenius expressions were determined (in units of L mol−1 s−1): succinic acid, k(T, AH2) (2.1 ± 0.1) × 1010 exp[(−1530 ± 250 K)/T], k(T, AH−) (1.8 ± 0.1) × 1010 exp[(−1070 ± 370 K)/T], k(T, A2−) (2.9 ± 0.2) × 1011 exp[(−1830 ± 350 K)/T] and pimelic acid, k(T, AH2) (7.3 ± 0.2) × 1010 exp[(−1040 ± 140 K)/T], k(T, AH−) (1.8 ± 0.1) × 1011 exp[(−1200 ± 240 K)/T], k(T, A2−) (1.4 ± 0.1) × 1012 exp[(−1830 ± 110 K)/T]. A general OH radical reactivity trend for dicarboxylic acids was found as k(AH2) < k(AH−) < k(A2−). By using the pH and temperature dependent rate constants, source and sinking processes in the tropospheric aqueous phase can be described precisely.

The oxidation mechanism of 3,4-dihydroxy-2-butanone in the aqueous phase for secondary organic aerosols formation

3,4-dihydroxy-2-butanone (DHBO) is a major oxidation product of IEPOX and can easily be oxidized in tropospheric aqueous phase. The aqueous oxidation mechanism of DHBO has investigated by DFT and initial reaction rate constants also have calculated through TST. In the aqueous phase, the following trend in reactivity of initial reaction can be obtained: OH ≫ SO4− > NO3, which bases on the calculated rate constants (k(OH) = 1.20 × 108 L mol−1 s−1, k(SO4−) = 8.51 × 105 L mol−1 s−1 and k(NO3) = 2.86 × 105 L mol−1 s−1) at 298 K and 1 atm. After initial reaction, the major products of DHBO further react with OH radical at presence of O2. The final products include acetic acid and methylglyoxal, which are important SOA precursors. This work provides a reference for oxidation mechanism of dihydroxycarbonyl of isoprene-driven in aqueous and help understand SOA formation.

Aqueous-Phase Oxidation of cis-β-Isoprene Epoxydiol by Hydroxyl Radicals and Its Impact on Atmospheric Isoprene Processing.

Isoprene epoxydiols are well-known intermediates of the isoprene oxidation in the gas phase under pristine conditions. According to their Henry's Law constants, they are well water-soluble and will undergo a phase transfer to the tropospheric aqueous phase to be further processed there. In the present study, the aqueous-phase oxidation by hydroxyl radicals (OH) of the isomer cis-β-isoprene epoxydiol (cis-β-IEPOX) was investigated with regards to its kinetics and reaction product distribution. For the reaction of cis-β-IEPOX with hydroxyl radicals, a second-order rate constant of (1.4 ± 0.1) × 109 L mol-1 s-1 was determined at 298 K. Short chain carbonyls, such as glycolaldehyde with a maximum molar fraction of 6.9%, hydroxyacetone (7.4%), methylglyoxal (10.3%), and glyoxal (6.6%), as well as acetic acid (13.9%), were observed as major oxidation products. A total molar recovery of 75% was obtained in the oxidation experiments. The overall contribution of the aqueous-phase oxidation of cis-β-IEPOX was estimated to range from 29.7 to 21.3% to the atmospheric processing depending on the scenario.

Oxidation of substituted aromatic hydrocarbons in the tropospheric aqueous phase: kinetic mechanism development and modelling

Monocyclic aromatic compounds are ubiquitous in the polluted troposphere and contribute to the formation of tropospheric ozone and anthropogenic secondary organic aerosol, including brown carbon. Currently available physico-chemical data including aqueous-phase kinetic and mechanistic data, as well as phase-transfer parameters have been compiled and reviewed, to construct a novel aqueous-phase oxidation mechanism for monocyclic aromatic compounds. The performed chemical mechanism development results in a comprehensive aqueous-phase oxidation mechanism (addressed as CAPRAM-AM1.0), which includes 292 processes considering the oxidation of different aromatic compounds. Detailed numerical simulations with the air parcel model SPACCIM are carried out for different urban environmental and seasonal conditions. Results show that the aqueous-phase chemistry of aromatic compounds, particularly in clouds, increases the organic aerosol mass by up to 10% in total. The absolute contribution to aqSOA in summertime is modelled to be 260 ng m-3 and 1.2 μg m-3 under moderate and strongly polluted conditions, respectively. Aqueous-phase oxidations of aromatic compounds are important not only for the degradation, but also for the formation of nitrated aromatic compounds. In-cloud chemistry contributes up to 54% to the nitrocatechol oxidation and up to 37% to its formation under polluted tropospheric conditions. Besides, nitrated aromatic compounds contribute up to 5.4 μg m-3 to modelled brown carbon concentration in cloud droplets and 140 ng m-3 in aerosol particles. Further, the model simulations indicate that besides OH radical oxidations, aromatic compounds with two hydroxyl groups are also strongly oxidised by O3 and HO2. O3 contributes with 49% to 68% and HO2 with 19% to 22% to the aqueous-phase oxidation of catechol under moderate and strong polluted environmental conditions studied.

Tropospheric Aqueous-Phase Oxidation of Isoprene-Derived Dihydroxycarbonyl Compounds.

The dihydroxycarbonyls 3,4-dihydroxy-2-butanone (DHBO) and 2,3-dihydroxy-2-methylpropanal (DHMP) formed from isoprene oxidation products in the atmospheric gas phase under low-NO conditions can be expected to form aqSOA in the tropospheric aqueous phase because of their solubility. In the present study, DHBO and DHMP were investigated concerning their radical-driven aqueous-phase oxidation reaction kinetics. For DHBO and DHMP the following rate constants at 298 K are reported: k(OH + DHBO) = (1.0 ± 0.1) × 109 L mol-1 s-1, k(NO3 + DHBO) = (2.6 ± 1.6) × 106 L mol-1 s-1, k(SO4-+ DHBO) = (2.3 ± 0.2) × 107 L mol-1 s-1, k(OH + DHMP) = (1.2 ± 0.1) × 109 L mol-1 s-1, k (NO3 + DHMP) = (7.9 ± 0.7) × 106 L mol-1 s-1, k(SO4- + DHMP) = (3.3 ± 0.2) × 107 L mol-1 s-1, together with their respective temperature dependences. The product studies of both DHBO and DHMP revealed hydroxydicarbonyls, short chain carbonyls, and carboxylic acids, such as hydroxyacetone, methylglyoxal, and lactic and pyruvic acid as oxidation products with single yields up to 25%. The achieved carbon balance was 75% for DHBO and 67% for DHMP. An aqueous-phase oxidation scheme for both DHBO and DHMP was developed on the basis of the experimental findings to show their potential to contribute to the aqSOA formation. It can be expected that the main contribution to aqSOA occurs via acid formation while other short-chain oxidation products are expected to back-partition into the gas phase to undergo further oxidation there.

Acute toxicity of emerging atmospheric pollutants from wood lignin due to biomass burning

Guaiacol (2-methoxyphenol) is an important atmospheric pollutant. It is the major component of wood lignin and is essentially emitted to the atmosphere during biomass burning. Its aging in the tropospheric aqueous phase leads to the generation of the following ring-retaining transformation products, also during nighttime: 4-nitroguaiacol, 6-nitroguaiacol, and dinitroguaiacol. This study presents the first toxicological data of guaiacol and its nitro derivatives and reveals their harmful potential for the ecosystem. Applying V. fischeri bioluminescence acute toxicity test, EC50 values range from 16.7 to 103mgL−1 after a 30-min incubation period, which classifies all investigated compounds as ‘harmful’ according to the European legislation. The investigation of environmentally relevant mixtures did not show significant joint actions between the four studied compounds. Therefore, their concentration addition can be considered for ecotoxicological purposes. However, a synergistic effect between guaiacol and a minor unidentified first-generation product of its aqueous-phase aging was observed and should be taken into account when assessing the reaction mixture toxicity. These results stress the need for further toxicological testing, including organisms of different trophic levels, to better evaluate the environmental hazard of guaiacol and especially its nitro derivatives.

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies

Kinetic and mechanistic studies were conducted on the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic and acrylic acid reacting with hydroxyl and nitrate radicals and sulfate radical anions in aqueous solution by use of the laser flash photolysis technique and a reversed-rate method for kinetics. High-performance liquid chromatography/mass spectrometry was applied for product analysis. The kinetic investigations show the highest reactivity of the hydroxyl radical followed by sulfate and nitrate radicals. For methacrolein and methyl vinyl ketone the following rate constants have been determined at 298 K: k(OH+methacrolein) = (9.4 ± 0.7) × 10(9) M(-1) s(-1), k(OH+methyl vinyl ketone) = (7.3 ± 0.5) × 10(9) M(-1) s(-1), k(NO3+methacrolein) = (4.0 ± 1.0) × 10(7) M(-1) s(-1), k(NO3+methyl vinyl ketone) = (9.7 ± 3.4) × 10(6) M(-1) s(-1), k(SO4(-)+methacrolein) = (9.9 ± 4.9) × 10(7) M(-1) s(-1) and k(SO4(-)+methyl vinyl ketone) = (1.0 ± 0.2) × 10(8) M(-1) s(-1). Temperature and pH dependencies of the reactions of OH, NO3 and SO4(-) with methacrolein, methyl vinyl ketone, methacrylic and acrylic acid as well as Arrhenius parameters have been obtained and discussed. Product studies were performed on the OH radical induced oxidation of methacrolein and methyl vinyl ketone. In the reaction of methacrolein + OH methylglyoxal and hydroxyacetone were identified as first oxidation products with yields of 0.099 and 0.162. Methylglyoxal was primarily produced in the oxidation of methyl vinyl ketone with a yield of 0.052. For both precursor compounds the formation of glycolaldehyde was observed for the first time with yields of 0.051 and 0.111 in the oxidation of methacrolein and methyl vinyl ketone, respectively. Furthermore, highly functionalised C4 compounds were determined from the oxidation of both precursor compounds, but for the first time for methyl vinyl ketone. Reaction schemes were developed based on known peroxyl radical reaction mechanisms. The aqueous phase conversion of the first generation isoprene oxidation products can potentially contribute to tropospheric aqueous phase budgets of important carbonyl and dicarbonyl components which are expected to be conducive to the formation of aqSOA.

Photochemical reactions in the tropospheric aqueous phase and on particulate matter

This paper is a tutorial review in the field of atmospheric chemistry. It describes some recent developments in tropospheric photochemistry in the aqueous phase and on particulate matter. The main focus is regarding the transformation processes that photochemical reactions induce on organic compounds. The relevant reactions can take place both on the surface of dispersed particles and within liquid droplets (e.g. cloud, fog, mist, dew). Direct and sensitised photolysis and the photogeneration of radical species are the main processes involved. Direct photolysis can be very important in the transformation of particle-adsorbed compounds. The significance of direct photolysis depends on the substrate under consideration and on the colour of the particle: dark carbonaceous material shields light, therefore protecting the adsorbed molecules from photodegradation, while a much lower protection is afforded for the light-shaded mineral fraction of particulate. Particulate matter is also rich in photosensitisers (e.g. quinones and aromatic carbonyls), partially derived from PAH photodegradation. These compounds can induce degradation of other molecules upon radiation absorption. Interestingly, substrates such as methoxyphenols, major constituents of wood-smoke aerosol, can also enhance the degradation of some sensitisers. Photosensitised processes in the tropospheric aqueous phase have been much less studied: it will be interesting to assess the photochemical properties of Humic-Like Substances (HULIS) that are major components of liquid droplets. The main photochemical sources of reactive radical species in aqueous solution and on particulate matter are hydrogen peroxide, nitrate, nitrite, and Fe(iii) compounds and oxides. The photogeneration of hydroxyl radicals can be important in polluted areas, while their transfer from the gas phase and dark generation are usually prevailing on an average continental scale. The reactions involving hydroxyl radicals can induce very fast transformation of compounds reacting with (*)OH at a diffusion-controlled rate (10(10) M(-1) s(-1)), with time scales of an hour or less. The hydroxyl-induced reactivity in solution can be faster than in the gas phase, influencing the degradation kinetics of water-soluble compounds. Moreover, photochemical processes in fog and cloudwater can be important sources of secondary pollutants such as nitro-, nitroso-, and chloro-derivatives.

FEBUKO and MODMEP: Field measurements and modelling of aerosol and cloud multiphase processes

An overview of the two FEBUKO aerosol–cloud interaction field experiments in the Thüringer Wald (Germany) in October 2001 and 2002 and the corresponding modelling project MODMEP is given. Experimentally, a variety of measurement methods were deployed to probe the gas phase, particles and cloud droplets at three sites upwind, downwind and within an orographic cloud with special emphasis on the budgets and interconversions of organic gas and particle phase constituents. Out of a total of 14 sampling periods within 30 cloud events three events (EI, EII and EIII) are selected for detailed analysis. At various occasions an impact of the cloud process on particle chemical composition such as on the organic compounds content, sulphate and nitrate and also on particle size distributions and particle mass is observed. Moreover, direct phase transfer of polar organic compound from the gas phase is found to be very important for the understanding of cloudwater composition. For the modelling side, a main result of the MODMEP project is the development of a cloud model, which combines a complex multiphase chemistry with detailed microphysics. Both components are described in a fine-resolved particle/drop spectrum. New numerical methods are developed for an efficient solution of the entire complex model. A further development of the CAPRAM mechanism has lead to a more detailed description of tropospheric aqueous phase organic chemistry. In parallel, effective tools for the reduction of highly complex reaction schemes are provided. Techniques are provided and tested which allow the description of complex multiphase chemistry and of detailed microphysics in multidimensional chemistry-transport models.

Kinetics and mechanisms of reactions of the nitrate radical (NO3) with substituted phenols in aqueous solution

Second order rate constants were obtained for the reactions of the nitrate radical (NO3) with substituted phenols in aqueous solutions at 298 K and pH = 0.5. The following compounds were investigated and the corresponding rate constants are reported: (1) 2-hydroxyphenol [k1 = (5.6 ± 0.8) × 108 M−1 s−1]; (2) 2-methylphenol [k2 = (8.5 ± 0.2) × 108 M−1 s−1]; (3) 2-ethylphenol [k3 = (6.7 ± 0.4) × 108 M−1 s−1]; (4) 2-methoxyphenol [k4 = (1.1 ± 0.1) × 108 M−1 s−1]; (5) 2-nitrophenol [k5 = (2.3 ± 0.4) × 107 M−1 s−1]; (6) 2-cyanophenol [k6 = (3.1 ± 0.3) × 108 M−1 s−1]; (7) 2-fluorophenol [k7 = (5.5 ± 0.4) × 108 M−1 s−1]; (8) 2-chlorophenol [k8 = (2.9 ± 0.3) × 108 M−1 s−1]; (9) 2-bromophenol [k9 = (2.7 ± 0.1) × 108 M−1 s−1]; (10) 2-phenylphenol [k10 = (2.4 ± 0.4) × 108 M−1 s−1]; (11) 4-hydroxyphenol [k11 = (8.8 ± 0.5) × 108 M−1 s−1]; (12) 4-aminophenol [k12 = (8.1 ± 0.3) × 108 M−1 s−1]; (13) 4-chlorophenol [k13 = (1.7 ± 0.2) × 109 M−1 s−1]; (14) 4-bromophenol [k14 = (1.0 ± 0.4) × 109 M−1 s−1]; (15) 4-hydroxybenzen ethyl ester [k15 = (8.0 ± 0.4) × 108 M−1 s−1]. Moreover, the temperature dependence of the reaction of NO3 with four ortho-substituted phenols, (a) 2-methylphenol, (b) 2-ethylphenol, (c) 2-hydroxyphenol and (d) 2-methoxyphenol were investigated in the temperature range of 278 ≤ T ≤ 318 K and the corresponding activation parameters were obtained for the first time. A comparison of the reactivity of NO3 towards other aromatics present in the tropospheric aqueous phase such as substituted benzenes and substituted benzoic acid was undertaken.

CAPRAM 2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application

A detailed and extended chemical mechanism describing tropospheric aqueous phase chemistry (147 species and 438 reactions) is presented here as Chemical Aqueous Phase Radical Mechanism (CAPRAM) 2.4 (MODAC mechanism). The mechanism based on the former version 2.3 [Herrmann et al., 2000] contains extended organic and transition metal chemistry and is formulated more explicitly based on a critical review of the literature. The aqueous chemistry has been coupled to the gas phase mechanism Regional Atmospheric Chemistry Modeling (RACM) [Stockwell et al., 1997], and phase exchange accounted for using the resistance model of Schwartz [1986]. A method for estimating mass accommodation coefficients (α) is described, which accounts for functional groups contained in a particular compound. A condensed version has also been developed to allow the use of CAPRAM 2.4 (MODAC mechanism) in higher‐scale models. Here the reproducibility of the concentration levels of selected target species (i.e., NOx, S(IV), H2O2, NO3, OH, O3, and H+) within the limits of ± 5% was used as a goal for eliminating insignificant reactions from the complete CAPRAM 2.4 (MODAC mechanism). This has been done using a range of initial conditions chosen to represent different atmospheric scenarios, and this produces a robust and concise set of reactions. The most interesting results are obtained using atmospheric conditions typical for an urban scenario, and the effects introduced by updating the aqueous phase chemistry are highlighted, in particular, with regard to radicals, redox cycling of transition metal ions and organic compounds. Finally, the reduced scheme has been incorporated into a one‐dimensional (1‐D) marine cloud model to demonstrate the applicability of this mechanism.

Autoxidation of sulphur dioxide in the presence of alcohols under conditions related to the tropospheric aqueous phase

In this work attempts were made to elucidate the monoterpenic alcohol inhibition of the S(IV) autoxidation by comparing the inhibiting activity of cis -verbenol (C 10 H 15 OH), myrtenol (C 10 H 15 OH) and nopol (C 11 H 17 OH) with that of ethanol (C 2 H 5 OH) and 2-propanol (C 3 H 7 OH). Results of laboratory experiments on the kinetics of S(IV) autoxidation in the presence of these alcohols were interpreted using the equation derived by Alyea and Bäckström (J. Am. Chem. Soc. 51 (1929) 90), brought into relationship with the actual mechanistic knowledge on the reactivity of the inhibitors with respect to sulphate radicals. The rate constants for the reaction: alc+SO 4 · − (+O 2 )→SO 4 2− +H + +HO 2 +ald involving cis -verbenol and myrtenol have been determined as equal to, respectively, 5.4×10 9 and 4.2×10 9 M −1 s −1 . These results were obtained under the assumption that the main chain termination is due to simultaneous scavenging SO 5 · − radical anions by Fe II and SO 4 · − radical anions by an alcohol. In the case of nopol the rough estimate gave for the rate constant of the latter reaction a value of 9.0×10 9 M −1 s −1 burdened with an error caused by the sulphoxy radical induced autoxidation of nopol. The studied airborne compounds of biological origin were shown to be potentially significant modifiers of the acidity formation in clouds and a sink for sulphoxy radicals participating in further transformations of these compounds.

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.