The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for rate constant prediction include empirical correlations as well as structure activity relationships (SAR) either with or without the usage of quantum chemical descriptors. Recently published estimation methods for OH, NO(3) and SO(4)(-) radical reactions in aqueous solution are finally summarized, compared and discussed.

Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO 4 2− ) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueousphase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO 4 2− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. ) contribute to the formation of new aerosol particles as well as secondary particulate matter and are, thus, important for human health and the Earth's climate (1). Globally, anthropogenic sulfur emissions in the form of sulfur dioxide (SO 2 ) dominate atmospheric production of gaseous H 2 SO 4 and particle-phase sulfate. However, the main natural source of sulfur is the oxidation of dimethyl sulfide (DMS) emitted by oceans (2), which is the most important precursor for non-sea salt sulfate (nss-SO 4 2− ) aerosols over the open ocean (3). Sulfate aerosols strongly influence the climate both by direct negative radiative forcing (4) and as a dominant source of cloud condensation nuclei (CCN) over the open ocean (5). Because oceans cover about 70% of Earth's surface (6) and have generally low albedo, DMS oxidation plays a major role in influencing the natural radiative forcing of sulfate aerosols as well as cloud properties (3).Investigations of the effect of DMS oxidation on natural sulfate aerosol concentrations and cloud and aerosol properties require an accurate, reduced DMS oxidation scheme in chemical transport models (CTMs) and global climate models (GCMs). Current parameterizations use fixed yields of SO 2 and methyl sulfonic acid (MSA) to calculate new nss...

An overall adsorption quantity for a heterogeneous solid is usually expressed by an integral equation, which contains a distribution function that describes heterogeneous properties of this solid. The calculation of this distribution function is an ill-posed problem. The current article shows that the difficulties arising from the ill-posed nature of an adsorption equation can be overcome with the regularization method. This work presents general principles of regularization for solving the ill-posed problems without detailed mathematical considerations. The application of the regularization method to calculate a distribution function from any overall adsorption functions is illustrated with both simulated and experimental adsorption isotherms.

Chlorine atoms (Cl) are highly reactive toward hydrocarbons in the Earth's troposphere, including the greenhouse gas methane (CH4). However, the regional and global CH4 sink from Cl is poorly quantified as tropospheric Cl concentrations ([Cl]) are uncertain by ~2 orders of magnitude. Here we describe the addition of a detailed tropospheric chlorine scheme to the TOMCAT chemical transport model. The model includes several sources of tropospheric inorganic chlorine (Cly), including (i) the oxidation of chlorocarbons of natural (CH3Cl, CHBr2Cl, CH2BrCl, and CHBrCl2) and anthropogenic (CH2Cl2, CHCl3, C2Cl4, C2HCl3, and CH2ClCH2Cl) origin and (ii) sea‐salt aerosol dechlorination. Simulations were performed to quantify tropospheric [Cl], with a focus on the marine boundary layer, and quantify the global significance of Cl atom CH4 oxidation. In agreement with observations, simulated surface levels of hydrogen chloride (HCl), the most abundant Cly reservoir, reach several parts per billion (ppb) over polluted coastal/continental regions, with sub‐ppb levels typical in more remote regions. Modeled annual mean surface [Cl] exhibits large spatial variability with the largest levels, typically in the range of 1–5 × 104 atoms cm−3, in the polluted northern hemisphere. Chlorocarbon oxidation provides a tropospheric Cly source of up to ~4320 Gg Cl/yr, sustaining a background surface [Cl] of <0.1 to 0.5 × 103 atoms cm−3 over large areas. Globally, we estimate a tropospheric methane sink of ~12–13 Tg CH4/yr due the CH4 + Cl reaction (~2.5% of total CH4 oxidation). Larger regional effects are predicted, with Cl accounting for ~10 to >20% of total boundary layer CH4 oxidation in some locations.

Article:Tilgner, A., Bräuer, P. orcid.org/0000-0002-3815-7631, Wolke, R. et al.(1 more author) (2013) Modelling multiphase chemistry in deliquescent aerosols and clouds using CAPRAM3.Abstract Modelling studies were performed with the multiphase mechanism RACM-MIM2ext/CAPRAM 3.0i to investigate the tropospheric multiphase chemistry in deliquesced particles and non-precipitating clouds using the SPACCIM model framework. Simulations using a non-permanent cloud scenario were carried out for two different environmental conditions focusing on the multiphase chemistry of oxidants and other linked chemical subsystems. Model results were analysed by time-resolved reaction flux analyses allowing advanced interpretations. The model shows significant effects of multiphase chemical interactions on the tropospheric budget of gas-phase oxidants and organic compounds. In-cloud gas-phase OH radical concentration reductions of about 90 % and 75 % were modelled for urban and remote conditions, respectively. The reduced in-cloud gasphase oxidation budget increases the tropospheric residence time of organic trace gases by up to about 30 %. Aqueous-phase oxidations of methylglyoxal and 1,4-butenedial were identified as important OH radical sinks under polluted conditions. The model revealed that the organic C 3 and C 4 chemistry contributes with about 38 %/48 % and 8 %/9 % considerably to the urban and remote cloud / aqueous particle OH sinks. Furthermore, the simulations clearly implicate the potential role of deliquescent particles to operate as a reactive chemical medium due to an efficient TMI/HO x,y chemical processing including e.g. an effective in-situ formation of OH radicals. Considerable chemical differences between deliquescent particles and cloud droplets, e.g. a circa 2 times more efficient daytime iron processing in the urban deliquescent particles, were identified. The in-cloud oxidation of methylglyoxal and its oxidation products is identified as efficient sink for NO 3 radicals in the aqueous phase.

To quantify the effects of an advanced iron photochemistry scheme, the chemical aqueous-phase radical mechanism (CAPRAM 3.0i) has been updated with several new Fe(III)-carboxylate complex photolysis reactions. Newly introduced ligands are malonate, succinate, tartrate, tartronate, pyruvate, and glyoxalate. Model simulations show that more than 50% of the total Fe(III) is coordinated by oxalate and up to 20% of total Fe(III) is bound in the newly implemented 1:1 complexes with tartronate, malonate, and pyruvate. Up to 20% of the total Fe(III) is found in hydroxo and sulfato complexes. The fraction of [Fe(oxalate)2](-) and [Fe(pyruvate)](2+) is significantly higher during nighttime than during daytime, which points toward a strong influence of photochemistry on these species. Fe(III) complex photolysis is an important additional sink for tartronate, pyruvate, and oxalate, with a complex photolysis contribution to overall degradation of 46, 40, and 99%, respectively, compared to all possible sink reactions with atmospheric aqueous-phase radicals, such as (•)OH, NO3(•), and SO4(•) (-). Simulated aerosol particles have a much lower liquid water content than cloud droplets, thus leading to high concentrations of species and, consequently, an enhancement of the photolysis sink reactions in the aerosol particles. The simulations showed that Fe(III) photochemistry should not be neglected when considering the fate of carboxylic acids, which constitute a major part of aqueous secondary organic aerosol (aqSOA) in tropospheric cloud droplets and aqueous particles. Failure to consider this loss pathway has the potential to result in a significant overestimate of aqSOA production.

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