Gas-Phase Formation of Sulfurous Acid (H2SO3) in the Atmosphere.

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical-initiated gas-phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295±0.5 K and 1 bar of air with a molar yield of 53 - 17 + 7 ${{53}_{-17}^{+\ 7}}$ %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH+CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O+H2SO3) <3×10-18 cm3 molecule-1 s-1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Direct sulfuric acid formation from the gas-phase oxidation of reduced-sulfur compounds.

Sulfuric acid represents a fundamental precursor for new nanometre-sized atmospheric aerosol particles. These particles, after subsequent growth, may influence Earth´s radiative forcing directly, or indirectly through affecting the microphysical and radiative properties of clouds. Currently considered formation routes yielding sulfuric acid in the atmosphere are the gas-phase oxidation of SO2 initiated by OH radicals and by Criegee intermediates, the latter being of little relevance. Here we report the observation of immediate sulfuric acid production from the OH reaction of emitted organic reduced-sulfur compounds, which was speculated about in the literature for decades. Key intermediates are the methylsulfonyl radical, CH3SO2, and, even more interestingly, its corresponding peroxy compound, CH3SO2OO. Results of modelling for pristine marine conditions show that oxidation of reduced-sulfur compounds could be responsible for up to ∼50% of formed gas-phase sulfuric acid in these areas. Our findings provide a more complete understanding of the atmospheric reduced-sulfur oxidation.

Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere.

Dimeric accretion products have been observed both in atmospheric aerosol particles and in the gas phase. With their low volatilities, they are key contributors to the formation of new aerosol particles, acting as seeds for more volatile organic vapors to partition onto. Many particle-phase accretion products have been identified as esters. Various gas- and particle-phase formation pathways have been suggested for them, yet evidence remains inconclusive. In contrast, peroxide accretion products have been shown to form via gas-phase peroxy radical (RO2) cross reactions. Here, we show that these reactions can also be a major source of esters and other types of accretion products. We studied α-pinene ozonolysis using state-of-the-art chemical ionization mass spectrometry together with different isotopic labeling approaches and quantum chemical calculations, finding strong evidence for fast radical isomerization before accretion. Specifically, this isomerization seems to happen within the intermediate complex of two alkoxy (RO) radicals, which generally determines the branching of all RO2-RO2 reactions. Accretion products are formed when the radicals in the complex recombine. We found that RO with suitable structures can undergo extremely rapid C-C ß scissions before recombination, often resulting in ester products. We also found evidence of this previously overlooked RO2-RO2 reaction pathway forming alkyl accretion products and speculate that some earlier peroxide identifications may in fact be hemiacetals or ethers. Our findings help answer several outstanding questions on the sources of accretion products in organic aerosol and bridge our knowledge of the gas phase formation and particle phase detection of accretion products. As esters are inherently more stable than peroxides, this also impacts their further reactivity in the aerosol.

Peroxy Radical and Product Formation in the Gas-Phase Ozonolysis of α-Pinene under Near-Atmospheric Conditions: Occurrence of an Additional Series of Peroxy Radicals O,O-C10H15O(O2)yO2 with y = 1-3.

Ozonolysis of α-pinene, C10H16, and other monoterpenes is considered to be one of the important chemical process in the atmosphere leading to condensable vapors, which are relevant to aerosol formation and, finally, for Earth's radiation budget. The formation of peroxy (RO2) radicals, O,O-C10H15(O2)xO2 with x = 0-3, and closed-shell products has been probed from the ozonolysis of α-pinene for close to atmospheric reaction conditions. (The "O,O" in the chemical formulas indicates the two carbonyl groups formed in the ozonolysis.) An additional series of RO2 radicals, O,O-C10H15O(O2)yO2 with y = 1-3, emerged in the presence of NO additions of (1.7-50) × 109 molecules cm-3, whose formation can be explained via different processes starting from alkoxy (RO) radicals, such as the RO-driven autoxidation. The main closed-shell product is a substance with the composition C10H16O3, probably pinonic acid, obtained with a molar yield (lower limit) of 0.26+0.27-0.14 independent of NO. Total molar product yields accounted for up to 0.71+0.72-0.38 indicating reasonable detection sensitivity of the analytical technique applied. For the isomeric O,O-C10H15O2 radicals, an average rate coefficient k(RO2 + NO) = (1.5 ± 0.3) × 10-11 cm3 molecule-1 s-1 at 295 ± 2 K was determined. Product analysis showed a lowering in the formation of highly oxygenated organic molecules (HOMs) by a factor of ∼2.2 when adding 5 × 1010 molecules cm-3 of NO. The comparison with former results revealed that total HOM suppression by NO in the α-pinene ozonolysis is slightly stronger than in the OH + α-pinene reaction.

Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol.

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Accretion Product Formation from Ozonolysis and OH Radical Reaction of α-Pinene: Mechanistic Insight and the Influence of Isoprene and Ethylene.

α-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C19 and C20 accretion products from α-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C10-RO2 radicals from α-pinene ozonolysis were O,O-C10H15(O2) xO2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O2)αO2 with α = 0, 1, 2. All detected C20 accretion products can be explained via the accretion reaction RO2 + R'O2 → ROOR' + O2 starting from the measured C10-RO2 radicals. We speculate that C19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C5-RO2 radicals, leads to C15 accretion products formed via cross-reactions with C10-RO2 radicals. This process is competing with the formation of C19/C20 products from the pure α-pinene oxidation. A similar behavior has been observed for ethylene additives that form C12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C19/C20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over α-pinene, respectively, as present in different forested areas.

Direct Probing of Criegee Intermediates from Gas-Phase Ozonolysis Using Chemical Ionization Mass Spectrometry.

Criegee intermediates (CIs), mainly formed from gas-phase ozonolysis of alkenes, are considered as atmospheric oxidants besides OH and NO3 radicals as well as ozone. Direct CI measurement techniques are inevitably needed for reliable assessment of CIs' role in atmospheric processes. We found that CIs from ozonolysis reactions can be directly probed by means of chemical ionization mass spectrometry with a detection limit of about 104-105 molecules cm-3. Results from quantum chemical calculations support the experimental findings. The simplest CI, CH2OO, is detectable as an adduct with protonated ethers, preferably with protonated tetrahydrofuran. Kinetic measurements yielded k(CH2OO + SO2) = (3.3 ± 0.9) × 10-11 and k(CH2OO + acetic acid) = (1.25 ± 0.30) × 10-10 cm3 molecule-1 s-1 at 295 ± 2 K, in very good agreement with recent measurements using diiodomethane photolysis for CH2OO generation. CIs from the ozonolysis of cyclohexene, acting as surrogate for cyclic terpenes, are followed as protonated species (CI)H+ using protonated amines as reagent ions. Kinetic investigations indicate a different reactivity of cyclohexene-derived CIs compared with that of simple CIs, such as CH2OO. It is supposed that the aldehyde group significantly influences the CI reactivity of the cyclohexene-derived CIs. The direct CI detection method presented here should allow study of the formation and reactivity of a wide range of different CIs formed from atmospheric ozonolysis reactions.

endo-Cyclization of unsaturated RO2 radicals from the gas-phase ozonolysis of cyclohexadienes.

Unsaturated RO2 radicals from the ozonolysis of cyclodienes can readily undergo an endo-cyclization step under atmospheric conditions forming a new ring-containing RO2 radical after further O2 addition. This path represents an extension of the atmospheric autoxidation scheme forming highly oxidized multifunctional organic compounds (HOMs). HOMs play an important role for Earth's organic aerosol burden.

Highly Oxidized Second-Generation Products from the Gas-Phase Reaction of OH Radicals with Isoprene.

The gas-phase reaction of OH radicals with isoprene has been investigated in an atmospheric pressure flow tube at 293 ± 0.5 K with special attention to the second-generation products. Reaction conditions were optimized to achieve a predominant reaction of RO2 radicals with HO2 radicals. Chemical ionization-atmospheric pressure interface-time-of-flight mass spectrometry served as the analytical technique in order to follow the formation of RO2 radicals and closed-shell products containing at least four O atoms in the molecule. The reaction products were detected as adducts with the reagent ions using acetate, lactate, or nitrate in the ionization process. Observed signals were attributed to a series of C5-products with multiple hydroxy, hydroperoxy, and probably carbonyl groups. H/D exchange experiments supported the product identification. The generation of the detected second-generation products can be mechanistically explained starting from the OH radical reaction of hydroxy hydroperoxide isomers, HO-C5H8-OOH. These isomers represent the dominant products of the initial OH radical attack on isoprene. Dihydroxy dihydroperoxides, (HO)2-C5H8-(OOH)2, were analyzed as the main second-generation products beside the dihydroxy epoxides. A simple kinetic analysis revealed that the observed second-generation products in total (other than dihydroxy epoxides) were formed with an estimated molar yield of 10.0-1.5+2.1 % with respect to converted hydroxy hydroperoxides. A formation yield of 5.8-0.9+1.3 % has been deduced for the main product (HO)2-C5H8-(OOH)2. The detected, highly oxidized isoprene products represent potential secondary organic aerosol precursors. An annual, global (HO)2-C5H8-(OOH)2 formation strength of (16-35) × 106 metric tons is estimated based on product measurements of this study and literature data regarding the formation of the dihydroxy epoxide isomers for an annual isoprene emission of 454 × 106 metric tons of carbon.

Gas-Phase Ozonolysis of Cycloalkenes: Formation of Highly Oxidized RO2 Radicals and Their Reactions with NO, NO2, SO2, and Other RO2 Radicals.

The gas-phase reaction of ozone with C5-C8 cycloalkenes has been investigated in a free-jet flow system at atmospheric pressure and a temperature of 297 ± 1 K. Highly oxidized RO2 radicals bearing at least 5 O atoms in the molecule and their subsequent reaction products were detected in most cases by means of nitrate-CI-APi-TOF mass spectrometry. Starting from a Criegee intermediate after splitting-off an OH-radical, the formation of these RO2 radicals can be explained via an autoxidation mechanism, meaning RO2 isomerization (ROO → QOOH) and subsequently O2 addition (QOOH + O2 → R'OO). Time-dependent RO2 radical measurements concerning the ozonolysis of cyclohexene indicate rate coefficients of the intramolecular H-shifts, ROO → QOOH, higher than 1 s(-1). The total molar yield of highly oxidized products (predominantly RO2 radicals) from C5-C8 cycloalkenes in air is 4.8-6.0% affected with a calibration uncertainty by a factor of about two. For the most abundant RO2 radical from cyclohexene ozonolysis, O,O-C6H7(OOH)2O2 ("O,O" stands for two O atoms arising from the ozone attack), the determination of the rate coefficients of the reaction with NO2, NO, and SO2 yielded (1.6 ± 0.5) × 10(-12), (3.4 ± 0.9) × 10(-11), and <10(-14) cm(3) molecule(-1) s(-1), respectively. The reaction of highly oxidized RO2 radicals with other peroxy radicals (R'O2) leads to detectable accretion products, RO2 + R'O2 → ROOR' + O2, which allows to acquire information on peroxy radicals not directly measurable with the nitrate ionization technique applied here. Additional experiments using acetate as the charger ion confirm conclusively the existence of highly oxidized RO2 radicals and closed-shell products. Other reaction products, detectable with this ionization technique, give a deeper insight in the reaction mechanism of cyclohexene ozonolysis.

Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K.

The rate coefficients of the reaction of ozone with the four atmospherically relevant sesquiterpenes ß-caryophyllene, α-humulene, α-cedrene and isolongifolene were investigated at 295 ± 2 K and atmospheric pressure by at least two independent experimental investigations for each reaction. Relative rate experiments were carried out in a flow tube using two different experimental approaches with GC-MS detection (RR 1) and PTR-MS analysis (RR 2) as the analytical techniques. Absolute rate coefficients were determined in a stopped-flow experiment following the ozone depletion by means of UV spectroscopy. The average rate coefficients from the combined investigations representing the mean values of the different experimental methods are (unit: cm(3) molecule(-1) s(-1)): k(O3+ß-caryophyllene) = (1.1 ± 0.3) × 10(-14) (methods: RR 1, RR 2, absolute), k(O3+α-humulene) = (1.2 ± 0.3) × 10(-14) (RR 1, RR 2), k(O3+α-cedrene) = (1.7 ± 0.5) × 10(-16) (RR 2, absolute) and k(O3+isolongifolene) = (1.1 ± 0.5) × 10(-17) (RR 2, absolute). The high ozonolysis rate coefficients for ß-caryophyllene and α-humulene agree well with the results by Shu and Atkinson (Int. J. Chem. Kinet., 1994, 26) and lead to short atmospheric lifetimes of about two minutes with respect to the ozone reaction. The relatively small rate coefficients for α-cedrene and isolongifolene differ from the available literature values by a factor of about 2.5-6. Possible reasons for the deviations are discussed. Finally, calibrated sesquiterpene FT-IR spectra were recorded for the first time.

Atmospheric reaction of OH radicals with 1,3-butadiene and 4-hydroxy-2-butenal.

The gas-phase reaction of OH radicals with 1,3-butadiene and 4-hydroxy-2-butenal in the presence of NO has been studied in a flow tube operated at 295 +/- 2 K and pressures of 950 mbar of synthetic air or 100 mbar of an O(2)/He mixture. OH radicals were generated using three different experimental approaches, namely, ozonolysis of tetramethylethylene (dark reaction), photolysis of methyl nitrite, or via the reaction of HO(2) with NO (HO(2) from the reaction of H-atoms with O(2)). Products of the reaction of OH radicals with 1,3-butadiene were HCHO (0.64 +/- 0.08), acrolein (0.59 +/- 0.06), 4-hydroxy-2-butenal (0.23 +/- 0.10), furan (0.046 +/- 0.014), and organic nitrates (0.06 +/- 0.02) accounting for more than 90% of the reacted carbon. There was no significant dependence of product yields on experimental conditions which were varied in a wide range. The formation of the 1,4-addition product 4-hydroxy-2-butenal was confirmed unambiguously for the first time. The rate coefficient k(OH + 4-hydroxy-2-butenal) = (5.1 +/- 0.8) x 10(-11) cm(3) molecule(-1) s(-1) was determined using a relative rate technique (p = 100 mbar, T = 295 +/- 2 K). Products of the reaction of OH radicals with 4-hydroxy-2-butenal were glycolaldehyde (0.40 +/- 0.06), glyoxal (0.17 +/- 0.04), trans-butenedial (0.093 +/- 0.033), and organic nitrates (0.043 +/- 0.015) as well as further carbonylic substances remaining unidentified so far. Corresponding reaction mechanisms describing the formation of the detected products are proposed, and the relevance of these data for atmospheric conditions is discussed.

Formation of phenol and carbonyls from the atmospheric reaction of OH radicals with benzene.

The gas-phase reaction of OH radicals with benzene has been studied in a flow tube operated at 295 +/- 2 K and 950 mbar of synthetic air or O2. Ozonolysis of tetramethylethylene (dark reaction) with a measured OH radical yield of 0.92 +/- 0.08 or photolysis of methyl nitrite in the presence of NO served as the OH sources. For investigations in the presence of NOx, the conditions were chosen so that more than 95% of the OH/benzene adduct reacted with O2 even for the highest NO2 concentration occurring in the experiment. In the absence of NOx, a phenol yield from the reaction of OH radicals with benzene of 0.61 +/- 0.07 was measured by means of long-path FT-IR and UV spectroscopy over a wide range of experimental conditions. This yield was confirmed by measurements performed in the presence of NOx. Detected carbonyls were glyoxal, cis-butenedial and trans-butenedial with formation yields of 0.29 +/- 0.10, 0.08 +/- 0.03 and 0.023 +/- 0.007, respectively, measured in synthetic air and in the presence of NOx. There was no significant difference in the product yields applying both experimental approaches for OH generation (dark reaction or photolysis). Nitrobenzene and o-nitrophenol were detected in traces. The yield of nitrobenzene increased with increasing NOx resulting in a maximum formation yield of 0.007. The detected products in the presence of NOx account for approximately 78% of the reacted carbon. Butenedial yields from benzene degradation are reported for the first time. In the absence of NOx, glyoxal, cis-butenedial and trans-butenedial were also detected, but with distinctly lower yields compared to the experiments with NOx.