Oxidation of Atmospheric SO2 by Products of the Ozone–Olefin Reaction

Cox, R. A.; Penkett, S. A.

doi:10.1038/230321a0

Cited by 93 publications

(72 citation statements)

References 10 publications

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“…Moreover, in some circumstances scavenging of SCI may not necessarily suppress particle formation. For example, in the presence of SO 2 , the reactions between SCI and SO 2 can lead to the formation of H 2 SO 4 , 5,74,93,96,97 an important nucleation precursor. 98,99 A quantitative evaluation of the atmospheric importance of RO 2 + SCI reactions is not possible at the moment because of the large uncertainties in the rate constants for bimolecular reactions of SCI, 45,67 especially those of RO 2 + SCI reactions for which experimental data are not available.…”

Section: Conclusion and Atmospheric Implicationsmentioning

confidence: 99%

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Zhao

Wingen

Perraud

et al. 2015

Phys. Chem. Chem. Phys.

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Section: Conclusion and Atmospheric Implicationsmentioning

confidence: 99%

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Zhao

Wingen

Perraud

et al. 2015

Phys. Chem. Chem. Phys.

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“…Heterogeneous oxidation (on the surface of aerosol particles and in cloud and fog droplets) is dominated by reactions with either dissolved ozone, hydrogen peroxide, or molecular oxygen, the latter pathway being catalyzed by transition metal ions (Harris et al, 2013;Berresheim and Jaeschke, 1986). However, recent studies have revived an interest in the formation and fate of atmospheric Criegee intermediates (radical species produced from reactions of ozone with alkenes; Calvert et al, 2000;Criegee, 1975), which to this day have eluded direct measurements in the atmosphere since Cox and Penkett (1971) first suggested their potentially important role. Field and laboratory measurements (Berndt et al, , 2014Stone et al, 2014;Taatjes et al, 2014;Mauldin III et al, 2012;Welz et al, 2012) as well as theoretical and modeling studies (Sarwar et al, 2014;Boy et al, 2013;Vereecken et al, 2012) now suggest that the reactivity of these types of radicals towards compounds such as SO 2 may have been underestimated by at least 2 orders of magnitude.…”

Section: H Berresheim Et Al: Missing So 2 Oxidant In the Coastal Atmentioning

confidence: 99%

Missing SO2 oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

et al. 2014

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Abstract. Diurnal and seasonal variations of gaseous sulfuric acid (H 2 SO 4 ) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 10 4 cm −3 at 5 min signal integration. The H 2 SO 4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 µm (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H 2 SO 4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO 2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO 2 oxidant was additionally confirmed by direct measurements of SO 2 in conjunction with calculated H 2 SO 4 concentrations. The calculated H 2 SO 4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO 2 by OH as the only source of H 2 SO 4 . Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J (O 1 D), and were followed by peaks in both H 2 SO 4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO 2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on ab initio calculations. Nevertheless, IO could contribute significantly to the observed CIMS background signal. A detailed analysis of this CIMS background signal in context with recently published kinetic data currently suggests that Criegee intermediates (CIs) produced from ozonolysis of alkenes play no significant role for SO 2 oxidation in the marine atmosphere at Mace Head. On the other hand, SO 2 oxidation by small CIs such as CH 2 OO produced photolytically or possibly in the photochemical degradation of methane is consistent with our observations. In addition, H 2 SO 4 formation from dimethyl sulfide oxidation via SO 3 as an intermediate instead of SO 2 also appears to be a viable explanation. Both pathways need to be further explored.

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“…SCIs have been shown in laboratory experiments and by theoretical calculations to oxidise SO 2 and NO 2 (e.g. Cox and Penkett, 1971;Taatjes et al, 2013;Ouyang et al, 2013;Stone et al, 2014) as well as a number of other trace gases found in the atmosphere. Recent field measurements in a boreal forest (Mauldin III et al, 2012) and at a coastal site (Berresheim et al, 2014) have both identified an apparently missing process oxidising SO 2 to H 2 SO 4 (in addition to reaction with OH) and have implied SCIs as a possible oxidant, acting alongside OH.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO2, H2O and dimethyl sulfide

et al. 2015

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Abstract. Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO 2 and NO 2 in the atmosphere; however the significance of this chemistry for SO 2 processing (affecting sulfate aerosol) and NO 2 processing (affecting NO x levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO 2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO 2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H 2 O. Under excess SO 2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + H 2 O) / k(SCI + SO 2 ), of 3.1 (±0.5) × 10 −5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO 2 ) is 3.0 (±3.2) × 10 11 cm −3 . Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprenederived SCIs are unlikely to make a substantial contribution to gas-phase SO 2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO 2 removal in the isopreneozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS) / k(SCI + SO 2 ), of 3.5 (±1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

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Oxidation of Atmospheric SO2 by Products of the Ozone–Olefin Reaction

Cited by 93 publications

References 10 publications

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Missing SO<sub>2</sub> oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

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Oxidation of Atmospheric SO2 by Products of the Ozone–Olefin Reaction

Cited by 93 publications

References 10 publications

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air

Missing SO&lt;sub&gt;2&lt;/sub&gt; oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O and dimethyl sulfide

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Missing SO<sub>2</sub> oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide