Nucleation by free radicals from the photooxidation of sulfur dioxide in air

Friend, James P.; Barnes, Robert A.; Vasta, R. M.

doi:10.1021/j100456a018

Cited by 54 publications

(36 citation statements)

References 25 publications

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“…Experiments in the absence of UV light (dark reaction) showed exactly the same results indicating that irradiation itself does not influence new particle formation. This observation is qualitatively in good accord with the similar, long overlooked experiments of Friend et al (1980).…”

Section: Introductionsupporting

confidence: 92%

“…2. It can be seen that the atmospheric data points (Sihto et al, 2006) are situated more or less in between the Friend et al (1980) and Berndt et al (2005Berndt et al ( , 2006 laboratory data sets. Uncertainties in the laboratory data on SO 2 induced nucleation include possible errors in calculated H 2 SO 4 concentrations due to uncertain chemical mechanisms and not well defined wall losses of H 2 SO 4 ; uncertainty in nucleation rate due to uncertain effective volume inside the flow chamber where nucleation occurred; and possible effects from gaseous impurities.…”

Section: Comparison Of Atmospheric and Laboratory Nucleation Ratesmentioning

confidence: 99%

“…The new particle formation is generally thought to occur due to homogeneous or ion-induced nucleation of sulphuric acid (H 2 SO 4 ) (Kulmala, 2003) formed in oxidation of sulphur dioxide (SO 2 ). However, it has so far remained unclear why the binary classical nucleation theory (CNT) seems to explain ambient observations of nucleation above the altitude of 4 km (Weber et al, 1999) as well as laboratory nucleation experiments with vaporized sulphuric acid (Ball et al, 1999;Zhang et al, 2004), but severely underpredicts nucleation below 4 km (Weber et al, 1999) and in laboratory experiments involving oxidized SO 2 (Friend et al, 1980;Berndt et al, 2005Berndt et al, , 2006.…”

Section: Introductionmentioning

confidence: 99%

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SO2 oxidation products other than H2SO4 as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

et al. 2008

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Abstract. Atmospheric new particle formation is generally thought to occur due to homogeneous or ion-induced nucleation of sulphuric acid. We compare ambient nucleation rates with laboratory data from nucleation experiments involving either sulphuric acid or oxidized SO 2 . Atmospheric nucleation occurs at H 2 SO 4 concentrations 2-4 orders of magnitude lower than binary or ternary nucleation rates of H 2 SO 4 produced from a liquid reservoir, and atmospheric H 2 SO 4 concentrations are very well replicated in the SO 2 oxidation experiments. We hypothesize these features to be due to the formation of free HSO 5 radicals in pace with H 2 SO 4 during the SO 2 oxidation. We suggest that at temperatures above ∼250 K these radicals produce nuclei of new aerosols much more efficiently than H 2 SO 4 . These nuclei are activated to further growth by H 2 SO 4 and possibly other trace species. However, at lower temperatures the atmospheric relative acidity is high enough for the H 2 SO 4 -H 2 O nucleation to dominate.

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Section: Introductionsupporting

confidence: 92%

Section: Comparison Of Atmospheric and Laboratory Nucleation Ratesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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SO2 oxidation products other than H2SO4 as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

et al. 2008

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“…Similar experiments were conducted by Boulaud et al (1977) in a reactor study, Mirabel and Clavelin (1978) in a thermal diffusion cloud chamber, and Friend et al (1980) in a laminar flow reactor. More recent experiments include those made by Wyslouzil et al (1991), Viisanen et al (1997), Ball et al (1999), Zhang et al (2004), Berndt et al (2006), Benson et al (2008), and Young et al (2008).…”

Section: Introductionmentioning

confidence: 67%

“…All the latter experiments relied on a flow-based measurement technique. Some experimentalists (Friend et al, 1980;Berndt et al, 2006;Benson et al, 2008 andYoung et al, 2008) employ photooxidation of SO 2 and some produce gaseous mixtures from liquid H 2 SO 4 , using saturators (Wyslouzil et al, 1991 andBall et al, 1999) or liquid samples (Viisanen et al, 1997). However, it should be pointed out that laboratory measurements are widely conducted at temperatures 10-30 • C higher than nucleation occurs in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results

et al. 2010

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Abstract. In this study we introduce a new flow tube suitable for binary and ternary homogeneous nucleation studies. The production of sulfuric acid and water vapor mixture, the experimental setup and the method of sulfuric acid concentration determination are discussed in detail. Wall losses were estimated from the measured sulfuric acid concentration profiles along the flow tube and compared to a theoretical prediction. In this investigation the experimental evidence of new particle formation was observed at a concentration of 10 9 molecules cm −3 of sulfuric acid and the nucleation rates measured at three relative humidities (RH) 10, 30 and 50%, cover six orders of magnitude, from 10 −3 to 10 3 particles cm −3 . Particle free air was used as a carrier gas. Our initial results are compared to the theoretical prediction of binary homogeneous nucleation, to results obtained by other investigators, and to atmospheric nucleation.

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Effect of ions on sulfuric acid‐water binary particle formation: 2. Experimental data and comparison with QC‐normalized classical nucleation theory

et al. 2016

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We report comprehensive, demonstrably contaminant‐free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion‐induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface‐time of flight‐mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (105 to 109 mol cm−3), relative humidity (11% to 58%), temperature (207 K to 299 K), and total ion concentration (0 to 6800 ions cm−3). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC‐normalized CNT), which is described in a companion paper. The formation rates predicted by the QC‐normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion‐induced) sulfuric acid‐water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion‐induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC‐normalized CNT as a powerful tool to study neutral and ion‐induced binary particle formation in atmospheric modeling.

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Nucleation by free radicals from the photooxidation of sulfur dioxide in air

Cited by 54 publications

References 25 publications

SO<sub>2</sub> oxidation products other than H<sub>2</sub>SO<sub>4</sub> as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

SO<sub>2</sub> oxidation products other than H<sub>2</sub>SO<sub>4</sub> as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results

Effect of ions on sulfuric acid‐water binary particle formation: 2. Experimental data and comparison with QC‐normalized classical nucleation theory

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Nucleation by free radicals from the photooxidation of sulfur dioxide in air

Cited by 54 publications

References 25 publications

SO&lt;sub&gt;2&lt;/sub&gt; oxidation products other than H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

SO&lt;sub&gt;2&lt;/sub&gt; oxidation products other than H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

Homogeneous nucleation of sulfuric acid and water mixture: experimental setup and first results

Effect of ions on sulfuric acid‐water binary particle formation: 2. Experimental data and comparison with QC‐normalized classical nucleation theory

Contact Info

Product

Resources

About

SO<sub>2</sub> oxidation products other than H<sub>2</sub>SO<sub>4</sub> as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

SO<sub>2</sub> oxidation products other than H<sub>2</sub>SO<sub>4</sub> as a trigger of new particle formation. Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications