A numerical investigation of the destruction of peroxy radical by Cu ion catalysed reactions on atmospheric particles

Ross, Howard B.; Noone, Kevin J.

doi:10.1007/bf00115775

Cited by 26 publications

(21 citation statements)

References 18 publications

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“…Furthermore, the activity of Cu and Fe in the aqueous phase is important factor, because of the non-ideality of the concentrated solutions. The values of activity coefficient for Cu and Fe are roughly estimated to be less than 0.1, based on (NH 4 ) 2 SO 4 particles at 68 % RH (Ross and Noone, 1991), suggesting the free form metal ions will be limited in the particles. In the following calculations, we assumed that the activity coefficients for Cu and Fe are 0.01-0.1.…”

Section: Measurement Of Uptake Coefficientmentioning

confidence: 99%

Measurement of overall uptake coefficients for HO2 radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

et al. 2012

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Abstract. HO 2 uptake coefficients for ambient aerosol particles, collected on quartz fiber filter using a high-volume air sampler in China, were measured using an aerosol flow tube coupled with a chemical conversion/laser-induced fluorescence technique at 760 Torr and 298 K, with a relative humidity of 75 %. Aerosol particles were regenerated with an atomizer using the water extracts from the aerosol particles. Over 10 samples, the measured HO 2 uptake coefficients for the aerosol particles at the Mt. Tai site were ranged from 0.13 to 0.34, while those at the Mt. Mang site were in the range of 0.09-0.40. These values are generally larger than those previously reported for single-component particles, suggesting that reactions with the minor components such as metal ions and organics in the particle could contribute to the HO 2 uptake. A box model calculation suggested that the heterogeneous loss of HO 2 by ambient particles could significantly affect atmospheric HO x concentrations and chemistry.

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Section: Measurement Of Uptake Coefficientmentioning

confidence: 99%

Measurement of overall uptake coefficients for HO2 radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

et al. 2012

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“…NH + 4 , H + , HSO − 4 , SO 2− 4 ) (Table S6). Activity coefficients for trace metal ions and neutral species are calculated based on specific ion interaction theory or estimated following Ross and Noone (1991) (supplemental material, summarized in Table S7). We also account for the salting out effect on Henry's law constants.…”

Section: Formulation Of Ho 2 Reactive Uptake By Aerosolsmentioning

confidence: 99%

Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

et al. 2013

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The hydroperoxyl radical (HO2) is a major precursor of OH and tropospheric ozone. OH is the main atmospheric oxidant, while tropospheric ozone is an important surface pollutant and greenhouse gas. Standard gas-phase models for atmospheric chemistry tend to overestimate observed HO2 concentrations, and this has been tentatively attributed to heterogeneous uptake by aerosol particles. It is generally assumed that HO2 uptake by aerosol involves conversion to H2O2, but this is of limited efficacy as an HO2 sink because H2O2 can photolyze to regenerate OH and from there HO2. Joint atmospheric observations of HO2 and H2O2 suggest that HO2 uptake by aerosols may in fact not produce H2O2. Here we propose a catalytic mechanism involving coupling of the transition metal ions Cu(I)/Cu(II) and Fe(II)/Fe(III) to rapidly convert HO2 to H2O in aqueous aerosols. The implied HO2 uptake and conversion to H2O significantly affects global model predictions of tropospheric OH, ozone, carbon monoxide (CO) and other species, improving comparisons to observations in the GEOS-Chem model. It represents a previously unrecognized positive radiative forcing of aerosols through the effects on the chemical budgets of major greenhouse gases including methane and hydrofluorocarbons (HFCs)

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“…HO,, reaction probability. Odd hydrogen radicals such as HO: and OH are likely to react on atmospheric dust particles, probably through catalytic pathways involving redox reactions with iron or copper [Ross and Noone, 1991]. A study by Matthijsen and Sedlak [1995] showed that in cloud droplets, in the presence of iron or copper, the destruction of HO: results in the formation of hydrogen peroxide through the reactions: [1992] observed uptake coefficients c• for HO 2 larger than 0.01-0.05 on water and H2SO 4 surfaces, respectively.…”

Section: Reaction Rates On Dust Particlesmentioning

confidence: 99%

Role of mineral aerosol as a reactive surface in the global troposphere

Dentener¹,

Carmichael²,

Zhang³

et al. 1996

J. Geophys. Res.

1,090

943

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Abstract. A global three-dimensional model of the troposphere is used to simulate the sources, abundances, and sinks of mineral aerosol and the species involved in the photochemical oxidant, nitrogen, and sulfur cycles. Although the calculated heterogeneous removal rates on mineral aerosol are highly uncertain, mainly due to poorly known heterogeneous reaction rates, the reaction of SO2 on calcium-rich mineral aerosol is likely to play an important role downwind of arid source regions. This is especially important for regions in Asia, which are important and increasing emitters of sulfur compounds. Our results indicate that the assumption that sulfate aerosol follows an accumulation mode size distribution, is particularly in Asia likely to overestimate the sulfate aerosol climatecooling effect. An even larger fraction of gas phase nitric acid may be associated with and neutralized by mineral aerosol. Interactions of N205, 03, and HO2-radicals with dust are calculated to affect the photochemical oxidant cycle, causing ozone decreases up to 10% in and nearby the dust source areas. Comparison of these results with limited available measurements indicates that the proposed reactions can indeed take place, although due to a lack of measurements a rigorous evaluation is not possible at this time.

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A numerical investigation of the destruction of peroxy radical by Cu ion catalysed reactions on atmospheric particles

Cited by 26 publications

References 18 publications

Measurement of overall uptake coefficients for HO<sub>2</sub> radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

Measurement of overall uptake coefficients for HO<sub>2</sub> radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

Role of mineral aerosol as a reactive surface in the global troposphere

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A numerical investigation of the destruction of peroxy radical by Cu ion catalysed reactions on atmospheric particles

Cited by 26 publications

References 18 publications

Measurement of overall uptake coefficients for HO&lt;sub&gt;2&lt;/sub&gt; radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

Measurement of overall uptake coefficients for HO&lt;sub&gt;2&lt;/sub&gt; radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols

Role of mineral aerosol as a reactive surface in the global troposphere

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Product

Resources

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Measurement of overall uptake coefficients for HO<sub>2</sub> radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)

Measurement of overall uptake coefficients for HO<sub>2</sub> radicals by aerosol particles sampled from ambient air at Mts. Tai and Mang (China)