The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

Penkett, S. A.; Jones, Brian M.; Brich, K.A.; Eggleton, A. E. J.

doi:10.1016/0004-6981(79)90251-8

Cited by 486 publications

(95 citation statements)

References 22 publications

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“…All of these other processes may be occurring but their inclusion would lead to a much more complex form of expression (1) and it is our purpose to keep our analysis of the data as simple as possible in this paper We do recognize that the influence of transport is important and that derivation of a calculated peroxide concentration using j values characteristic of the latitude of the measurements may lead to underestimates if the air mass has moved rapidly from equatorial to midlatitudes for instance. Finally, we also recognize that multiphase oxidation of SO2 by H202 can reduce the peroxide concentration in plumes of polluted air [Penkett et al, 1979]. This is only likely to be a major loss process for H202, though, in cloudy conditions close to continental sources of SO2 at lower altitudes.…”

Section: Production Of Peroxides From Photolysis Of Ozone In the Presmentioning

confidence: 81%

Comparison of calculated and measured peroxide data collected in marine air to investigate prominent features of the annual cycle of ozone in the troposphere

Penkett¹,

Reeves²,

Bandy³

et al. 1998

J. Geophys. Res.

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Abstract. Large amounts of data on the concentration of peroxides have been collected in vertical profiles over the North Atlantic Ocean by a Hercules aircraft. The measured peroxide concentrations have been compared with concentrations calculated by a simple algorithm derived assuming that the standing peroxide concentration is in equilibrimn with its production and loss processes. In clean air where the peroxide and ozone concentrations are anticorrelated throughout the profile measured and calculated peroxide concentrations coincide, whereas in layers of polluted air within the profile, as determined from positive ozone peroxide correlations, calculated peroxide concentrations are greatly in excess of measured values. Using the degree of correlation between measured and calculated peroxide concentrations as a diagnostic, it is possible to show that many aspects of the seasonal cycle of ozone are caused by in situ tropospheric chemistry. Thus the summer minimum in the seasonal cycle of ozone, observed at clean marine ground-based sites such as Mace Head, is due to photochemical destruction, and elevated levels of ozone are associated with the transport of polluted air, on occasion over thousands of kilometers. Of particular interest if our analysis is correct, the broad maximum of ozone occurring between March and May at ground-based sites has a large contribution from ozone formed by tropospheric as well as stratospheric chemistry.

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Section: Production Of Peroxides From Photolysis Of Ozone In the Presmentioning

confidence: 81%

Comparison of calculated and measured peroxide data collected in marine air to investigate prominent features of the annual cycle of ozone in the troposphere

Penkett¹,

Reeves²,

Bandy³

et al. 1998

J. Geophys. Res.

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“…In a study by Kim et al (2002), as pointed out earlier, it is shown that cloud processing of airmasses may have different effects on the mixing ratios of H 2 O 2 depending on the general chemical conditions, including NO x concentrations and the time of day. The scavenging efficiency is also strongly dependent on the temperature of the cloud, the state of the hydrometeors and on the SO 2 concentration within the aqueous phase, which reacts with H 2 O 2 molecules (Penkett et al, 1979;Heikes et al, 1987;Mohnen and Kadlecek, 1989;Penkett et al, 1989;Clegg and Abbatt, 2001). …”

Section: Figmentioning

confidence: 99%

“…Atmospheric H 2 O 2 gained attention in the late 1970s, when it was identified as one of the key oxidants of sulfur dioxide (SO 2 ) in cloud droplets (for pH < 4.5) leading to acidification of cloud water and subsequently to acid precipitation, which was a major environmental issue (Penkett et al, 1979;Robbin Martin and Damschen, 1981;Kunen et al, 1983;Calvert et al, 1985). Today it is clear that besides being an important oxidant, H 2 O 2 and the organic peroxides, together with HCHO, play an important role as reservoir species for the HO x family, thus modulating the oxidation power and self cleaning capacity of the atmosphere (Lelieveld and Crutzen, 1990;Crutzen et al, 1999).…”

Section: Introductionmentioning

confidence: 99%

Distribution of hydrogen peroxide and formaldehyde over Central Europe during the HOOVER project

et al. 2011

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Abstract. In this study we report measurements of hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HO x OVer EuRope (HOOVER) project (HO x = OH+HO 2 ). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54 • N, 9 • E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H 2 O 2 and CH 3 OOH * . In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H 2 O 2 and CH 3 OOH * show maxima above the boundary layer at 2-5 km, being more distinct over southern than over northern Europe.We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H 2 O 2 . Large uncertainties about retention coefficients and Correspondence to: H. Fischer (horst.fischer@mpic.de) cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H 2 O 2 . A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H 2 O 2 as simulations improve significantly with this effect switched off.

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“…1. H 2 O 2 is also a major oxidant of sulphur dioxide (SO 2 ) in clouds (Penkett et al, 1979) so alongside O 3 and OH, its measurement is needed to assess the oxidative capacity of the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Processes controlling the concentration of hydroperoxides at Jungfraujoch Observatory, Switzerland

et al. 2006

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Abstract. An automated, ground-based instrument was used to measure gas-phase hydroperoxides at the Jungfraujoch High Altitude Research Station as part of the Free Tropospheric EXperiment (FREETEX) during February/March 2003. A nebulising reflux concentrator sampled ambient air twice hourly, prior to on-site analysis by HPLC speciation, coupled with post-column peroxidase derivatisation and fluorescence detection. Hydrogen peroxide (H 2 O 2 ) concentrations reached up to 1330 pptv over the 13-day period with a mean of 183±233 pptv (± one standard deviation). Methyl hydroperoxide (CH 3 OOH) reached up to 379 pptv with a mean of 51±55 pptv. No other organic hydroperoxides were detected. The lack of an explicit diurnal cycle suggests that hydroperoxide concentrations are chiefly influenced by transport processes rather than local photochemistry at this mountainous site. There was some evidence that elevated concentrations of H 2 O 2 existed in air-masses originating from the south-west, suggesting higher concentrations of HO x due to more active photochemistry. Air which had been recently polluted exhibited low H 2 O 2 concentration due to a combination of suppression of HO 2 by NO x and deposition. The concentrations of H 2 O 2 sampled here are consistent with previous box modelling studies of hydroperoxides, except in periods influenced by the boundary layer, where agreement required a depositional sink.

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The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

Cited by 486 publications

References 22 publications

Comparison of calculated and measured peroxide data collected in marine air to investigate prominent features of the annual cycle of ozone in the troposphere

Comparison of calculated and measured peroxide data collected in marine air to investigate prominent features of the annual cycle of ozone in the troposphere

Distribution of hydrogen peroxide and formaldehyde over Central Europe during the HOOVER project

Processes controlling the concentration of hydroperoxides at Jungfraujoch Observatory, Switzerland

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