Investigation of the effect of water complexes in the determination of peroxy radical ambient concentrations: Implications for the atmosphere

Reichert, L.; Hernández, Maria Dolores Andrés; Stöbener, Dirk; Burkert, J.; Burrows, J. P.

doi:10.1029/2002jd002152

Cited by 51 publications

(41 citation statements)

References 43 publications

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“…Unpublished measurements made at the Max Planck Institute for Chemistry in Mainz (Thomas Klüpfel, personal communication) using a Teflon inlet showed a nearly identical response of the chemical amplification factor with respect to water to that observed by Mihele and Hastie (2000). Investigations using a different experimental technique and with an inlet made from plexiglass by Reichert (2000) (see also Reichert et al, 2003) found a much greater sensitivity to water vapour. The interpretation of the various studies is complicated by the fact that Reichert used a different material for the inlet, and a different experimental technique to measure the water effect.…”

Section: Methodsmentioning

confidence: 89%

“…The interpretation of the various studies is complicated by the fact that Reichert used a different material for the inlet, and a different experimental technique to measure the water effect. Reichert et al (2003) suggest that the water effect is not solely due to wall loss but is due to reactions involving water complexes and CO or NO. They use a model to reproduce both the measurements of Reichert et al and of Mihele and Hastie (1998).…”

Section: Methodsmentioning

confidence: 99%

“…The CA technique has been found to be sensitive to the relative humidity in the sample air (Reichert et al, 2003;Reichert, 2000;Mihele and Hastie, 2000;Mihele et al, 1999;Mihele and Hastie, 1998). The CA measurements were corrected for this effect using a parametrisation of the data of Mihele and Hastie (2000), which were obtained using a CA with a Teflon inlet and similar operating parameters to that of the CA used here.…”

Section: Methodsmentioning

confidence: 99%

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Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals

Handisides¹,

Plaß-Dülmer

Gilge

et al. 2003

Atmos. Chem. Phys.

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Abstract. Measurements of OH, total peroxy radicals, nonmethane hydrocarbons (NMHCs) and various other trace gases were made at the Meteorological Observatory Hohenpeissenberg in June 2000. The data from an intensive measurement period characterised by high solar insolation (18-21 June) are analysed. The maximum midday OH concentration ranged between 4.5×10 6 molecules cm −3 and 7.4×10 6 molecules cm −3 . The maximum total RO x (RO x =OH+RO+HO 2 +RO 2 ) mixing ratio increased from about 55 pptv on 18 June to nearly 70 pptv on 20 and 21 June. A total of 64 NMHCs, including isoprene and monoterpenes, were measured every 1 to 6 hours. The oxidation rate of the NMHCs by OH was calculated and reached a total of over 14×10 6 molecules cm −3 s −1 on two days. A simple photostationary state balance model was used to simulate the ambient OH and peroxy radical concentrations with the measured data as input. This approach was able to reproduce the main features of the diurnal profiles of both OH and peroxy radicals. The balance equations were used to test the effect of the assumptions made in this model. The results proved to be most sensitive to assumptions about the impact of unmeasured volatile organic compounds (VOC), e.g. formaldehyde (HCHO), and about the partitioning between HO 2 and RO 2 . The measured OH concentration and peroxy radical mixing ratios were reproduced well by assuming the presence of 3 ppbv HCHO as a proxy for oxygenated hydrocarbons, and a HO 2 /RO 2 ratio between 1:1 and 1:2. The most important source of OH, and conversely the greatest sink for peroxy radicals, was the recycling of HO 2 radicals to OH. This reaction was responsible for the recycling of more than 45×10 6 molecules cm −3 s −1 on two days. The most important sink for OH, and the largest source of peroxy radicals, was the oxidation of NMHCs, in particular, of isoprene and the monoterpenes.

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Section: Methodsmentioning

confidence: 89%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals

Handisides¹,

Plaß-Dülmer

Gilge

et al. 2003

Atmos. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…The calibration source of a Chemical Ionization Mass Spectrometer (CIMS, Slusher et al, 2004) In fact, the chain lengths determined by the two procedures differed by less than 10%, a difference that is well within the range of the estimated measurement error of the PERCA. Previous work has shown the PERCA chain length to be dependent on both ambient humidity and temperature (Salisbury et al, 2002;Reichert et al, 2003). Therefore, it is usually determined in dry air and then corrected using a calibration factor.…”

Section: Percamentioning

confidence: 99%

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

et al. 2011

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Abstract. During the Texas Air Quality Study II (Tex-AQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO 2 + RO 2 ). Day-time mixing ratios of HO 2 + RO 2 between 25 and 110 ppt were observed throughout the study area -the Houston/Galveston region and the Gulf coast of the US -and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region.The measurements of HO 2 + RO 2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity Correspondence to: R. Sommariva (r.sommariva@uea.ac.uk) to understand the relationship between ozone formation and local VOC emissions.The measurements of HO 2 + RO 2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NO x -limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photo-oxidation products, such as formaldehyde.

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“…Switching the two inlets between phases on a minute time scale leads to a continuous amplification and termination signal. Mihele et al (1998Mihele et al ( , 1999 have shown that the chain length of a chemical amplifier is reduced in the presence of atmo-spheric water vapour (see also Reichert et al, 2003). Salisbury et al (2002) demonstrated that the chain length of the Leicester-UEA PERCA instrument falls approximately linearly with increasing specific humidity.…”

Section: Peroxy Radical Measurements (Perca)mentioning

confidence: 99%

Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

et al. 2006

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Abstract. Peroxy radical (HO 2 + RO 2 ) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundarylayer chemistry. A suite of other chemical parameters (NO, NO 2 , NO 3 , CO, CH 4 , O 3 , VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HO x . A good correlation exists between j (HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HO x source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO x ] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO 2 /(HO 2 + RO 2 ) ratios are dependent on [NO x ] ranging between 0.2 and 0.6, with the ratio increasing linearly with NO x . Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO 3 -alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv Correspondence to: P. S. Monks (p.s.monks@le.ac.uk) h −1 . The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O 3 ))/dln(NO)=1.0). The results imply that the N(O 3 ) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NO x loadings in the European continental boundary layer.

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Investigation of the effect of water complexes in the determination of peroxy radical ambient concentrations: Implications for the atmosphere

Cited by 51 publications

References 43 publications

Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals

Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

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