A high-performance liquid chromatography system with an immobilized enzyme reactor for detection of hydrophilic organic peroxides

Kurth, H; Gaeb, S.; Turner, Walter V.; Kettrup, A.

doi:10.1021/ac00022a010

Cited by 38 publications

(23 citation statements)

References 18 publications

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“…Units for the organic signal are given in equivalent ppb because this channel was calibrated using H202 instead of CH3OOH or hydroxymethylhydroperoxide (HMHP). It was shown previously [Kurth et al, 1991] [1988]. This technique had a detection limit of 120 ppt (30.).…”

mentioning

confidence: 78%

On the budget of photooxidants in the marine boundary layer of the tropical South Atlantic

Junkermann¹,

Stockwell²

1999

J. Geophys. Res.

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Abstract. Measurements of ozone, hydrogen peroxide, methylhydroperoxide, and formaldehyde in the marine boundary layer of the tropical southern Atlantic Ocean were performed on board the research vessel Polarstem during its cruise from Bremerhaven, Germany (54øN, 8øE), to Punta Arenas, Chile (53øS, 71øW), in October and November 1994. Model calculations were made to estimate the deposition rates of H20 2 and CH3OOH. The modeling required that long-range transport and advection processes of photochemical aged air masses that originated in African biomass burning plumes be taken into account. For H20 2 the dry deposition rate was estimated to be 1 x 10-5/s and the air-sea flux was estimated to be 4.5 x 10 •ø molecules/cm 2 s, while for CH3OOH the dry deposition and the air-sea flux were estimated to be 0.8 x 10-5/s and 3 x 10 •ø molecules/cm 2 s, respectively. These values compared well with other estimates. Because of the uncertainties in the rate constants for the photochemical production and loss of methyl hydrogen peroxide the accuracy of the calculated deposition rates for both CH3OOH and H20 2 is limited. These chemical rate constants are not accurate enough to provide an unambiguous estimate of the deposition rate constants through simulation of field observations. IntroductionPeroxides ( [1994] reported that the organic fraction represented a fairly high contribution to the total peroxide content. Thus the organic chemistry plays a significant role in the radical budget and organic radicals must be taken into account in the modeling of the observed mixing ratios of H202, CH3OOH , and CH20 and the derivation of their dry deposition loss rates because of the large fraction of HOx consumed in the production of CH3OOH and possibly other hydroperoxides.In this paper we present data on the mixing ratios of ozone, H202, CH3OOH, and CH20 in the marine boundary layer of the tropical southern Atlantic Ocean. The results of model calculations that were made to estimate the deposition rate of H202 and CH3OOH and CH20 are also presented. The modeling results suggested that measurements were affected by long-range transport and advection of photochemical aged air masses that originated in African biomass burning plumes. Experimental ProcedureThe experiments were performed on board the RV Polarstern during its cruise from Bremerhaven, Germany (54øN, 8øE) to Punta Arenas, Chile (53øS, 71øW) in October and

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confidence: 78%

On the budget of photooxidants in the marine boundary layer of the tropical South Atlantic

Junkermann¹,

Stockwell²

1999

J. Geophys. Res.

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“…The basis of this method is to quantify the fluorescent dimer produced by the stoichiometric reaction of POPHA and hydroperoxides through catalysis (Gäb et al, 1985;Hellpointner and Gäb, 1989;Kurth et al, 1991;Lee et al, 1995;Sauer et al, 1996Sauer et al, , 1997Sauer et al, , 1999Sauer et al, , 2001Grossmann et al, 2003;François et al, 2005;Xu and Chen, 2005;Walker et al, 2006). The catalyst used in this study was Hemin (Xu and Chen, 2005;Chen et al, 2008).…”

Section: Measurement Methodsmentioning

confidence: 99%

Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols

et al. 2008

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Abstract. Atmospheric hydrogen peroxide (H 2 O 2 ) and organic hydroperoxides were measured from 18 to 30 July in 2006 during the PRIDE-PRD'06 campaign at Backgarden, a rural site located 48 km north of Guangzhou, a mega-city in southern China. A ground-based instrument was used as a scrubbing coil collector to sample ambient air, followed by on-site analysis by high-performance liquid chromatography (HPLC) coupled with post-column derivatization and fluorescence detection. The H 2 O 2 mixing ratio over the 13 days ranged from below the detection limit to a maximum of 4.6 ppbv, with a mean (and standard deviation) of (1.26±1.24) ppbv during the daytime (08:00-20:00 LT). Methyl hydroperoxide (MHP), with a maximum of 0.8 ppbv and a mean (and standard deviation) of (0.28±0.10) ppbv during the daytime, was the dominant organic hydroperoxide. Other organic peroxides, including bis-hydroxymethyl hydroperoxide (BHMP), peroxyacetic acid (PAA), hydroxymethyl hydroperoxide (HMHP), 1-hydroxy-ethyl hydroperoxide (1-HEHP) and ethyl hydroperoxide (EHP), were detected occasionally. The concentration of H 2 O 2 exhibited a pronounced diurnal variation on sunny days, with a peak mixing ratio in the afternoon (12:00-18:00 LT), but lacked an explicit diurnal cycle on cloudy days. Sometimes a second peak mixing ratio of H 2 O 2 was observed during the evening, suggesting that H 2 O 2 was produced by the ozonolysis of Correspondence to: Z. M. Chen (zmchen@pku.edu.cn) alkenes. The diurnal variation profile of MHP was, in general, consistent with that of H 2 O 2 . The estimation indicated that in the morning the H 2 O 2 detected was formed mostly through local photochemical activity, with the rest probably attributable to vertical transport. It is notable that relatively high levels of H 2 O 2 and MHP were found in polluted air. The unexpectedly high level of HO 2 radicals detected in this region can account for the production of hydroperoxides, while the moderate level of NO x suppressed the formation of hydroperoxides. High concentrations of hydroperoxides were detected in samples of rainwater collected in a heavy shower on 25 July when a typhoon passed through, indicating that a considerable mixing ratio of hydroperoxides, particularly MHP, resided above the boundary layer, which might be transported on a regional scale and further influence the redistribution of HO x and RO x radicals. It was found that hydroperoxides, in particular H 2 O 2 , play an important role in the formation of secondary sulfate in the aerosol phase, where the heterogeneous reaction might contribute substantially. A negative correlation between hydroperoxides and water-soluble organic compounds (WSOC), a considerable fraction of the secondary organic aerosol (SOA), was observed, possibly providing field evidence for the importance of hydroperoxides in the formation of SOA found in previous laboratory studies. We suggest that hydroperoxides act as an important link between sulfate and organic aerosols, which needs further study and should be considered in cu...

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“…After passing through the coil collector, 2 ml of the stripping solution (acidified 18 MOhm water, H 3 PO 4 at pH 3.5) were injected into a sample vial of an autosampler, from which 500 µl were processed by the HPLC. Peroxide mixing ratios were determined by reversed-phase HPLC with post-column derivatisation involving p-hydroxyphenyl acetic acid and horseradish peroxidase (Hellpointner and Gäb, 1989;Kurth et al, 1991;Gäb et al, 1995;Sauer et al, 1996Sauer et al, , 1997Sauer, 1997;Grossmann, 1999). Fluorescence detection of the biphenyl derivative formed in the derivatisation reaction was done at wavelengths of λ ex = 287 nm and λ em = 412 nm with a programmable Hewlett Packard 1046b fluorescence detector.…”

Section: H 2 O 2 and Organic Peroxidesmentioning

confidence: 99%

Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Moortgat

Grossmann

Boddenberg

et al. 2002

Tropospheric Chemistry

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Abstract. Gas-phase H 2 O 2 , organic peroxides and carbonyl compounds were determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide (MHP, CH 3 OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH 2 OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based on O-pentafluorobenzyl hydroxylamine as derivatisation agent. Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20-21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H 2 O 2 was formed through recombination reactions of HO 2 radicals, but there is some evidence that H 2 O 2 is also formed from ozonolysis of anthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C 2 to C 10 , isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o-and m-tolylaldehyde) and pinonaldehyde.

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A high-performance liquid chromatography system with an immobilized enzyme reactor for detection of hydrophilic organic peroxides

Cited by 38 publications

References 18 publications

On the budget of photooxidants in the marine boundary layer of the tropical South Atlantic

On the budget of photooxidants in the marine boundary layer of the tropical South Atlantic

Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols

Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

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