A study of relationships between isoprene, its oxidation products, and ozone, in the Lower Fraser Valley, BC

Biesenthal, T.; Wu, Qin; Shepson, P. B.; Wiebe, H. A.; Anlauf, K. G.; Mackay, G. I.

doi:10.1016/s1352-2310(96)00318-4

Cited by 115 publications

(90 citation statements)

References 25 publications

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“…The night-time ratio decreased to values in the range 1.5-1.0, and is consistent with the enhanced role of ozoneinitiated reactions with isoprene and the unsaturated carbonyl compounds. Similar diurnal variation of MVK/MACR ratio was also observed by Martin et al (1991), Yokouchi (1994), Montzka et al (1995) and Biesenthal et al (1997) in rural sites.…”

Section: Photooxidation Products Of Isoprenesupporting

confidence: 82%

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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Section: Photooxidation Products Of Isoprenesupporting

confidence: 82%

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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“…The gas phase mixing ratios of isoprene's oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also simultaneously monitored, as were the mixing ratios of several other C3-C5 carbonyl compounds. Different incarnations of the measurement system have been described previously Biesenthal and Shepson, 1997]; the particular version used in this study will be summarized briefly here.…”

Section: Biogenic Hydrocarbons and Oxidation Productsmentioning

confidence: 99%

The chemistry of biogenic hydrocarbons at a rural site in eastern Canada

Biesenthal¹,

Bottenheim²,

Shepson³

et al. 1998

J. Geophys. Res.

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Abstract. An intensive field study was undertaken in southern Nova Scotia, on the east coast of Canada, for several weeks during the summer of 1996 as part of the North American Research Strategy for Tropospheric Ozone -Canada East ( NARSTO-CE ) 1996 field measurement campaign. Clean air conditions prevailed during most of the study period, which allowed an examination of biogenic hydrocarbon chemistry with minimal influence from anthropogenic pollutants. Low NOx mixing ratios during the study had an impact on the ratio of isoprene's oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) to isoprene. The effects include changes to the fate of isoprene peroxy radicals and to the concentration of OH compared to conditions of higher [NOx]. Comparison to other studies indicate that there is a relationship between the ratio (MVK+MACR)/isoprene and the mixing ratio ofNOx. Biogenic hydrocarbons were the dominant reactive volatile organic compound (VOC) precursors to ozone production in this region, although the net ozone production rate predicted by a box-model simulation of the measurement data was only < 1 ppbv h -•. The evidence confirms that ozone production at this site is very NOx-sensitive.Model simulations indicated that the ozonolysis of biogenic hydrocarbons is an important source of the hydroxyl radical at this site and that OH was, in fact, the dominant oxidant during the nighttime under the observed low NOx conditions. Although the OH source did affect the nighttime mixing ratios of biogenic hydrocarbons, it could not fully explain the rapid noctumal decay of isoprene observed on most evenings.

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“…Since cities like Manaus lie within the largest terrestrial sources of biogenic VOC (Guenther et al, 1995), there are global scale motivations for characterizing their local atmospheric chemistry. While in the absence of anthropogenic NO x emissions, biogenic VOC are considered to contribute little to ozone formation (or may even lead to a reduction in ambient ozone mixing ratios), it is common knowledge that the photooxidation of isoprene in the presence of sufficient NO x results in formation of ozone and can give rise to strongly elevated ozone levels in both urban and rural environments in summer Chameides et al, 1992;Biesenthal et al, 1997;Starn et al, 1998;Roberts et al, 1998;Wiedinmyer et al, 2001). The polluted outflow plume of Manaus City enters the otherwise unpolluted atmosphere of the tropical rainforest (dubbed "green ocean air" by Williams et al, 2002), where NO x levels are near the crossover point from net loss of O 3 to net production.…”

Section: Introductionmentioning

confidence: 99%

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

et al. 2010

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Abstract. As a contribution to the Large-Scale BiosphereAtmosphere Experiment in Amazonia -Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O 3 , NO, NO 2 , CO, VOC, CO 2 , and H 2 O. Aerosol loads were characterized by concentrations of total aerosol number (CN) and cloud condensation nuclei (CCN), and by light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levCorrespondence to: U. Kuhn (uwe.kuhn@art.admin.ch) els of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios within the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h −1 .Within the plume core, aerosol concentrations were strongly enhanced, with CN/ CO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. CN/ CO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large Published by Copernicus Publications on behalf of the European Geosciences Union. 9252 U. Kuhn et al.: Impact of Manaus City on the Amazon Green Ocean atmosphere fraction of the total particle number served as CCN (about 60-80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16 ± 12 %) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The COnormalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species.We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NO x and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NO x ) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NO x . The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the b...

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A study of relationships between isoprene, its oxidation products, and ozone, in the Lower Fraser Valley, BC

Cited by 115 publications

References 25 publications

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

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

The chemistry of biogenic hydrocarbons at a rural site in eastern Canada

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

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