Secondary limonene endo-ozonide: A major product from gas-phase ozonolysis of R-(+)-limonene at ambient temperature

Nørgaard, Asger W.; Nøjgaard, Jakob Klenø; Larsen, Kim Lambertsen; Sporring, Sune; Wilkins, C.K.; Clausen, Per Axel; Wolkoff, Peder

doi:10.1016/j.atmosenv.2006.02.007

Cited by 31 publications

(21 citation statements)

References 27 publications

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“…The IR spectra also indicated the formation of products containing ‐C‐O functionalities, possibly secondary ozonides as a result of primary product rearrangement and secondary reactions. However, thermal liability of these compounds prevented identification under the present experimental conditions (Norgaard et al., 2006).…”

Section: Resultsmentioning

confidence: 92%

Heterogeneous oxidation of squalene film by ozone under various indoor conditions

2009

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The effects of indoor conditions (ozone concentration, temperature, relative humidity (RH), and the presence of NO(x)) on heterogeneous squalene oxidation were studied with Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy. The heterogeneous kinetics of squalene-ozone reaction revealed a pseudo-first-order reaction rate constant of 1.22 x 10(-5)/s at [O(3)] = 40 ppb. Oxidation kinetics were insensitive to temperature over the range of 24-58 +/- 2 degrees C as well as to RH and presence of NO(x). Products, however, were affected by the environmental parameters. As temperature was increased, fewer surface products and more low molecular weight gaseous products were observed. Lower air exchange rates also enhanced gas phase reactions, allowing for formation of secondary gas phase products. As RH increased, there was a shift in product distribution from ketones to aldehydes, and the presence of NO(x) during squalene ozonolysis resulted in the formation of nitrated oxidation products. Identified surface products included 6-methyl-5-hepten-2-one, geranyl acetone, and long chain ketones and aldehydes, while gas phase products included formaldehyde, acetone, 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid. Practical Implications Heterogeneous oxidation of squalene resulted in surface products including long chain aldehydes and ketones, and gas phase products including formaldehyde, a known human carcinogen (IARC 2006), and bicarbonyl compounds like: 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid that are characterized as asthma triggers and sensitizers (Anderson et al., 2007; Jarvis et al., 2005). In addition, ozonolysis experiments in the presence of NO(x) showed the formation of nitrated surface oxidation products. Such nitrated products may have higher mutagenicity, carcinogenicity, or allergenic potential than their nitrate free counterparts (Franze et al., 2005; Pitts, 1983). Kinetic studies determined that at moderate ozone levels of 40 ppb (Uhde and Salthammer, 2007), and an estimated skin surface density of 4 x 10(15) molecules/cm(2), surface reaction would lead to a minimum product formation flux of 4 x 10(10) molecules cm(2)/s. As squalene is naturally occurring and continually produced by the human body, its concentration in the indoor environment cannot be controlled. However, this study highlights the importance of regulating air exchange rate, temperature, and ozone level in the indoor environment on the formation of potentially harmful or irritating squalene oxidation products.

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Section: Resultsmentioning

confidence: 92%

Heterogeneous oxidation of squalene film by ozone under various indoor conditions

2009

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“…of limonene has been studied extensively to characterize the chemical composition of condensable and volatile products (Hewitt and Kok, 1991;Grosjean et al, 1993;Hakola et al, 1994;Glasius et al, 2000;Koch et al, 2000;Feltham et al, 2000;Leungsakul et al, 2005a;Norgaard et al, 2006;Heaton et al, 2007;Iinuma et al, 2007;Walser et al, 2008), determine the yield of limonene SOA (Hoffmann et al, 1997;Weschler and Shields, 1999;Griffin et al, 1999;Wainman et al, 2000;Bonn et al, 2002;Rohr et al, 2003;Jonsson et al, 2006;Ng et al, 2006;Zhang et al, 2006), characterize the hygroscopic properties of organic particles in limonene SOA (Virkkula et al, 1999;Hartz et al, 2005;van Reken et al, 2005), and evaluate health effects of limonene oxidation products (Karlberg et al, 1992;Wolkoff et al, 2000;Wilkins et al, 2003;Kleno and Wolkoff, 2004;Nojgaard et al, 2005;Sunil et al, 2007;Wolkoff et al, 2008).…”

Section: Case High Intermediate Lowmentioning

confidence: 99%

Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

Pan¹,

Underwood²,

Xing³

et al. 2009

Preprint

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Abstract. Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone and D-limonene concentrations (0.1–300 ppm) used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA material. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

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“…Tandem mass spectrometry (MS/MS) of the ascorbate ozonide AOZ Ϫ reveals the onset of collisionally induced dissociation (CID) above an accelerating voltage of 1.00 V into m/z ϭ 135 and 189 daughter ions, associated with 2CO 2 (Ϫ88 Da) and H 2 O 2 (Ϫ34 Da) neutral losses, respectively. As a direct precedent, the major decomposition channel of the secondary endoozonide of limonene, unique among those of substituted cyclohexenes, also involves H 2 O 2 extrusion (29). Ozonolysis of L-[3-13 C] AH 2 exclusively yields 13 (Fig.…”

Section: The Techniquementioning

confidence: 99%

Acidity enhances the formation of a persistent ozonide at aqueous ascorbate/ozone gas interfaces

Enami

Hoffmann

Colussi

2008

Proc. Natl. Acad. Sci. U.S.A.

103

164

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The pulmonary epithelium, like most aerial biosurfaces, is naturally protected against atmospheric ozone (O3) by fluid films that contain ascorbic acid (AH 2) and related scavengers. This mechanism of protection will fail, however, if specific copollutants redirect AH2 and O3(g) to produce species that can transduce oxidative damage to underlying tissues. Here, the possibility that the synergistic adverse health effects of atmospheric O 3(g) and acidic particulate matter revealed by epidemiological studies could be mediated by hitherto unidentified species is investigated by electrospray mass spectrometry of aqueous AH 2 droplets exposed to O3(g). The products of AH2 ozonolysis at the relevant air-water interface shift from the innocuous dehydroascorbic acid at biological pH to a C 4-hydroxy acid plus a previously unreported ascorbate ozonide (m/z ‫؍‬ 223) below pH Ϸ5. The structure of this ozonide is confirmed by tandem mass spectrometry and its mechanism of formation delineated by kinetic studies. Present results imply enhanced production of a persistent ozonide in airway-lining fluids acidified by preexisting pathologies or inhaled particulate matter. Ozonides are known to generate cytotoxic free radicals in vivo and can, therefore, transduce oxidative damage.ascorbic acid ͉ oxidative damage ͉ particulate matter ͉ lung ͉ biosurfaces

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Secondary limonene endo-ozonide: A major product from gas-phase ozonolysis of R-(+)-limonene at ambient temperature

Cited by 31 publications

References 27 publications

Heterogeneous oxidation of squalene film by ozone under various indoor conditions

Heterogeneous oxidation of squalene film by ozone under various indoor conditions

Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

Acidity enhances the formation of a persistent ozonide at aqueous ascorbate/ozone gas interfaces

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