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

A 16 s old gas-phase ambient temperature and 1% relative humidity reaction mixture of ozone and R-limonene (ca. 1:10) was sampled on XAD-2 resin followed by pressurized liquid extraction with dichloromethane at ambient temperature. Low temperature on-column injection and gas chromatography (GC) revealed equal amounts of diastereomeric secondary endo-limonene ozonides, in addition to 4-acetyl-l-methyl-cyclohexene (AMCH), 3-isopropyl-6-oxo-heptanal (IPOH), and endo-limonene mono-epoxides. The secondary endo-limonene ozonides began to decrease at extraction temperature above 150 degrees C and were absent at 200 degrees C. Their formation was unaffected by an increase of the relative humidity to 15%. The identification of the secondary limonene ozonides was confirmed by (1) unique consecutive losses of OH and H2O2, respectively, from the protonated quasi-molecular ion in GC-chemical ionization mass spectrometry mode (isobutane), in addition to high resolution mass determination of [M-OH] and [M-H2O2] ions in EI mode; (2) comparison of mass spectral data to that of synthesized secondary endo-limonene ozonides; and (3) oxidation of dimethyl sulfide to dimethyl sulfoxide and subsequent increase of IPOH.

[1]  Peder Wolkoff,et al.  Formation of strong airway irritants in a model mixture of (+)-α-pinene/ozone , 1999 .

[2]  L. Stieglitz,et al.  Product Analysis of the Chemical/Photochemical Conversion of Monoterpenes with Airborne Pollutants (O3/NO2) , 1988 .

[3]  S. M. Aschmann,et al.  Hydroxyaldehyde products from hydroxyl radical reactions of Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol quantified by SPME and API-MS. , 2003, Environmental Science and Technology.

[4]  S. M. Aschmann,et al.  Products of the Gas-Phase Reaction of O 3 with Cyclohexene , 2003 .

[5]  P. Ziemann,et al.  Gas chromatography of trimethylsilyl derivatives of alpha-methoxyalkyl hydroperoxides formed in alkene-O3 reactions. , 2004, Journal of chromatography. A.

[6]  P Wolkoff,et al.  Formation of strong airway irritants in mixtures of isoprene/ozone and isoprene/ozone/nitrogen dioxide. , 2001, Environmental health perspectives.

[7]  P Wolkoff,et al.  Organic compounds in office environments - sensory irritation, odor, measurements and the role of reactive chemistry. , 2006, Indoor air.

[8]  Dimitrios Kotzias,et al.  Carboxylic Acids in Secondary Aerosols from Oxidation of Cyclic Monoterpenes by Ozone , 2000 .

[9]  Peder Wolkoff,et al.  UPPER AIRWAY AND PULMONARY EFFECTS OF OXIDATION PRODUCTS OF (+)- α -PINENE, d -LIMONENE, AND ISOPRENE IN BALB/ c MICE , 2002, Inhalation toxicology.

[10]  Per Axel Clausen,et al.  Are We Measuring the Relevant Indoor Pollutants , 1997 .

[11]  P. Mathy,et al.  Air Pollution and Ecosystems , 1988 .

[12]  D. Kotzias,et al.  Gas Phase Terpene Oxidation Products. A Review. , 1999 .

[13]  K. Griesbaum,et al.  Ozonides of mono-, bi- and tricyclic terpenes , 1996 .

[14]  Peder Wolkoff,et al.  The effect on human eye blink frequency of exposure to limonene oxidation products and methacrolein. , 2005, Toxicology letters.

[15]  H. Hakola,et al.  Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes , 1994 .

[16]  P Wolkoff,et al.  Formation of strong airway irritants in terpene/ozone mixtures. , 2000, Indoor air.

[17]  Charles J Weschler,et al.  Indoor hydrogen peroxide derived from ozone/d-limonene reactions. , 2002, Environmental science & technology.

[18]  U. Brinkman,et al.  Current use of pressurised liquid extraction and subcritical water extraction in environmental analysis. , 2002, Journal of chromatography. A.

[19]  Ulrika Nilsson,et al.  Hydroperoxides in oxidized d-limonene identified as potent contact allergens , 2004, Archives of Dermatological Research.

[20]  R. Kamens,et al.  Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone. , 2005, Environmental science & technology.

[21]  William W. Nazaroff,et al.  Cleaning products and air fresheners: exposure to primary and secondary air pollutants , 2004 .

[22]  Peder Wolkoff,et al.  Degradation of the adsorbent Tenax TA by nitrogen oxides, ozone, hydrogen peroxide, OH radical, and limonene oxidation products. , 2002, Environmental science & technology.

[23]  Roger Atkinson,et al.  Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review , 2003 .

[24]  V. Miclǎuş,et al.  Isolation of Ozonides from Gas-Phase Ozonolyses of Terpenes , 1998 .

[25]  John D. Spengler,et al.  Indoor Air Quality Handbook , 2000 .

[26]  P Wolkoff,et al.  Chemical and biological evaluation of a reaction mixture of R-(+)-limonene/ozone: formation of strong airway irritants. , 2001, Environment international.

[27]  S. Koch,et al.  Formation of new particles in the gas phase ozonolysis of monoterpenes , 2000 .

[28]  R. Fajgar,et al.  Observation of secondary 2-butene ozonide in the ozonation of trans-2-butene in the gas phase , 1996 .

[29]  Yong Bin Lim,et al.  Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3. , 2005, Environmental science & technology.