28664-02-0Relevant articles and documents
Mechanisms for the formation of secondary organic aerosol components from the gas-phase ozonolysis of α-pinene
Ma, Yan,Russell, Andrew T.,Marston, George
, p. 4294 - 4312 (2008/12/22)
Gas-phase ozonolysis of α-pinene was studied in static chamber experiments under 'OH-free' conditions. A range of multifunctional products-in particular low-volatility carboxylic acids-were identified in the condensed phase using gas chromatography coupled to mass spectrometry after derivatisation. The dependence of product yields on reaction conditions (humidity, choice of OH radical scavengers, added Criegee intermediate scavengers, NO2etc.) was investigated to probe the mechanisms of formation of these products; additional information was obtained by studying the ozonolysis of an enal and an enone derived from α-pinene. On the basis of experimental findings, previously suggested mechanisms were evaluated and detailed gas-phase mechanisms were developed to explain the observed product formation. Atmospheric implications of this work are discussed. the Owner Societies.
An analytical approach for a comprehensive study of organic aerosols
Schrader, Wolfgang,Geiger, Jutta,Godejohann, Markus,Warscheid, Bettina,Hoffmann, Thorsten
, p. 3998 - 4001 (2007/10/03)
Unknown products identified precisely: The coupling of liquid chromatography to NMR spectroscopy, mass spectrometry, and infrared spectroscopy and the use of high-resolution mass spectrometry is utilized to investigate the formation of atmospheric-relevan
Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone
Glasius, Marianne,Lahaniati, Maria,Calogirou, Aggelos,Di Bella, Dario,Jensen, Niels R.,Hjorth, Jens,Kotzias, Dimitrios,Larsen, Bo R.
, p. 1001 - 1010 (2007/10/03)
A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e. dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1 (cis-3- carboxy-2,2-dimethylcyclobutylethanoic acid) from α-and β-pinene; cis- pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis- 10-hydroxypinonic acid AB6 (cis-2,2-dimethyl-3- hydroxyacetylcyclobutylethanoic acid) from α-pinene and β-pinene; cis-3- caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3- caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3-(hydroxy-2- oxopropyl)cyclopropanylethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6- oxo-heptanoic acid), 7-hydroxylimononic acid L6 (3-isopropenyl-7-hydroxy-6- oxoheptanoic acid), and 7-hydroxylimononic acid L6' (7-hydroxy-3-isopropenyl- 6-oxoheptanoic acid) from limonene. A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e. dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1 (cis-3-carboxy-2,2-dimethylcyclobutylethanoic acid) from α- and β-pinene; cis-pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis-10-hydroxypinonic acid AB6 (cis-2,2-dimethyl-3-hydroxyacetylcyclobutyl-ethanoic acid) from α-pinene and β-pinene; cis-3-caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3-caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3-(hydroxy-2-oxopropyl)cyclopropanyl-ethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6-oxo-heptanoic acid), 7-hydroxy-limononic acid L6 (3-isopropenyl-7-hydroxy-6-oxoheptanoic acid), and 7-hydroxylimononic acid L6′ (7-hydroxy-3-isopropenyl-6-oxoheptanoic acid) from limonene.
Identification of products containing -COOH, -OH, and -C=O in atmospheric oxidation of hydrocarbons
Yu, Jianzhen,Flagan, Richard C.,Seinfeld, John H.
, p. 2357 - 2370 (2007/10/03)
Atmospheric oxidation of hydrocarbons by hydroxyl radicals and ozone leads to products containing -COOH, -OH, and -C=O functional groups. The high polarity of such compounds precludes direct GC-MS analysis. In addition, many such compounds often exist in a single sample at trace levels. An analytical method has been developed to identify compounds containing one or more functional groups of carbonyl, carboxy, and hydroxy in atmospheric samples. In the method, -C=O groups are derivatized using O-(2,3,4,5,6- pentafluorobenzyl) hydroxy amine (PFBHA), and -COOH and -OH groups are derivatized using a silylation reagent N,O-bis(trimethylsilyl)- trifluoroacetamide (BSTFA). The derivatives are easily resolved by a GC column. The chemical ionization mass spectra of these derivatives exhibit several pseudomolecular ions, allowing unambiguous determination of molecular weights. Functional group identification is accomplished by monitoring the ions in the electron ionization mass spectra that are characteristic of each functional group derivative: m/z 181 for carbonyl and m/z 73 and 75 for carboxyl and hydroxy groups. The method is used to identify products in laboratory studies of ozone oxidation of α-pinene and Δ3-carene. Among products from ozone oxidation of α-pinene, we have detected pinonaldehyde, norpinonaldehyde, pinonic acid, norpinonic acid, C10 hydroxy dicarbonyls, pinic acid, 2,2-dimethyl-3-(formylmethyl)-cyclobutane-formic acid, and a product that has a molecular weight of 156 and contains a C=O and a COOH/OH group. The latter two products have not been reported previously. Δ3- Carene is structurally analogous to α-pinene in that both have an internal unsaturated bond where ozone oxidation takes place. We have also identified the corresponding analogous products, of which all but caronaldehyde are reported for the first time. An analytical method was developed to identify compounds containing one or more functional groups of carbonyl, carboxyl and hydroxyl in atmospheric samples. -C-to-O double bond groups are derivatized using 0-(2,3,4,5,6-pentafluorobenzyl)hydroxyl amine, and -COOH and -OH groups are derivatized using a silylation reagent N,O-bis(trimethylsilyl)-trifluoroacetamide. The derivatives are resolved using a gas chromatography column coupled with mass spectrometry. The method identified products in laboratory studies of ozone oxidation of α-pinene and Δ3-carene.
