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Published August 15, 1998 | public
Journal Article

Identification of Products Containing −COOH, −OH, and −C=O in Atmospheric Oxidation of Hydrocarbons


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 Δ^3-carene. Among products from ozone oxidation of α-pinene, we have detected pinonaldehyde, norpinonaldehyde, pinonic acid, norpinonic acid, C_(10) 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 CO and a COOH/OH group. The latter two products have not been reported previously. Δ^3-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.

Additional Information

© 1998 American Chemical Society. Received for review February 6, 1998. Revised manuscript received May 26, 1998. Accepted May 28, 1998. Publication Date (Web): July 3, 1998. This work was supported by the U.S. Environmental Protection Agency Center on Airborne Organics, the Coordinating Research Council, the Chevron Cooperation, and the National Science Foundation (ATM-9614105). Special thanks go to Robert Griffin and David Cocker for their help in collecting samples.

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