HR: 1340h
AN: A43C-0056 [Abstracts]
TI: Atmospheric Photooxidation of Fluorotelomer Alcohols: A Global Source of Long Chain Perflurinated
Carboxylic Acid Pollution?
AU: * Sulbaek Andersen, M P
EM: mads@sulbaek.dk
AF: University of Copenhagen, Department of Chemistry, C514
Universitetsparken 5
, Copenhagen OE, 2100
Denmark
AU: Nielsen, O
AF: University of Copenhagen, Department of Chemistry, C514
Universitetsparken 5
, Copenhagen OE, 2100
Denmark
AU: Wallington, T
AF: Ford Motor Company, MD 3083/ SRL Building
P.O. Box 2053, Dearborn, MI 48121-2053
United States
AU: Hurley, M
AF: Ford Motor Company, MD 3083/ SRL Building
P.O. Box 2053, Dearborn, MI 48121-2053
United States
AU: Ball, J
AF: Ford Motor Company, MD 3083/ SRL Building
P.O. Box 2053, Dearborn, MI 48121-2053
United States
AU: Mabury, S
AF: University of Toronto, Department of Chemistry
80 St. George St., Toronto, ON M5S 3H6
Canada
AU: Ellis, D
AF: University of Toronto, Department of Chemistry
80 St. George St., Toronto, ON M5S 3H6
Canada
AU: Martin, J
AF: University of Toronto, Department of Chemistry
80 St. George St., Toronto, ON M5S 3H6
Canada
AB:
Humans and animals in urban and remote locations are contaminated with trace amounts of persistent and bioaccumulative
perfluorinated carboxylic acids (PFCAs) [1-3]. There are no known natural sources of long chain PFCAs, these compounds are
not expected to be mobile in the environment, and it is puzzling that they are observed in remote locations. Fluorotelomer
alcohols (FTOHs) are a class of industrially important chemicals with the general formula C$_{x}$F$_{2x+1}$CH$_{2}$CH$_{2}$OH
that have been observed in the atmosphere. The atmospheric oxidation of FTOHs is a potential source of PFCAs. Smog-chamber
studies of the kinetics and mechanism of the OH radical initiated degradation of FTOHs have been conducted [4]. It was
observed that reactions of HO$_{2}$ with C$_{x}$F$_{2x+1}$C(O)O$_{2}$ radicals formed during FTOH oxidation are a source of
PFCAs [5]. The reactions proceed by 3 pathways leading to formation of C$_{x}$F$_{2x+1}$C(O)OOH and O$_{2}$,
C$_{x}$F$_{2x+1}$C(O)OH and O$_{3}$, or C$_{x}$F$_{2x+1}$C(O)O radicals, OH radicals and O$_{2}$. In the presence of excess
of NO$_{x}$, acid formation was not observed, but evidence for the existence of a previously unrecognized stabilized alpha-
hydroxy peroxy radical was found.
The likelihood that FTOHs contribute significantly to the observed global budget of PFCAs will be the subject of this
presentation.
{\it References}
1. Masunaga, S., Kannan, K., Doi, R. Nakanishi, J. Giesy, J.P. Levels of perfluorooctane sulfonate (PFOS) and other related
compounds in the blood of Japanese people.
Organohalogen Compounds (Dioxin 2002). 59, 888 - 891 (2002).
2. Martin, J.W., Smithwick, M.M., Braune, B.M., Hoekstra, P.F., Muir, D.C.G., Mabury, S.A. Identification of Long-chain
Perfluorinated Acids in Biota from the Canadian Arctic. Environ. Sci. Tech. 38, 373-380 (2004).
3. Kannan, K Choi, J-W., Iseki, N., Senthilkumar, K., Kim, D.H., Masunaga, S., Giesy, J.P. Concentrations of perfluorinated
acids in livers of birds from Japan and Korea. Chemosphere. 49, 225 - 231 (2002).
4. Ellis, D.A., Martin, J.W., Mabury, S.A., Hurley, M.D., Sulbaek Andersen, M.P., Wallington, T.J. Atmospheric lifetime of
fluorotelomer alcohols. Environ. Sci. Tech. 37, 3816-3820 (2003).
5. Sulbaek Andersen, M.P., Hurley, M.D., Wallington, T.J., Martin, J.W., Ellis, D.A., Mabury, S.A. Atmospheric chemistry of
C2F5CHO: mechanism of the C2F5C(O)O2 + HO2 reaction. Chem. Phys. Lett. 381, 14-21 (2003).
DE: 0317 Chemical kinetic and photochemical properties
DE: 0345 Pollution--urban and regional (0305)
DE: 0365 Troposphere--composition and chemistry
DE: 0368 Troposphere--constituent transport and chemistry
SC: Atmospheric Sciences [A]
MN: 2004 AGU Fall Meeting