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fluorotelomer alcohols the data from this work and from Ellis
et al.4 indicate that the OH reaction will also be the major
atmospheric loss process giving lifetimes of around 12 days.
The atmospheric degradation of these long-chain fluorotelomer
alcohols produce the primary aldehydes CnF2n+1CH2CHO by a
series of reactions analogous to those described for CF3CH2-
CH2OH. These aldehydes are expected to react predominantly
with OH to form CnF2n+1CHO but may provide a source of
CnF2n+1CH2C(O)OH by the reaction of CnF2n+1CH2C(O)O2 with
HO2. Reaction of OH with CnF2n+1CHO will generate mainly
perfluoroalkoxy radicals, although reaction of CnF2n+1C(O)O2
with HO2 under low NOx conditions could yield CnF2n+1C(O)-
OH. It is expected that the major loss processes for long-chain
perfluoroalkoxy radicals will be via sequential carbon-carbon
bond breaking to form CF2O. Recently Ellis et al.5 have
suggested that in the absence of NOx the dominant loss of
perfluoroalkyl peroxy radicals is likely to be reaction with other
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radical reaction leads to formation of perfluoro alcohols. Loss
of HF from these alcohols forms perfluoroacyl fluorides, which
will hydrolyze in the atmosphere to form perfluorocarboxylic
acids. The long-chain fluoroaldehydes are likely to be relatively
insoluble in cloud droplets but will behave as surfactants and
form CnF2n+1CH(OH)2 at the surface of water droplets. Evapo-
ration of the droplet followed by reaction of the gaseous hydrates
may produce the acids CnF2n+1C(O)OH in a manner similar to
that proposed for CF3CH(OH)2. Thus, oxidation of long-chain
fluorotelomer alcohols might generate fluorinated carboxylic
acids in their atmospheric degradation, although an important
degradation product will be CF2O. This compound is unreactive
with OH and will not photolyze under tropospheric conditions.
The most probable loss process is uptake in cloud droplets
followed by hydrolysis. The atmospheric lifetimes of the fluoro
alcohols and their oxidation products are sufficiently short that
their contribution to radiative forcing will be negligible.
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Acknowledgment. Part of this work has been carried out
in conjunction with the research project “Impact of Fluorinated
Alcohols and Ethers on the Environment”, which is supported
by the Commission of the European Communities under the
Energy, Environment and Sustainable Development Programme
through contract EVK2-CT-1999-00009. G.L.B. thanks Total
company (Dr Jean Marie Libre) and Telomer Research Pro-
gramme for also supporting part of this work.
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