atoms (from 12 to 40 h) are similar to those for their reaction
with OH (from 22 to 76 h), and therefore the reactions with
chlorine atoms can provide effective tropospheric loss path-
ways for such alcohols. Cl reactions are expected to play a
significant role in the tropospheric chemistry of the marine
boundary layer and in coastal urban areas, where the Cl
concentration peaks at dawn, much earlier than OH does.
That may also be the case in some contaminated urban areas,
where high levels of chlorine may be originated from industrial
emissions.40 However, on a global scale, Rudolph et al.41
estimated the upper limits of the average tropospheric Cl atom
concentration of less than 103 atoms cmꢁ3 and nearly 2 ꢂ 103
atoms cmꢁ3, for the Northern and Southern hemispheres,
respectively. These global average Cl concentrations give rise
to lifetimes 50 to 100 longer than the previously calculated
ones. Therefore, despite their high reactivity, Cl atom con-
centrations are too low to compete with OH radicals in
influencing the oxidizing capacity of the global troposphere.
In the light of the products detected in this work, such as the
oxidant PAN, these reactions may contribute to the photo-
chemical smog observed in polluted coastal urban areas.
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Acknowledgements
The authors gratefully thank the Spanish Ministerio de Edu-
cacion y Ciencia (Project No. CGL2004-03355/CLI) and the
´
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Junta de Comunidades de Castilla-La Mancha (Project No.
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