Near-ultraviolet absorption cross sections of nitrophenols and their potential influence on tropospheric oxidation capacity

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Date
2011-09-29
Authors
Chen, Jun
Wenger, John C.
Venables, Dean S.
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American Chemical Society
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Abstract
Nitrophenols and methylnitrophenols have been identified as photolytic precursors of nitrous acid, HONO, but their gas-phase absorption has not previously been reported. In this study, the absorption cross sections of 2-nitrophenol, 3-methyl-2-nitrophenol, and 4-methyl-2-nitrophenol were measured from 320 to 450 nm using incoherent broad-band cavity enhanced absorption spectroscopy (IBBCEAS). The benzaldehyde absorption spectrum wasmeasured to validate the approach and was in good agreement with literature spectra. The nitrophenol absorption cross sections are large (ca. 10-17 cm2 molecule-1)  and blue-shifted about 20 nm compared to previously measured solution spectra. Besides forming HONO, nitrophenol absorption influences other photochemistry by reducing the available actinic flux. The magnitudes of both effects are evaluated as a function of solar zenith angle, and nitrophenol absorption is shown to lower the photolysis rates of O3 and NO2.
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Keywords
Photolysis , Benzaldehyde , Broadband cavity enhanced absorption spectroscopy , Atmospheric simulation chamber , tropospheric oxidation
Citation
CHEN, J., WENGER, J. C. & VENABLES, D. S. 2011. Near-Ultraviolet Absorption Cross Sections of Nitrophenols and Their Potential Influence on Tropospheric Oxidation Capacity. The Journal of Physical Chemistry A, 115, 12235-12242. doi: http://dx.doi.org/10.1021/jp206929r
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Copyright © 2011 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jp206929r