Atmos. Chem. Phys. Discuss., 12, 14551-14589, 2012
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Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene
T. Nakayama1, K. Sato2, Y. Matsumi1, T. Imamura2, A. Yamazaki3, and A. Uchiyama3
1Solar-Terrestrial Environment Laboratory and Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan
2National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba 305-8506, Japan
3Meteorological Research Institute, Japan Meteorological Agency, 1-1, Nagamine, Tsukuba 305-0052, Japan

Abstract. Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of lightabsorbing organic compounds "brown carbon" in the urban atmosphere. However, the atmospheric importance of these SOAs remains unclear due to limited information about their optical properties. In this study, the complex refractive index (RI, m=nki) values at 405, 532, and 781 nm of the SOAs generated during the photooxidation of toluene (toluene-SOAs) under a variety of initial nitrogen oxide (NOx= NO + NO2) conditions were examined by photoacoustic spectroscopy (PAS) and cavity ring down spectroscopy (CRDS). The complex RI values obtained in the present study and reported in the literature indicate that the k value, which represents the light absorption of the toluene-SOAs steeply increased to shorter wavelengths at <405 nm, while the n value gradually increased to shorter wavelengths from 781 to 355 nm. The k values at 405 nm were found to increase from 1.8 × 10−3 to 7.2 × 10−3 with increasing initial NOx concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a highresolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NOx concentration. The RI values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NOx (1,3,5-TMB-SOAs) were also determined to investigate the influence of the chemical structure of the precursor on the optical properties of the SOAs, and it was found that the light absorption of the 1,3,5-TMB-SOAs is negligible at all of the wavelengths investigated (405, 532, and 781 nm). These results can be reasonably explained by the hypothesis that nitro-aromatic compounds such as nitro-cresols are the major contributors to the light absorption of the toluene-SOAs. Using the obtained RI values, mass absorption cross sections of the toluene-SOAs at 405 and 532 nm were estimated to be 0.08–0.48 and 0.002–0.081 m2 g−1, respectively, under typical conditions in an urban atmosphere during the daytime. These results indicate that light absorption by the SOAs potentially contributes to the radiation balance at ultraviolet wavelengths below ~400 nm, specifically when the mass concentrations of the anthropogenic SOAs are significant compared with those of black carbon particles.

Citation: Nakayama, T., Sato, K., Matsumi, Y., Imamura, T., Yamazaki, A., and Uchiyama, A.: Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene, Atmos. Chem. Phys. Discuss., 12, 14551-14589, doi:10.5194/acpd-12-14551-2012, 2012.
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