[1] It has recently been suggested that some organic aerosols can absorb solar radiation, especially at the shorter visible and UV wavelengths. Although quantitative characterization of the optical properties of secondary organic aerosols (SOAs) is required in order to confirm the effect of SOAs on the atmospheric radiation balance, the light absorption of SOAs has not yet been thoroughly investigated. In this study, we conducted laboratory experiments to measure the optical properties of SOAs generated during the photooxidation of toluene in the presence of NO x and the ozonolysis of a-pinene. Extinction and scattering coefficients of the SOAs were measured by a cavity ring-down aerosol extinction spectrometer and an integrating nephelometer, respectively. Refractive indices of the SOAs were determined so that the measured particle size dependence of the extinction and scattering efficiencies could be reproduced by calculations using Mie scattering theory. As a result, significant light absorption was found at 355 nm for the toluene SOAs. In contrast, no significant absorption was found either at 355 or 532 nm for the a-pinene SOAs. Using the obtained refractive index, mass absorption cross-section values of the toluene SOAs were calculated to be 0.3-3 m 2 g −1 at 355 nm. The results indicate that light absorption by the SOAs formed from the photooxidation of aromatic hydrocarbons have a potential to influence the total aerosol light absorption, especially at UV wavelengths.Citation: Nakayama, T., Y. Matsumi, K. Sato, T. Imamura, A. Yamazaki, and A. Uchiyama (2010), Laboratory studies on optical properties of secondary organic aerosols generated during the photooxidation of toluene and the ozonolysis of a-pinene,

Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of light-absorbing 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 (NO x = NO + NO 2 ) 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, increased to shorter wavelengths at <532 nm, and the n-value also increased to shorter wavelengths from 781 to 355 nm. The k-values at 405 nm were found to increase from 0.0018 to 0.0072 with increasing initial NO x concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a high-resolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NO x concentration. The RI-values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NO x (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 ni-troaromatic compounds, such as nitrocresols, 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 nm were estimated to be 0.08-0.52 m 2 g −1 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 other light-absorbing particles.

In principle, mass concentrations of black carbon (BC) (M BC)

No abstract

Laboratory experiments were conducted for characterizing the performance of two commercially available instruments employed for the measurement of light absorption and scattering coefficients of aerosols at λ = 405, 532, and 781 nm (using three-wavelength photoacoustic soot spectrometer; PASS-3) as well as at 375 nm (using photoacoustic extinctiometer; PAX) based on photoacoustic spectroscopy and reciprocal nephelometry, respectively. The calibration factors (conversion factors from the readout to real values) associated with scattering measurements, estimated using gaseous molecules, mono-disperse polystyrene latex and ammonium sulfate particles, and/or polydisperse ammonium sulfate particles, are in good agreement with one another, typically within 5 %, 5 %, and 10 % at 375, 405, and 781 nm, respectively. In contrast, a significant particle size dependency was observed for the calibration factors at 532 nm, which is possibly because of a combination of differences in the polarization states of the lasers relative to the scattering planes and large truncation angle. Considering the estimated effective truncation angle, the typical uncertainties in calibration factors for scattering when measuring non-or weakly light-absorbing particles, with volume-based geometrical diameters of less than 700 nm, were estimated to be 12 %, 7 %, 34 %, and 17 %, at 375, 405, 532, and 781 nm, respectively. The typical uncertainties in the calibration factors for absorption measurements, which were determined using poly-disperse propane soot particles, were estimated to be 6 %, 4 %, 8 %, and 11 %, at 375, 405, 532, and 781 nm, respectively. The calibration factors for absorption determined by the poly-disperse soot particles at 375 and 405 nm were 48 % and 36 % smaller than those by light absorption of NO 2 molecules possibly because of NO 2 photolysis, although good agreement was observed at 532 nm. These results suggest that the photolysis effect should be taken into account when light absorption by NO 2 is used for calibration at 375 and 405 nm.