Poor air quality is globally the largest environmental health risk. Epidemiological studies have uncovered clear relationships of gaseous pollutants and particulate matter (PM) with adverse health outcomes, including mortality by cardiovascular and respiratory diseases. Studies of health impacts by aerosols are highly multidisciplinary with a broad range of scales in space and time. We assess recent advances and future challenges regarding aerosol effects on health from molecular to global scales through epidemiological studies, field measurements, health-related properties of PM, and multiphase interactions of oxidants and PM upon respiratory deposition. Global modeling combined with epidemiological exposure-response functions indicates that ambient air pollution causes more than four million premature deaths per year. Epidemiological studies usually refer to PM mass concentrations, but some health effects may relate to specific constituents such as bioaerosols, polycyclic aromatic compounds, and transition metals. Various analytical techniques and cellular and molecular assays are applied to assess the redox activity of PM and the formation of reactive oxygen species. Multiphase chemical interactions of lung antioxidants with atmospheric pollutants are crucial to the mechanistic and molecular understanding of oxidative stress upon respiratory deposition. The role of distinct PM components in health impacts and mortality needs to be clarified by integrated research on various spatiotemporal scales for better evaluation and mitigation of aerosol effects on public health in the Anthropocene.

[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,

The photooxidation of toluene is a potential source of secondary organic aerosol (SOA) in urban air, but only a small portion of the compounds present in SOA have been identified. In this study, we analyzed the chemical compositions of SOA produced by photoirradiation of the toluene/NOx/air system in laboratory chamber experiments by a combination of liquid chromatography-mass spectrometry, hybrid high-performance liquid chromatography-mass spectrometry, and iodometry-spectrophotometry. The dependence of the chemical composition on the initial NOx concentration was examined at initial NO concentrations ([NO]0) of 0.2 and 1 ppmv. Fifteen semivolatile products, including aromatic and ring-cleavage compounds, were quantified. However, the quantified products comprised only a small portion ( approximately 1 wt %) of the total aerosol mass. The total SOA yield ( approximately 13 wt %), the ratio of organic peroxides to total SOA mass ( approximately 17 wt %), and the density of SOA ( approximately 1.4 g cm-3) were independent of the NOx level, suggesting that the reaction mechanisms of the formation of major SOA products at [NO]0 = 0.2 and 1 ppmv are essentially the same. The negative-ion mass spectra of SOA samples showed that ion signals attributed to hemiacetal oligomers and/or decomposition products of peroxy hemiacetal oligomers were detected in the range of mass-to-charge ratios (m/z) between 200 and 500. The highest signals were detected at m/z = 155 and 177, and these were tentatively assigned to C7 unsaturated oxacyclic oxocarboxylic acids and C7 unsaturated oxacyclic dicarboxylic acids, respectively. We conclude that the major chemical components of the aerosol are hemiacetal and peroxy hemiacetal oligomers and low-molecular-weight dicarboxylic acids.

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.

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