Atmospheric aerosols absorb and reflect solar radiation causing surface cooling and heating of the atmosphere. The interaction between aerosols and radiation depends on their complex index of refraction, which is related to the particles' chemical composition. The contribution of light absorbing organic compounds, such as HUmic-LIke Substances (HULIS) to aerosol scattering and absorption is among the largest uncertainties in assessing the direct effect of aerosols on climate. Using a Cavity Ring Down Aerosol Spectrometer (CRD-AS), the complex index of refraction of aerosols containing HULIS extracted from pollution, smoke, and rural continental aerosols, and molecular weight-fractionated fulvic acid was measured at 390 nm and 532 nm. The imaginary part of the refractive index (absorption) substantially increases towards the UV range with increasing molecular weight and aromaticity. At both wavelengths, HULIS extracted from pollution and smoke particles absorb more than HULIS from the rural aerosol. Sensitivity calculations for a pollution-type aerosol containing ammonium sulfate, organic carbon (HULIS), and soot suggests that accounting for absorption by HULIS leads in most cases to a significant decrease in the single scattering albedo and to a significant increase in aerosol radiative forcing efficiency, towards more atmospheric absorption and heating. This indicates that HULIS in biomass smoke and pollution aerosols, in addition to black carbon, can contribute significantly to light absorption in the ultraviolet and visible spectral regions.

Abstract. Application of cavity ring down (CRD) spectrometry for measuring the optical properties of pure and mixed laboratory-generated aerosols is presented. The extinction coefficient (αext), extinction cross section (σext) and extinction efficiency (Qext) were measured for polystyrene spheres (PSS), ammonium sulphate ((NH4)2(SO4), sodium chloride (NaCl), glutaric acid (GA), and Rhodamine-590 aerosols. The refractive indices of the different aerosols were retrieved by comparing the measured extinction efficiency of each aerosol type to the extinction predicted by Mie theory. Aerosols composed of sodium chloride and glutaric acid in different mixing ratios were used as model for mixed aerosols of two non-absorbing materials, and their extinction and complex refractive index were derived. Aerosols composed of Rhodamine-590 and ammonium sulphate in different mixing ratios were used as model for mixing of absorbing and non-absorbing species, and their optical properties were derived. The refractive indices of the mixed aerosols were also calculated by various optical mixing rules. We found that for non-absorbing mixtures, the linear rule, Maxwell-Garnett rule, and extended effective medium approximation (EEMA), give comparable results, with the linear mixing rule giving a slightly better fit than the others. Overall, calculations for the mixed aerosols are not as good as for single component aerosols. For absorbing mixtures, the differences between the refractive indices calculated using the mixing rules and those retrieved by CRD are generally higher.

Abstract. The heterogeneous reaction between gas phase glyoxal and ammonium sulfate (AS) aerosols, a proxy for inorganic atmospheric aerosol, was studied in terms of the dependence of the optical, physical and chemical properties of the product aerosols on initial particle size and ambient relative humidity (RH). Our experiments imitate an atmospheric scenario of a dry particle hydration at ambient RH conditions in the presence of glyoxal gas followed by efflorescence due to decrease of the ambient RH. The reactions were studied under different RH conditions, starting from dry conditions (∼20 % RH) and up to 90 % RH, covering conditions prevalent in many atmospheric environments, and followed by consequent drying of the reacted particles before their analysis by the aerosol mass spectrometer (AMS), cavity ring down (CRD) and scanning mobility particle sizer (SMPS) systems. At λ = 355 nm, the reacted aerosols demonstrate a substantial growth in optical extinction cross section, as well as in mobility diameter under a broad range of RH values (35-90 %). The ratio of the product aerosol to seed aerosol geometric cross section reached up to ∼3.5, and the optical extinction cross-section up to ∼250. The reactions show a trend of increasing physical and optical growth with decreasing seed aerosol size, from 100 nm to 300 nm, as well as with decreasing RH values from 90 % to ∼40 %. Optically inactive aerosols, at the limit of the Mie range (100 nm diameter) become optically active as they grow due to the reaction. AMS analyses of the reaction of 300 nm AS at RH values of 50 %, 75 % and 90 % show that the main products of the reaction are glyoxal oligomers, formed by acetal formation in the presence of AS. In addition, imidaCorrespondence to: Y. Rudich (yinon.rudich@weizmann.ac.il) zole formation, which is a minor channel, is observed for all reactions, yielding a product which absorbs at λ = 290 nm, with possible implications on the radiative properties of the product aerosols. The ratio of absorbing substances (C-N compounds, including imidazoles) increases with increasing RH value. A core/shell model used for the investigation of the optical properties of the reaction products of AS with gas phase glyoxal, shows that the refractive index (RI) of the reaction products are n = 1.68(±0.10) + 0.01(±0.02) at 50 % RH and n = 1.65(±0.06) + 0.02(±0.01) at 75 % RH at 355 nm. The observed increase in the ratio of the absorbing substances is not indicated in the imaginary part of the products at RH 50 % and 75 %. A further increase in the ratio of absorbing substances and a resulting increase in the imaginary part of the RI at higher RH values is expected, and may become even more substantial after longer reaction times, possibly in cloud or fog droplets. This study shows that the reaction of abundant substances present in atmospheric aerosols, such as AS, and gas phase glyoxal alters the aerosols' optical, physical and chemical properties and may have implications on the radiative effect of these aerosols.

Credible climate change predictions require reliable fundamental scientific knowledge of the underlying processes. Despite extensive observational data accumulated to date, atmospheric aerosols still pose key uncertainties in the understanding of Earth’s radiative balance due to direct interaction with radiation and because they modify clouds’ properties. Specifically, major gaps exist in the understanding of the physicochemical pathways that lead to aerosol growth in the atmosphere and to changes in their properties while in the atmosphere. Traditionally, the driving forces for particle growth are attributed to condensation of low vapor pressure species following atmospheric oxidation of volatile compounds by gaseous oxidants. The current study presents experimental evidence of an unaccounted-for new photoinduced pathway for particle growth. We show that heterogeneous reactions activated by light can lead to fast uptake of noncondensable Volatile Organic Compounds (VOCs) at the surface of particles when only traces of a photosensitizer are present in the seed aerosol. Under such conditions, size and mass increase; changes in the chemical composition of the aerosol are also observed upon exposure to volatile organic compounds such as terpenes and near-UV irradiation. Experimentally determined growth rate values match field observations, suggesting that this photochemical process can provide a new, unaccounted-for pathway for atmospheric particle growth and should be considered by models.

This study focuses on the retrieval of the normalized mass absorption cross section (MAC) of soot using theoretical calculations that incorporate new measurements of the optical properties of organic carbon (OC) intrinsic to fresh diesel soot. Intrinsic OC was extracted by water and an organic solvent, and the complex refractive index of the extracted OC was derived at 532 and 355-nm wavelengths using cavity ring-down aerosol spectrometry. The extracted OC was found to absorb weakly in the visible wavelengths and moderately at blue wavelengths. The mass ratio of OC and elemental carbon (EC) in the collected particles was evaluated using a thermo-optical method. The measured EC/OC ratio in the soot exhibited substantial variability from measurement to measurement, ranging between 2 and 5. To test the sensitivity of the MAC to this variability, three different EC/OC ratios (2∶1, 1∶1, and 1∶2) were chosen as representative. Particle size and spherule morphology were estimated using scanning electron microscopy, and the soot was found to be primarily in the form of aggregates with a dominant aggregate diameter mode in the range 200-250 nm. The measured refractive index of the extracted OC was used with a variety of theoretical models to calculate the MAC of internally mixed diesel soot at 532 and 355 nm. We conclude that RayleighDebye-Gans theory on clusters of coated spherules and T-matrix of a solid EC spheroid coated by intrinsic OC are both consistent with previous measurements; however, Rayleigh-Debye-Gans theory provides a more realistic physical model for the calculation black carbon | cavity ring-down | coated particles | mass absorption cross section