The temporal variability of microphysical parameters of pyrolysis smoke, retrieved by inverting the characteristics of aerosol scattering and extinction, has been studied. The polarization scattering phase functions and spectral extinction coefficients were measured for 65 hours in smoke aerosols produced from thermal decomposition of pine wood during low-temperature pyrolysis in the Big Aerosol Chamber (BAC) of Institute of Atmospheric Optics, Siberian Branch, Russian Academy of Sciences. The microstructure parameters (volume concentration and mean radius of particles with division into fine and coarse fractions) and the complex refractive index of pyrolysis smoke are retrieved following the developed algorithm for inverting optical measurements. The real part of the refractive index is found to be in the vicinity of n = 1.55, and the imaginary part is in the range 0.007 < kappa < 0.009; the mean radius of fine particles varies in the narrow range 0.137-0.146 mu m. During smoke aging, the particle ensemble-mean radius monotonically increased from 0.19 to 0.6 mu m mainly due to a relative increase in the content of coarse aerosol. Results of this work are important for estimation of the radiative forcing of aerosol and improvement of climate models and algorithms of remote optical sounding.

According to the monitoring data of the optical and microphysical characteristics of smoke aerosol at AERONET stations during forest fires in the summer of 2019 in Alaska, the anomalous selective absorption of smoke aerosol has been detected in the visible and near-infrared spectral range from 440 to 1020 nm. With anomalous selective absorption, the imaginary part of the refractive index of smoke aerosol reached 0.315 at a wavelength of 1020 nm. A power-law approximation of the spectral dependence of the imaginary part of the refractive index with an exponent from 0.26 to 2.35 is proposed. It is shown that, for anomalous selective absorption, power-law approximations of the spectral dependences of the aerosol optical extinction and absorption depths are applicable with an angstrom ngstrom exponent from 0.96 to 1.65 for the aerosol optical extinction depth and from 0.97 to -0.89 for the aerosol optical absorption depth, which reached 0.72. Single scattering albedo varied from 0.62 to 0.96. In the size distribution of smoke aerosol particles with anomalous selective absorption, the fine fraction of particles of condensation origin dominated. The similarity of the fraction of particles distinguished by anomalous selective absorption with the fraction of tar balls (TBs) detected by electron microscopy in smoke aerosol, which, apparently, arise during the condensation of terpenes and their oxygen-containing derivatives, is noted.

Refractive indices (RI) of particles are important in determining their radiative forcing. We measured optical coefficients of particles classified according to their aerodynamic diameter, allowing retrieval of RI using a Mie model. At 405 nm, the RI of BC from a diesel engine was 1.870 (+/- 0.132) + 0.640 (+/- 0.015) i. The RI of secondary organic aerosol (SOA), using a-pinene and o-cresol as precursors, were 1.584 +/- 0.015 and 1.738 (+/- 0.021) + 0.0316 (+/- 0.0018) i, respectively. Neither SOAs demonstrated absorption at 660 nm and their RIs were 1.551 +/- 0.011 and 1.586 +/- 0.011, the similar value suggesting that a single RI may be sufficient for simulating the radiative forcing of SOA at this wavelength. In addition, organics were condensed onto BC to test optical models for coated particles. For BC particles coated with non-absorbing organics, the extinction is predicted accurately by all models. The absorption is significantly over-estimated by core-shell, volume mixing, and effective medium approximations and under-estimated by external mixing. For BC particles coated with weakly absorbing organics, the extinction and absorption are best described by external mixing when the coating ratio is less than 2.5. When the coating ratio is over 2.5, the difference between the external mixing predictions and measurements increases with the coating ratio. Our results show that the absorption of coated BC particles may not be predicted accurately based solely on the equivalent diameter, coating ratio, and pure component RIs, and considerations of additional factors such as morphology may be necessary. Black carbon (BC) and brown carbon (BrC) are extensively investigated components of atmospheric aerosol due to their ability to absorb solar radiation and contribute to atmospheric heating, resulting in a positive radiative forcing. Although BC and BrC are very important for climate, they are poorly represented in atmospheric models. This is in part due to the lack of accurate refractive index (RI) descriptions for both BC and BrC. Previous studies have used mobility selection approaches to select BC/BrC particles upstream of optical spectroscopy instruments to allow RI characterizations, but these retrievals suffer from issues caused by multiple charging. We solved this issue by using a new aerosol classification technique, enabling optical measurements for an aerosol sample classified according to a single physical size without multiple charge artifacts, which improves the subsequent RI retrieval. In addition, non-absorbing and weakly absorbing organic materials were condensed onto BC to form coated soot particles, allowing different optical models for mixed particles to be evaluated. We found that the absorption of coated BC particles may not be predicted with sufficient accuracy from knowledge of only the equivalent diameter, coating composition, and RI, and considering additional factors such as morphology may be necessary for accurate predictions.

Estimation of aerosol radiative forcing continues to suffer from large uncertainties, partially from a lack of observations of aerosol optical properties. Limited measurements of the atmospheric aerosol imaginary refractive index (iRI) have been made, especially in some of the world's most polluted regions. In this study, we measured aerosol optical and micro-physical properties at a regional site, Rohtak, India, representative of polluted cities in the Indo-Gangetic plains in northern India. The average PM2.5 measured during the campaign was 163 mu g/m(3) with a single-scatter albedo of 0.7, indicating the presence of strongly absorbing aerosol components. Measurements of aerosol absorption, scattering, and particle number size distributions were used to estimate the effective refractive index using an established Mie inversion technique. The calculated iRI was spectrally invariant in the visible region with values ranging between 0.076 and 0.145. Brown carbon absorption, estimated using an existing Mie optimization method, ranged 34-88 Mm(-1), with strongly absorbing mass absorption cross-sections (similar to 1.9 m(2)/g). Higher iRI were observed during periods with higher brown carbon absorption, which are likely directly emitted from combustion sources. Low volatility organic carbon fractions dominated during these periods, with likely persistence of atmospheric absorption. The iRI values are at the upper end of previously reported ranges of urban aerosol iRI. In a sensitivity analysis to measured parameters, the absorption had the dominant effect on estimated iRI. Measured single scatter albedos, were lower than those from climate model simulations over the region, demonstrating the need for intrinsic property measurements to evaluate and constrain climate models.

Dust aerosol has an impact on both the regional radiation balance and the global radiative forcing estimation. The Taklimakan Desert is the focus of the present research on the optical and micro-physical characteristics of the dust aerosol characteristics in Central Asia. However, our knowledge is still limited regarding this typical arid region. The DAO-K (Dust Aerosol Observation-Kashgar) campaign in April 2019 presented a great opportunity to understand further the effects of local pollution and transported dust on the optical and physical characteristics of the background aerosol in Kashgar. In the present study, the consistency of the simultaneous observations is tested, based on the optical closure method. Three periods dominated by the regional background dust (RBD), local polluted dust (LPD), and Taklimakan transported dust (TTD), are identified through the backward trajectories, combined with the dust scores from AIRS (Atmospheric Infrared Sounder). The variations of the optical and micro-physical properties of dust aerosols are then studied, while a direct comparison of the total column and near surface is conducted. Generally, the mineral dust is supposed to be primarily composed of silicate minerals, which are mostly very weakly absorbing in the visible spectrum. Although there is very clean air (with PM2.5 of 21 mu g/m(3)), a strong absorption (with an SSA of 0.77, AAE of 1.62) is still observed during the period dominated by the regional background dust aerosol. The near-surface observations show that there is PM2.5 pollution of similar to 98 mu g/m(3), with strong absorption in the Kashgar site during the whole observation. Local pollution can obviously enhance the absorption (with an SSA of 0.72, AAE of 1.58) of dust aerosol at the visible spectrum. This is caused by the increase in submicron fine particles (such as soot) with effective radii of 0.14 mu m, 0.17 mu m, and 0.34 mu m. The transported Taklimakan dust aerosol has a relatively stable composition and strong scattering characteristics (with an SSA of 0.86, AAE of similar to 2.0). In comparison to the total column aerosol, the near-surface aerosol has the smaller size and the stronger absorption. Moreover, there is a very strong scattering of the total column aerosol. Even the local emission with the strong absorption has a fairly minor effect on the total column SSA. The comparison also shows that the peak radii of the total column PVSD is nearly twice as high as that of the near-surface PVSD. This work contributes to building a relationship between the remote sensing (total column) observations and the near-surface aerosol properties, and has the potential to improve the accuracy of the radiative forcing estimation in Kashgar.

Portable aethalometers are commonly used for online measurements of light-absorbing carbonaceous particles (LAC). However, they require strict calibration. In this study, the performance of a micro-aethalometer (MA200 with polytetrafluoroethylene filter) in charactering brown carbon aerosol (BrC) absorption was evaluated in comparison with reference materials and techniques that included bulk solution absorbance and Mie-theory based particle extinction retrieval via broadband cavity enhanced spectrometer (BBCES). Continuous-wavelength resolved (300-650 nm) imaginary refractive index (k(BrC)) was derived with these methods for various BrC proxies and standard materials representing a wide range of sources and absorbing abilities, including the strongly absorbing nigrosin, pahokee peat fluvic acid (PPFA), tar aerosol from wood pyrolysis, humic-like substance (HULIS) separated from wood smoldering burning emissions, and secondary organic aerosols (SOA) from photochemical oxidation of indole and naphthalene in the presence of NOx. The BrC and nigrosin optical results by bulk solution absorption are comparable with the properties retrieved from BBCES. The MA200 raw measurements provide reliable absorption Angstrom exponent (AAE) but overestimate kBrC largely. The parameterized overestimates against reference methods depend on light absorption strength, so that the MA200 overestimates more for the less absorbing BrC. The correction factor for MA200 can be expressed well as an exponential function of kBrC or particle single scattering albedo (SSA), and also as a power-law function of the MA200 raw results derived BrC mass absorption efficiency (MAE). The ensemble correction factor regressed for all these BrC and nigrosin is 2.8 based on bulk absorption and 2.7 using BBCES result as reference. Simple radiative forcing (SRF) calculations for different scenarios using the correction for MA200, show consistent SRF when using the aethalometer results after the k(BrC)-dependent correction. (C) 2021 Elsevier B.V. All rights reserved.

The refractive index of ambient aerosols is one of the most important parameters indicating the scattering and absorption properties of aerosols. We proposed a new method for retrieving the refractive index (RI) of ambient particles. The main advantage of our method is that it assimilates the single particle mixing states measured by a single-particle soot photometer, when compared to the traditional optical method of retrieving the ambient aerosol RI. This method was validated by good consistency between the determined RI with this method and retrieved RI with the method of Zhao et al. (2019c) using datasets from field measurements conducted in East China in June of 2018. The results show that the real part of the refractive index of the black carbon (BC)-free particles ranged between 1.37 and 1.51 and this value changed little across different tested wavelengths. The mean complex refractive index for the refractory BC was 1.67 +/- 0.67i at 525 nm. The mean imaginary parts of the other non-BC components were 0.019 and 0.023 at 450 nm and 370 nm respectively. Brown carbon contributed to 5%, 13% and 29% of the ambient aerosol light absorption at 525 nm, 450 nm and 370 nm respectively in East China. This study provides the ability to determine the ambient aerosol complex refractive index and these data can be used in models to reduce the uncertainties in estimating aerosol radiative forcing.

Aerosols generated from aqueous samples of readily obtainable humic material standards are often used as proxies for organic particulates found in the atmosphere in various investigations, such as consideration of radiative forcing effects. Here, we present results for the retrieved complex index of refraction, m = n + ik, at a wavelength of 403 nm for aerosols prepared from six humic material standards using a calibrated cavity ring-down spectrometer: a humic acid sodium salt, Pahokee peat humic and fulvic acids, Elliott soil humic and fulvic acids, and Suwannee river fulvic acid. In addition, we have conducted UV-vis spectrometric studies to measure the mass absorption coefficients, molar absorptivities, and absorption Angstrom exponents of bulk aqueous solutions of the humic materials. We find clear differences between the humic acid (HA) and fulvic acid (FA) samples with the HA having larger values for the imaginary part of the refractive index, k. The mean value for the HA samples is k = 0.170 while the mean is k = 0.037 for the FA materials. We have examined correlations between the retrieved refractive index and humic material characteristics obtained from spectroscopic and elemental analysis, including aromatic content and the oxygen-to-carbon atomic ratio, where the molar absorption coefficient yields the strongest correlation. Finally, we compare the humic material optical properties to those of authentic and laboratory generated organic carbon samples in order to assess the usefulness of these humic standards as proxies for light absorbing aerosol.

Atmospheric carbonaceous aerosols consisting of black carbon and organic carbon influence Earth's radiative balance by interacting with solar radiation. A subset of organic aerosols known as brown carbon is absorbing in nature and poorly characterized in terms of optical properties. Brown carbon can warm the local and regional atmosphere depending upon its absorbing capacity, mixing state, and meteorological conditions. We report a diurnal spectral absorbing refractive index of brown carbon over North India and its influence on regional radiative forcing. Measurements show the presence of highly absorbing brown carbon consisting of soluble and non-soluble fractions having distinct spectral absorption. The brown carbon refractive index at 365 nm shows a 5096 reduction during daytime when compared to nighttime as a result of combined effects of reduced primary emissions and photobleaching/volatilization. Brown carbon and the lensing effect as a result of a thin absorbing coating exert a forcing of -0.93 +/- 0.27 and 0.13 +/- 0.06 W m(-2), respectively, at the top of atmosphere. Externally mixed absorbing organic carbon in radiative forcing calculations produces 4896 less cooling when compared to the forcing induced by scattering organic carbon. The presence of internally mixed absorbing organic carbon as a shell over black carbon induces 31% more warming compared to a similar shell made of scattering organic carbon. Overall results suggest that brown carbon and the lensing effect need to he included in global climate models while calculating radiative forcing parameters.

The impact of water droplets on soils has recently been found to drive emissions of airborne soil organic particles (ASOP). The chemical composition of ASOP include macromolecules such as polysaccharides, tannins, and lignin (derived from degradation of plants and biological organisms), which determine light absorbing (brown carbon) particle properties. Optical properties of ASOP were inferred from the quantitative analysis of the electron energy-loss spectra acquired over individual particles using transmission electron microscopy. The optical constants of ASOP are compared with those measured for laboratory generated particles composed of Suwanee River Fulvic Acid (SRFA) reference material, which is used as a laboratory surrogate of ASOP. The chemical composition of the particles was analyzed using energy dispersive X-ray spectroscopy, electron energy-loss spectroscopy, and synchrotron-based scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy. ASOP and SRFA exhibit similar carbon composition, with minor differences in other elements present. When ASOP are heated to 350 degrees C their absorption increases as a result of pyrolysis and partial volatilization of semivolatile organic constituents. The retrieved refractive index (RI) at 532 nm of SRFA particles, ASOP, and heated ASOP were 1.22-0.07i, 1.29-0.07i, and 1.90-0.38i, respectively. Retrieved imaginary part of the refractive index of SRFA particles derived from EELS measurements was higher and the real part was lower compared to data from more common optical methods. Therefore, corrections to the EELS data are needed for incorporation into models. These measurements of ASOP optical constants confirm that they have properties characteristic of atmospheric brown carbon and therefore their potential effects on the radiative forcing of climate need to be assessed in atmospheric models.