Light scattering and absorption by soot in the presence of sulfate aerosols

The radiative properties of aerosol-soot mixtures, both internal and external, are determined in the visible and near-infrared bands by use of exact indirect mode-matching solutions to electromagnetic-wave scattering from a sphere with an eccentric spherical inclusion and from a cluster of spheres. Spherical sulfate droplets are assumed to represent aerosol particles. Soot particles are represented by volume-equivalent carbon spheres, the size distribution of which is obtained from the number distribution of the primary carbon particles that aggregate into soot grains. The mean gram-specific absorption cross section and the mean albedo of aerosol-soot mixtures are obtained by integration of the corresponding characteristics of composite sulfate-carbon particles over the size range of carbon spheres. Enhanced absorption of light by soot in aerosol-soot mixtures, a result of lensing by sulfate droplets, is highlighted by maps of the electromagnetic field in a sulfate-carbon particle.     

Ultraviolet-visible bulk optical properties of randomly distributed soot

The presence of soot in the lower stratosphere was recently established by in situ measurements. To isolate their contribution to optical measurements from that of background aerosol, the soot's bulk optical properties must be determined. Laboratory measurements of extinction and polarization of randomly distributed soot were conducted. For all soot, measurements show a slight reddening extinction between 400 and 700 nm and exhibit a maximum of 100% polarization at a scattering angle of 75 +/- 5 degrees. Such results cannot be reproduced by use of Mie theory assumptions. The different optical properties of soot and background stratospheric aerosol could allow isolation of soot in future analyses of stratospheric measurements.     

Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 2. Closure study

Spectral particle extinction coefficients of atmospheric aerosols were measured with, to the best of our knowledge, a newly designed differential optical absorption spectroscopy (DOAS) instrument. A closure study was carried out on the basis of optical and microphysical aerosol properties obtained from nephelometer, particle soot/absorption photometer, hygroscopic tandem differential mobility analyzer, twin differential mobility particle sizer, aerodynamic particle sizer, and Berner impactors. The data were collected at the urban site of Leipzig during a period of 10 days in March 2000. The performance test also includes a comparison of the optical properties measured with DOAS to particle optical properties calculated with a Mie-scattering code. The computations take into account dry and ambient particle conditions. Under dry particle conditions the linear regression and the correlation coefficient for particle extinction are 0.95 and 0.90, respectively. At ambient conditions these parameters are 0.89 and 0.97, respectively. An inversion algorithm was used to retrieve microphysical particle properties from the extinction coefficients measured with DOAS. We found excellent agreement within the retrieval uncertainties.     

Optical properties of internally mixed ammonium sulfate and soot particles--a study of individual aerosol particles and ambient aerosol populations

Optical parameters of simulated ambient individual ammonium sulfate and soot-mixed particles were calculated using the discrete-dipole approximation method with different model geometries. Knowledge of the mixing state and the approximation by a suited idealized geometry reduces the errors of the optical properties by +/-50% to +/-10%. The influence of the soot content and the mixing state on the optical properties of the total aerosol was estimated. For the total aerosol population, the size distribution and the absolute soot content had the largest influence. The exact geometry of the ammonium sulfate and soot-mixed particles can be neglected.     

Effective medium theories for irregular fluffy structures: aggregation of small particles

The extinction efficiencies as well as the scattering properties of particles of different porosity are studied. Calculations are performed for porous pseudospheres with small size (Rayleigh) inclusions using the discrete dipole approximation. Five refractive indices of materials covering the range from 1.20+0.00i to 1.75+0.58i were selected. They correspond to biological particles, dirty ice, silicate, and amorphous carbon and soot in the visual part of the spectrum. We attempt to describe the optical properties of such particles using Lorenz-Mie theory and a refractive index found from some effective medium theory (EMT) assuming the particle is homogeneous. We refer to this as the effective model. It is found that the deviations are minimal when utilizing the EMT based on the Bruggeman mixing rule. Usually the deviations in the extinction factor do not exceed approximately 5% for particle porosity P = 0 - 0.9 and size parameters x(porous) = 2 pi r(s,porous)/lambda < or approximately = 25. The deviations are larger for scattering and absorption efficiencies and smaller for particle albedo and the asymmetry parameter. Our calculations made for spheroids confirm these conclusions. Preliminary consideration shows that the effective model represents the intensity and polarization of radiation scattered by fluffy aggregates quite well. Thus the effective models of spherical and nonspherical particles can be used to significantly simplify the computations of the optical properties of aggregates containing only Rayleigh inclusions.     

Particle backscatter, extinction, and lidar ratio profiling with Raman lidar in south and north China

Aerosol Raman lidar observations of profiles of the particle extinction and backscatter coefficients and the respective extinction-to-backscatter ratio (lidar ratio) were performed under highly polluted conditions in the Pearl River Delta (PRD) in southern China in October 2004 and at Beijing during a clear period with moderately polluted to background aerosol conditions in January 2005. The anthropogenic haze in the PRD is characterized by volume light-extinction coefficients of particles ranging from approximately 200 to 800 Mm(-1) and lidar ratios mostly between 40 and 55 sr (average of 47+/-6 sr). Almost clean air masses were observed throughout the measurements of the Beijing campaign. These air masses originated from arid desert-steppe-like regions (greater Gobi area). Extinction values usually varied between 100 and 300 Mm(-1), and the lidar ratios were considerably lower (compared with PRD values) with values mostly from 30 to 45 sr (average of 38+/-7 sr). Gobi dust partly influenced the observations. Unexpectedly low lidar ratios of approximately 25 sr were found for a case of background aerosol with a low optical depth of 0.05. The low lidar ratios are consistent with Mie-scattering calculations applied to ground-based observations of particle size distributions.     

Explosion dust particle size measurements

In situ measurements of the sizes and concentrations of dust particles generated by the detonation of high explosives in clay soil near Leesville, La., sandy clay soil near Huntsville, Ala., and sandy soils near Orogrande, N.M. are reported. Measurements were generally made within 1 m of the surface (in one case 10 m) at distances ranging from 10 to approximately 50 m from the detonation point with a combination of Knollenberg lightscattering counters (for particles with equivalent radius in the submicron to 15-microm range) and a Knollenberg optical array probe (for particles of 10-150 microm). Measurements were made for periods of several tens of seconds following detonation. All dust size distributions, irrespective of soil or explosive type, exhibit a bimodal character with mass mean radii of approximately 7 and 70 microm. Peak aerosol mass loadings inferred from the distributions have values ranging from 0.05 to 10 g gm-3 with the larger mode of particles contributing most to the mass loading. Predictions of dust extinction coefficients at visible (0.55-microm) and IR (10.4-microm) wavelengths were made using the measured size distributions together with estimates of dust refractive indices. These predictions suggest that extinction should be nearly neutral (wavelength independent) in agreement with transmission measurements made during some of the tests. Predicted mass extinction coefficients, under the assumption of dust material density of 2.5 g cm-3, are of the order of 0.05 m2 g-1 at both visible and IR wavelengths. This value is also in good agreement with a test-averaged measured value of 0.03 m3 g-1 (at lambda = 10.6 microm) obtained using a short path transmissometer and hi-vol sampler.     

Inversion of multiwavelength Raman lidar data for retrieval of bimodal aerosol size distribution

We report on the feasibility of deriving microphysical parameters of bimodal particle size distributions from Mie-Raman lidar based on a triple Nd:YAG laser. Such an instrument provides backscatter coefficients at 355, 532, and 1064 nm and extinction coefficients at 355 and 532 nm. The inversion method employed is Tikhonov's inversion with regularization. Special attention has been paid to extend the particle size range for which this inversion scheme works to approximately 10 microm, which makes this algorithm applicable to large particles, e.g., investigations concerning the hygroscopic growth of aerosols. Simulations showed that surface area, volume concentration, and effective radius are derived to an accuracy of approximately 50% for a variety of bimodal particle size distributions. For particle size distributions with an effective radius of < 1 microm the real part of the complex refractive index was retrieved to an accuracy of +/- 0.05, the imaginary part was retrieved to 50% uncertainty. Simulations dealing with a mode-dependent complex refractive index showed that an average complex refractive index is derived that lies between the values for the two individual modes. Thus it becomes possible to investigate external mixtures of particle size distributions, which, for example, might be present along continental rims along which anthropogenic pollution mixes with marine aerosols. Measurement cases obtained from the Institute for Tropospheric Research six-wavelength aerosol lidar observations during the Indian Ocean Experiment were used to test the capabilities of the algorithm for experimental data sets. A benchmark test was attempted for the case representing anthropogenic aerosols between a broken cloud deck. A strong contribution of particle volume in the coarse mode of the particle size distribution was found.     

Wavelength-dependent optical extinction of carbonaceous particles in atmospheric aerosols and interstellar dust

Optical extinction spectra for particles of structurally disordered carbonaceous material (carbon black, soot) are discussed in terms of the effects of size and shape and the difference between coagulated and coalesced particles. For this purpose, the orientation-averaged specific extinction for several compact and open aggregates of spherical particles is calculated and compared with the specific extincton by homogeneous particles, i.e., volume-equivalent sphere and elongated spheroids. The extinction spectra are calculated for wavelengths from 0.2 to 1000 microm by use of the optical constants for the carbonaceous materials of J?ger et al. [Astron. Astrophys. 332, 291 (1998)] and Schnaiter et al. [Astrophys. J. 498, 486 (1998)]. Comparisons with the model case of particles composed of graphite and with measurements of diesel soot aerosols are made.     

Laser-induced breakdown spectroscopy for ambient air particulate monitoring: correlation of total and speciated aerosol particle counts

A statistical analysis of ambient air particle monitoring, namely PM2.5, is presented to elucidate the correlations between laser-induced breakdown spectroscopy (LIBS)-based speciated aerosol monitoring and non-speciated aerosol monitoring (i.e., total particle counts). LIBS was used in a real-time, conditional-processing mode to identify individual aerosol particles containing detectable quantities of either calcium or sodium, as based on the resulting atomic emission signals. Using this technique, real-time measurements of speciated aerosol particle concentrations and analyte mass concentrations were evaluated for a total of 60 1-hour sampling periods spread over a 5-week period. For each 1-hour sampling period, total aerosol counts were simultaneously monitored using a commercial light scattering-based instrument. Over the 30 sampling periods, aerosol counts (both total and LIBS-based) were found to vary by more than one order of magnitude. For aerosol particles in the 500 nm to 2.5 microm size range, significant correlations were found between the two sampling methods, resulting in correlation coefficients (r2) ranging from 0.22 to 0.93. In addition, transient fluctuations in aerosol counts on a timescale of 5 to 10 minutes were successfully observed simultaneously with the two monitoring techniques, thereby demonstrating the temporal resolution of LIBS.     

Enhancing the detection of sulfate particles for laser ablation aerosol mass spectrometry

A major limitation to the application of laser ablation aerosol mass spectrometry for the detection of particles less than 200 nm in diameter is a low ablation efficiency for sulfate particles. (Ablation efficiency is the probability that an ablated particle produces a detectable ion signal.) A method is described here to enhance the ablation efficiency of sulfate particles by coating them with a UV-absorbing compound. The method can be applied in-line with the aerosol mass spectrometer in a manner that does not significantly alter the aerosol size distribution. It is shown that a 12-nm coating of 1-naphthyl acetate increases the ablation efficiency of 136-nm ammonium sulfate particles by at least a factor of 20, while similar coatings on oleic acid and ammonium nitrate particles do not significantly alter the ablation efficiency. The results suggest that "undetected" particles, presumably sulfate, in ambient aerosol can be assessed.     

Characterization of atmospheric aerosols from infrared measurements: simulations, testing, and applications

An inversion method for the characterization of atmospheric condensed phases from infrared (IR) spectra is described. The method is tested with both synthetic IR spectra and the spectra of particles that flow in a cryogenic flow tube. The method is applied to the IR spectra recorded by the Atmospheric Trace Molecule Spectroscopy instrument carried by the Space Shuttle during three missions in 1992, 1993, and 1994. The volume density and particle size distribution for sulfate aerosol are obtained as a function of altitude. The density and size distribution of ice particles in several cirrus clouds are also retrieved. The probable radius of the ice particles in the high-altitude (10-15-km) cirrus clouds is found to be approximately 6-7 microm.     

Microphysical particle parameters from extinction and backscatter lidar data by inversion with regularization: simulation

A sensitivity study with an inversion scheme that permits one to retrieve physical parameters of tropospheric particle size distributions, e.g., effective radius, volume, surface-area, and number concentrations, as well as the mean complex refractive index from backscatter and extinction coefficients at multiple wavelengths is presented. The optical data for the analysis are derived from Mie-scattering calculations for monomodal and bimodal logarithmic-normal distributions in the particle size range between 0.01 and 10 microm. The complex refractive index is taken between 1.33 and 1.8 in the real part and between 0 and 0.1 in the imaginary part. The choice of these parameters takes account of properties of optically active atmospheric particles. The wavelengths were chosen at 355, 400, 532, 710, 800, and 1064 nm for the backscatter and at 355 and 532 nm for the extinction data, which are the available wavelengths of the two lidar systems at the Institute for Tropospheric Research. Cases of erroneous optical data of the order of as much as 20%, an unknown refractive index, which may also be wavelength and size dependent, as well as the a priori unknown modality of the particle size distribution were considered. It is shown that both extinction channels are necessary for determining the above-mentioned parameters within reasonable limits, i.e., effective radius, surface-area, and volume concentrations to an accuracy of +/-50%, the real part of the complex refractive index to +/-0.1, and the imaginary part to +/-50%. The number concentration may have errors larger than 50%. The overall performance of the inversion scheme permits the evaluation of experimental data on a routine basis.     

Error analysis for retrieval of urban atmospheric aerosol properties from downwelling infrared radiation spectra

The possibility of retrieval of urban aerosol physical properties from downwelling atmospheric infrared radiation spectra between 700 and 1400 cm(-1) with 0.24-cm(-1) spectral resolution, which can be obtained from the tropospheric infrared interferometric sounder developed by the Central Research Institute of Electric Power Industry, was estimated from error analysis of the least-squares fit method. The error analysis for retrieval of the aerosol extinction coefficient spectra in three atmospheric layers (boundary, free troposphere, and stratosphere) showed the retrievability only of the boundary layer. Based on this result, we propose the retrieval for particle number density of each aerosol component, which is one of the parameters for the aerosol size distribution function, using the boundary aerosol extinction coefficient spectra. We assume that aerosols in urban areas consist of three types of component, namely, water soluble, soot, and dustlike. Under this assumption, we estimated the error of the retrieved volume density for each aerosol component. For the estimation we used the least-squares fit of Mie-generated spectral extinction coefficients. The estimated error shows that the volume density of each aerosol component in an urban boundary layer is equivalent to the retrieval target. We also show that the aerosol properties can be retrieved with higher accuracy when the effects of multiple scattering by aerosols are included in the retrieval procedure.     

Information content of multiwavelength lidar data with respect to microphysical particle properties derived from eigenvalue analysis

The multiwavelength Raman lidar technique in combination with sophisticated inversion algorithms has been recognized as a new tool for deriving information about the microphysical properties of atmospheric aerosols. The input optical parameter sets, provided by respective aerosol Raman lidars, are at the theoretical lower limit at which these inversion algorithms work properly. For that reason there is ongoing intense discussion of the accuracy of these inversion methods and the possibility of simultaneous retrieval of the particle size distribution and the complex refractive index. We present results of the eigenvalue analysis, used to study the information content of multiwavelength lidar data with respect to microphysical particle properties. Such an analysis provides, on a rather mathematical basis, more insight into the limitations of these inversion algorithms regarding the accuracy of the retrieved parameters. We show that the effective radius may be retrieved to 50% accuracy and the real and imaginary part of the complex refractive index to +/- 0.05 and +/- 0.005i, if the imaginary part is < 0.02i. These results are in accordance with the classic approach of simulation studies with synthetic particle size distributions. Major difficulties are found with a particle effective radius of < 0.15 microm. In that case the complex refractive index may not be derived with sufficient accuracy. The eigenvalue analysis also shows that the accuracy of the derived parameters degrades if the imaginary part is > 0.02i. Furthermore it shows the importance of the simultaneous use of backscatter and extinction coefficients for the retrieval of microphysical parameters.     

Extending ATOFMS measurements to include refractive index and density

An absolute calibration of the light scattering region in an aerosol time-of-flight mass spectrometer (ATOFMS) has been performed enabling a direct comparison of the average experimentally measured light scattering intensity to theory. A fitting procedure allows for the determination of both refractive index and density for spherical homogeneous particles. The scattering information has been correlated with the other single-particle information measured by the ATOFMS. Size, chemical composition, and scattering intensity can all be linked to establish a better understanding of the relationships between the chemical and physical properties of aerosol particles. Currently, inputs into climate models are derived from data acquired from bulk aerosol composition measurements, and therefore, assumptions must be made regarding the chemical associations within individual particles (mixing state) to enable modelers to calculate the relevant aerosol optical properties. These new measurements aim for the goal of directly testing the model assumptions by utilizing single-particle chemical information to derive the optical properties of the different particle classes.     

Laser-induced incandescence: excitation intensity

Assumptions of theoretical laser-induced incandescence (LII) models along with possible effects of high-intensity laser light on soot aggregates and the constituent primary particles are discussed in relation to selection of excitation laser fluence. Ex situ visualization of laser-heated soot by use of transmission electron microscopy reveals significant morphological changes (graphitization) induced by pulsed laser heating. Pulsed laser transmission measurements within a premixed laminar sooting flame suggest that soot vaporization occurs for laser fluences greater than 0.5 J/cm(2) at 1064 nm. Radial LII intensity profiles at different axial heights in a laminar ethylene gas jet diffusion flame reveal a wide range of signal levels depending on the laser fluence that is varied over an eight fold range. Results of double-pulse excitation experiments in which a second laser pulse heats in situ the same soot that was heated by a prior laser pulse are detailed. These two-pulse measurements suggest varying degrees of soot structural change for fluences below and above a vaporization threshold of 0.5 J/cm(2) at 1064 nm. Normalization of the radial-resolved LII signals based on integrated intensities, however, yields self-similar profiles. The self-similarity suggests robustness of LII for accurate relative measurement of soot volume fraction despite the morphological changes induced in the soot, variations in soot aggregate and primary particle size, and local gas temperature. Comparison of LII intensity profiles with soot volume fractions (f(v)) derived by light extinction validates LII for quantitative determination of f(v) upon calibration for laser fluences ranging from 0.09 to 0.73 J/cm(2).     

Geometrical renormalization approach to calculating optical properties of fractal carbonaceous soot

We develop a theoretical approach to calculating optical properties of carbonaceous soot in the long-wavelength limit. Our method is based on geometrical renormalization of clusters; it avoids both the inaccuracy of the dipole approximation in its pure form and the numerical complexity of rigorous direct methods of solving the EM boundary problem. The results are verified by comparison with the experimental measurements for specific extinction of diesel soot in the spectral region from 0.488 microm to 0.857 cm that were performed by Bruce et al. [Appl. Opt. 30, 1537 (1991)]. The theory leads to analytical expressions that are applicable to different soots, with various geometrical properties and optical constants. We show that the functional form of the long-wavelength asymptote of the specific extinction can depend critically on a parameter characterizing the sample geometry, and we identify the critical value of this parameter.     

Optical properties of dispersed aerosols in the near ultraviolet (355 nm): measurement approach and initial data

An aerosol albedometer combining cavity ring-down spectroscopy (CRDS) with integrating sphere nephelometry was developed for use at λ = 355 nm. The instrument measures extinction and scattering coefficients of dispersed particulate matter in the near ultraviolet (UV) spectral region. Several samples have been analyzed, including: ammonium sulfate, secondary organic aerosols (SOA) resulting from the ozonolysis of α-pinene and photooxidation of toluene, redispersed soil dust samples, biomass burning aerosols, and ambient aerosols. When particle size and number density were experimentally controlled, extinction coefficients and scattering coefficients were found to have a linear relationship with particle number concentration, in good agreement with light scattering theory. For ammonium sulfate and pinene samples, extinction cross sections for size-selected (D(p) = 300 nm) samples were within the range of 1.65-2.60 × 10(-9) cm(2) with the largest value corresponding to ammonium sulfate and the lowest value for pinene SOA. The scattering cross sections of pinene and ammonium sulfate aerosols were indistinguishable from the extinction cross sections, indicating that these particle types had minimal light absorption at 355 nm. However, soil dusts and biomass burning aerosols showed significant absorption with single scatter albedo (SSA) between 0.74 and 0.84. Ambient aerosols also had transient absorption at 355 nm that correlated well with a particle-soot absorption photometer (PSAP) measuring visible light absorption.     

Measured infrared optical cross sections for a variety of chemical and biological aerosol simulants

We conducted a series of spectral extinction measurements on a variety of aerosolized chemical and biological simulants over the spectral range 3-13 microm using conventional Fourier-transform IR (FTIR) aerosol spectroscopy. Samples consist of both aerosolized particulates and atomized liquids. Materials considered include Bacillus subtilis endospores, lyophilized ovalbumin, polyethylene glycol, dimethicone (SF-96), and three common background materials: kaolin clay (hydrated aluminum silicate), Arizona road dust (primarily SiO2), and diesel soot. Aerosol size distributions and mass density were measured simultaneously with the FTIR spectra. As a result, all optical parameters presented here are mass normalized, i.e., in square meters per gram. In an effort to establish the utility of using Mie theory to predict such parameters, we conducted a series of calculations. For materials in which the complex indices of refraction are known, e.g., silicone oil (SF-96) and kaolin, measured size distributions were convolved with Mie theory and the resultant spectral extinction calculated. Where there was good agreement between measured and calculated extinction spectra, absorption, total scattering, and backscatter were also calculated.