James G. Radney

Dependence of soot optical properties on particle morphology: measurements and model comparisons.

We report the first mass-specific absorption and extinction cross sections for size- and mass-selected laboratory-generated soot aerosol. Measurement biases associated with aerosols possessing multiple charges were eliminated using mass selection to isolate singly charged particles for a specified electrical mobility diameter. Aerosol absorption and extinction coefficients were measured using photoacoustic and cavity ring-down spectroscopy techniques, respectively, for lacey and compacted soot morphologies. The measurements show that the mass-specific absorption cross sections are proportional to particle mass and independent of morphology, with values between 5.7 and 6 m(2) g(-1). Mass-specific extinction cross sections were morphology dependent and ranged between 12 and 16 m(2) g(-1) for the lacey and compact morphologies, respectively. The resulting single-scattering albedos ranged from 0.5 to 0.6. Results are also compared to theoretical calculations of light absorption and scattering from simulated particle agglomerates. The observed absorption is relatively well modeled, with minimum differences between the calculated and measured mass absorption cross sections ranging from ∼ 5% (lacey soot) to 14% (compact soot). The model, however, was unable to satisfactorily reproduce the measured extinction, underestimating the single-scattering albedo for both particle morphologies. These discrepancies between calculations and measurements underscore the need for validation and refinement of existing models of light scattering and absorption by soot agglomerates.

Laboratory Validation of Aerosol Extinction Coefficient Measurements by a Field-Deployable Pulsed Cavity Ring-Down Transmissometer

A pulsed cavity ring-down transmissometer is shown here to be capable of sensitively measuring the aerosol extinction coefficient at two wavelengths (λ = 532, 1064 nm) simultaneously. This instrument can be coupled with a nephelometer (yielding a measurement of the 530 nm scattering coefficient of the same aerosol) and a particle counter to allow the in situ measurement of extensive and intensive optical properties and particle number concentrations of aerosols. From the scattering and extinction coefficient measurements, the aerosol absorption coefficient can be calculated and the intensive properties single scattering albedo and extinction Ångström exponent can be determined. In this report, the pulsed cavity-ring down transmissometer (CRDT) is validated through a series of laboratory experiments. Agreement between the extinction coefficients from the cavity ring-down transmissometer and the scattering coefficient from the nephelometer is demonstrated for purely scattering sub-micron particles. Then agreement between measured extinction and Mie theory is demonstrated when using size-selected particles of measured number concentration. The agreement with Mie theory ranges from excellent (less than 1% deviation) to marginal (12%) depending on the particle size and composition. Similar deviations from Mie theory have been observed (Baynard et al. 2007) and we suggest that they could be due to the influence of multiply charged particles in the size-selection (DMA) process. The 95% confidence level limits of detection and quantitation for the extinction measurement by the CRD transmissometer are estimated to be bext = 4.0 Mm−1 and 13.4 Mm−1, respectively (Skoog et al. 2004).

Practical limitations of aerosol separation by a tandem differential mobility analyzer–aerosol particle mass analyzer

ABSTRACT A cavity ring-down spectrometer and condensation particle counter were used to investigate the limitations in the separation of singly and multiply charged aerosol particles by a tandem differential mobility analyzer (DMA) and aerosol particle mass analyzer (APM). The impact of particle polydispersity and morphology was investigated using three materials: nearly monodisperse polystyrene latex nanospheres (PSL); polydisperse, nearly spherical ammonium sulfate (AS), and polydisperse lacey fractal soot agglomerates. PSL and AS particles were easily resolved as a function of charge. For soot, the presence of multiply charged particles severely affects the isolation of the singly charged particles. In cases where the DMA–APM was unable to fully resolve the singly charged particles of interest, the peak mass deviated by up to 13% leading to errors in the mass specific extinction cross section of over 100%. For measurements of nonspherical particles, nonsymmetrical distributions of concentration as a function of mass were a sign of the presence of multiply charged particles. Under these conditions, the effects of multiply charged particles can be reduced by using a second charge neutralizer after the DMA and prior to the APM. Dilution of the aerosol stream serves to decrease the total number concentration of particles and does not remove the contributions of multiply charged particles.

Direct Measurements of Mass-Specific Optical Cross Sections of Single-Component Aerosol Mixtures

The optical properties of atmospheric aerosols vary widely, being dependent upon particle composition, morphology, and mixing state. This diversity and complexity of aerosols motivates measurement techniques that can discriminate and quantify a variety of single- and multicomponent aerosols that are both internally and externally mixed. Here, we present a new combination of techniques to directly measure the mass-specific extinction and absorption cross sections of laboratory-generated aerosols that are relevant to atmospheric studies. Our approach employs a tandem differential mobility analyzer, an aerosol particle mass analyzer, cavity ring-down and photoacoustic spectrometers, and a condensation particle counter. This suite of instruments enables measurement of aerosol particle size, mass, extinction and absorption coefficients, and aerosol number density, respectively. Taken together, these observables yield the mass-specific extinction and absorption cross sections without the need to model particle morphology or account for sample collection artifacts. Here we demonstrate the technique in a set of case studies which involve complete separation of aerosol by charge, separation of an external mixture by mass, and discrimination between particle types by effective density and single-scattering albedo.

Measurement of Gas and Aerosol Phase Absorption Spectra across the Visible and Near-IR Using Supercontinuum Photoacoustic Spectroscopy.

We demonstrate a method to measure the absorption spectra of gas and aerosol species across the visible and near-IR (500 to 840 nm) using a photoacoustic (PA) spectrometer and a pulsed supercontinuum laser source. Measurements of gas phase absorption spectra were demonstrated using H2O(g) as a function of relative humidity (RH). The measured absorption intensities and peak shapes were able to be quantified and compared to spectra calculated using the 2012 High Resolution Transmission (HITRAN2012) database. Size and mass selected nigrosin aerosol was used to measure absorption spectra across the visible and near-IR. Spectra were measured as a function of aerosol size/mass and show good agreement to Mie theory calculations. Lastly, we measured the broadband absorption spectrum of flame generated soot aerosol at 5% and 70% RH. For the high RH case, we are able to quantifiably separate the soot and water absorption contributions. For soot, we observe an enhancement in the mass specific absorption cross section ranging from 1.5 at 500 nm (p < 0.01) to 1.2 at 840 nm (p < 0.2) and a concomitant increase in the absorption Ångström exponent from 1.2 ± 0.4 (5% RH) to 1.6 ± 0.3 (70% RH).

Measured Wavelength-Dependent Absorption Enhancement of Internally Mixed Black Carbon with Absorbing and Nonabsorbing Materials

Optical absorption spectra of laboratory generated aerosols consisting of black carbon (BC) internally mixed with nonabsorbing materials (ammonium sulfate, AS, and sodium chloride, NaCl) and BC with a weakly absorbing brown carbon surrogate derived from humic acid (HA) were measured across the visible to near-IR (550 to 840 nm). Spectra were measured in situ using a photoacoustic spectrometer and step-scanning a supercontinuum laser source with a tunable wavelength and bandwidth filter. BC had a mass-specific absorption cross section (MAC) of 7.89 ± 0.25 m(2) g(-1) at λ = 550 nm and an absorption Ångström exponent (AAE) of 1.03 ± 0.09 (2σ). For internally mixed BC, the ratio of BC mass to the total mass of the mixture was chosen as 0.13 to mimic particles observed in the terrestrial atmosphere. The manner in which BC mixed with each material was determined from transmission electron microscopy (TEM). AS/BC and HA/BC particles were fully internally mixed, and the BC was both internally and externally mixed for NaCl/BC particles. The AS/BC, NaCl/BC, and HA/BC particles had AAEs of 1.43 ± 0.05, 1.34 ± 0.06, and 1.91 ± 0.05, respectively. The observed absorption enhancement of mixed BC relative to the pure BC was wavelength dependent for AS/BC and decreased from 1.5 at λ = 550 nm with increasing wavelength while the NaCl/BC enhancement was essentially wavelength independent. For HA/BC, the enhancement ranged from 2 to 3 and was strongly wavelength dependent. Removal of the HA absorption contribution to enhancement revealed that the enhancement was ≈1.5 and independent of wavelength.

Evolution of multispectral aerosol optical properties in a biogenically-influenced urban environment during the CARES campaign

Ground-based aerosol measurements made in June 2010 within Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area are used to investigate the evolution of multispectral optical properties as the urban aerosols aged and interacted with biogenic emissions. Along with black carbon and non-refractory aerosol mass and composition observations, spectral absorptio (β abs ), scattering (β sca ), and extinction (β ext ) coefficients for wavelengths ranging from 355 to 1064 nm were measured at both sites using photoacoustic (PA) instruments with integrating nephelometers and using cavity ring-down (CRD) instruments. The daytime average Angstrom exponent of absorption (AEA) was ~1.6 for the wavelength pair 405 and 870 nm at T0, while it was ~1.8 for the wavelength pair 355 and 870 nm at T1, indicating a modest wavelength-dependent enhancement of absorption at both sites throughout the study. The measured and Mie theory calculations of multispectral β sca showed good correlation ( R 2 =0.85–0.94). The average contribution of supermicron aerosol (mainly composed of sea salt particles advected in from the Pacific Ocean) to the total scattering coefficient ranged from less than 20% at 405 nm to greater than 80% at 1064 nm. From 22 to 28 June, secondary organic aerosol mass increased significantly at both sites due to increased biogenic emissions coupled with intense photochemical activity and air mass recirculation in the area. During this period, the short wavelength scattering coefficients at both sites gradually increased due to increase in the size of submicron aerosols. At the same time, BC mass-normalized absorption cross-section (MAC) values for ultraviolet wavelengths at T1 increased by ~60% compared to the relatively less aged urban emissions at the T0 site. In contrast, the average MAC values for 870 nm wavelength were identical at both sites. These results suggest formation of moderately brown secondary organic aerosols formed in biogenically-influenced urban air.

Direct In Situ Mass Specific Absorption Spectra of Biomass Burning Particles Generated from Smoldering Hard and Softwoods

Particles from smoldering biomass burning (BB) represent a major source of carbonaceous aerosol in the terrestrial atmosphere. In this study, mass specific absorption spectra of laboratory-generated smoldering wood particles (SWP) from 3 hardwood and 3 softwood species were measured in situ. Absorption data spanning from λ = 500 to 840 nm were collected using a photoacoustic spectrometer coupled to a supercontinuum laser with a tunable wavelength and bandwidth filter. SWP were size- (electrical mobility) and mass-selected prior to optical characterization allowing data to be reported as mass-specific absorption cross sections (MAC). The median measured MAC at λ = 660 nm for smoldering oak particles was 1.1 (0.57/1.8) × 10-2 m2 g-1 spanning from 83 femtograms (fg) to 517 fg (500 nm ≤ mobility diameter ≤950 nm), MAC values in parentheses are the 16th and 84th percentiles of the measured data (i.e., 1σ). The collection of all six wood species (Oak, Hickory, Mesquite, Western redcedar, Baldcypress, and Blue spruce) had median MAC values ranging from 1.4 × 10-2 m2 g-1 to 7.9 × 10-2 m2 g-1 at λ = 550 nm with absorption Ångström exponents (AAE) between 3.5 and 6.2. Oak, Western redcedar, and Blue spruce possessed statistically similar (p > 0.05) spectra while the spectra of Hickory, Mesquite, and Baldcypress were distinct (p < 0.01) as calculated from a point-by-point analysis using the Wilcox rank-sum test.

Light source effects on aerosol photoacoustic spectroscopy measurements

Photoacoustic spectroscopy measurements of flame-generated soot aerosol coated with small amounts of water yielded absorption enhancements that were dependent on the laser used: quasi-continuous wave (Q-CW, ≈ 650 ps pulse duration and 78 MHz repetition rate) versus continuous wave (CW). Water coating thickness was controlled by exposing the aerosol to a set relative humidity (RH). At ≈ 85 % RH, the mass of the soot particles increased by an amount comparable to a monolayer of water being deposited and enhanced the measured absorption by 36 % and 15 % for the Q-CW and CW lasers, respectively. Extinction measurements were also performed using a cavity ring-down spectrometer (extinction equals the sum of absorption and scattering) with a CW laser and negligible enhancement was observed at all RH. These findings demonstrate that source choice can impact measurements of aerosols with volatile coatings and that the absorption enhancements at high RH previously measured by Radney and Zangmeister (2015) [1] are the result of laser source used (Q-CW) and not from an increase in the particle absorption cross section.

Photoacoustic spectroscopy accurately measures atmospheric 12CO2 and 13CO2 concentrations and optical properties of carbonaceous aerosols

Understanding of todays climate and predictions of future climate require accurate input data to model the energy balance between the suns irradiance and Earth’s atmosphere, oceans, land, and surface ice. An important driver of climate change is the absorption and scattering of sunlight by carbon-based aerosols (soot, smoke, etc) that have widely-varying, source-dependent, and history-dependent optical properties. We use a resonant photoacoustic spectrometer (PAS) to measure the optical absorption cross-section of various carbonaceous aerosols that we generate and characterize in situ. The photoacoustic signal is directly proportional to the energy absorbed by the particles. When combined with simultaneous measurements of the total extinction using cavity ring-down spectroscopy, we obtain the particles’ wavelength-dependent albedo (fraction of incident light scattered). Another important driver of climate change is atmospheric carbon dioxide, a greenhouse gas. With the remarkable linearity, sensitivity,...