W. Patrick Arnott

Towards Aerosol Light-Absorption Measurements with a 7-Wavelength Aethalometer: Evaluation with a Photoacoustic Instrument and 3-Wavelength Nephelometer

Two extreme cases of aerosol optics from the Reno Aerosol Optics Experiment are used to develop a model-based calibration scheme for the 7-wavelength aethalometer. The cases include those of very white and very dark aerosol samples. The former allows for an assessment of the scattering offset associated with this filter-based method, with the wavelength-dependent scattering measured from a 3-wavelength nephelometer, and interpolated and extrapolated to the 7 wavelengths of the aethalometer. A photoacoustic instrument operating at 532 nm is used to evaluate the filter loading effect caused by aerosol light absorption. Multiple scattering theory is used to analytically obtain a filter-loading correction function. This theory shows that the exponential behavior of light absorption in the strong multiple scattering limit scales as the square root of the total absorption optical depth rather than linearly with optical depth as is commonly assumed with Beers law. The multiple scattering model also provides a theoretical justification for subtracting a small fraction of aerosol light scattering away from measured apparent light absorption by the filter method. The model is tested against ambient measurements and is found to require coefficients that are situation specific. Several hypotheses are given for this specificity, and suggested methods for reducing it are discussed. Specific findings are as follows. Simultaneous aerosol light-scattering measurements are required for accurate interpretation of aethalometer data for high aerosol single-scattering albedo. Instantaneous errors of up to ±50% are possible for uncorrected data, depending on filter loading. The aethalometer overpredicts black carbon (BC) concentration on a fresh filter and underpredicts BC on a loaded filter. BC and photoacoustic light absorption can be tightly correlated if the data are averaged over the full range of filter loadings and the aerosol source is constant. Theory predicts that the Aethalometer response may be sensitive to filter face velocity, and hence flow rate, to the extent that particle penetration depth depends on face velocity.

The Reno Aerosol Optics Study: An Evaluation of Aerosol Absorption Measurement Methods

The Reno Aerosol Optics Study (RAOS) was designed and conducted to compare the performance of many existing and new instruments for the in situ measurement of aerosol optical properties with a focus on the determination of aerosol light absorption. For this study, simple test aerosols of black and white particles were generated and combined in external mixtures under low relative humidity conditions and delivered to each measurement system. The aerosol mixing and delivery system was constantly monitored using particle counters and nephelometers to ensure that the same aerosol number concentration and amount reached the different instruments. The aerosol light-scattering measurements of four different nephelometers were compared, while the measurements of seven light-absorption instruments (5 filter based, 2 photoacoustic) were evaluated. Four methods for determining the aerosol light-extinction coefficient (3 cavity ring-down instruments and 1 folded-path optical extinction cell) were also included in the comparisons. An emphasis was placed on determining the representativeness of the filter-based light absorption methods, since these are used widely and because major corrections to the raw attenuation measurements are known to be required. The extinction measurement from the optical extinction cell was compared with the scattering measurement from a high-sensitivity integrating nephelometer on fine, nonabsorbing ammonium sulfate aerosols, and the two were found to agree closely (within 1% for blue and green wavelengths and 2% for red). The wavelength dependence of light absorption for small kerosene and diesel soot particles was found to be very near λ− 1, the theoretical small-particle limit. Larger, irregularly shaped graphite particles showed widely variable wavelength dependencies over several graphite runs. The light-absorption efficiency at a wavelength of 530 nm for pure kerosene soot with a number size distribution peak near 0.3 μ m diameter was found to be 7.5 ± 1.2 m2 g− 1. The two most fundamental independent absorption methods used in this study were photoacoustic absorption and the difference between suspended-state light extinction and scattering, and these showed excellent agreement (typically within a few percent) on mixed black/white aerosols, with the photoacoustic measurement generally slightly lower. Excellent agreement was also observed between some filter-based light-absorption measurements and the RAOS reference absorption method. For atmospherically relevant levels of the aerosol light-absorption coefficient (< 25 Mm− 1), the particle soot absorption photometer (PSAP) absorption measurement at mid-visible wavelengths agreed with the reference absorption measurement to within ∼ 11% for experiment tests on externally mixed kerosene soot and ammonium sulfate. At higher absorption levels (characterized by lower single-scattering albedo aerosol tests), this agreement worsened considerably, most likely due to an inadequate filter loading correction used for the PSAP. The PSAP manufacturers filter loading correction appears to do an adequate job of correcting the PSAP absorption measurement at aerosol single-scattering albedos above 0.80–0.85, which represents most atmospheric aerosols, but it does a progressively worse job at lower single-scattering albedos. A new filter-based light-absorption photometer was also evaluated in RAOS, the multiangle absorption photometer (MAAP), which uses a two-stream radiative transfer model to determine the filter and aerosol scattering effects for a better calculation of the absorption coefficient. The MAAP absorption measurements agreed with the reference absorption measurements closely (linear regression slope of ∼ 0.99) for all experimental tests on externally mixed kerosene soot and ammonium sulfate.

Evaluation of Multiangle Absorption Photometry for Measuring Aerosol Light Absorption

A new multiangle absorption photometer for the measurement of aerosol light absorption was recently introduced that builds on the simultaneous measurement of radiation transmitted through and scattered back from a particle-loaded fiber filter at multiple detection angles. The absorption coefficient of the filter-deposited aerosol is calculated from the optical properties of the entire filter system, which are determined by a two-stream-approximation radiative transfer scheme. In the course of the Reno Aerosol Optics Study (RAOS), the response characteristics of multiangle absorption photometry (MAAP) for white aerosol, pure black carbon aerosol from different sources, external mixtures of black and white aerosol, and ambient aerosol was investigated. The MAAP response characteristics were compared to basic filter transmittance and filter reflectance measurements. MAAP showed close agreement with a reference absorption measurement by extinction minus scattering. The slopes of regression lines vary between 0.99 ± 0.01 and 1.07 ± 0.02 for pure black carbon particles and external mixtures with ammonium sulphate to 1.03 ± 0.05 for ambient aerosol. No effect of the filter aerosol loading or the single-scattering albedo ω0 of the sampled aerosol on the MAAP response characteristics was observed. In contrast, transmittance and reflectance methods showed a clear impact of ω0 and the filter loading on the response characteristics, which requires the application of a correction function for the reliable determination of the aerosol absorption coefficient. In the case of nonabsorbing aerosol, the MAAP approach reduced the magnitude of the apparently measured absorption coefficient by one order of magnitude compared to a basic transmittance measurement.

A model predicting the evolution of ice particle size spectra and radiative properties of cirrus clouds. Part 2: Dependence of absorption and extinction on ice crystal morphology

Abstract This study builds upon the microphysical modeling described in Part I by deriving formulations for the extinction and absorption coefficients in terms of the size distribution parameters predicted from the microphysical model. The optical depth and single scatter albedo of a cirrus cloud can then be determined, which, along with the asymmetry parameter, are the input parameters needed by cloud radiation models. Through the use of anomalous diffraction theory, analytical expressions were developed describing the absorption and extinction coefficients and the single scatter albedo as functions of size distribution parameters, ice crystal shapes (or habits), wavelength, and refractive index. The extinction coefficient was formulated in terms of the projected area of the size distribution, while the absorption coefficient was formulated in terms of both the projected area and mass of the size distribution. These properties were formulated as explicit functions of ice crystal geometry and were not bas...

Emissions from the laboratory combustion of wildland fuels : Particle morphology and size

[1] The morphology of particles emitted by wildland fires contributes to their physical and chemical properties but is rarely determined. As part of a study at the USFS Fire Sciences Laboratory (FSL) investigating properties of particulate matter emitted by fires, we studied the size, morphology, and microstructure of particles emitted from the combustion of eight different wildland fuels (i.e., sagebrush, poplar wood, ponderosa pine wood, ponderosa pine needles, white pine needles, tundra cores, and two grasses) by scanning electron microscopy. Six of these fuels were dry, while two fuels, namely the tundra cores and one of the grasses, had high fuel moisture content. The particle images were analyzed for their density and textural fractal dimensions, their monomer and agglomerate number size distributions, and three different shape descriptors, namely aspect ratio, root form factor, and roundness. The particles were also probed with energy dispersive X-ray spectroscopy confirming their carbonaceous nature. The density fractal dimension of the agglomerates was determined using two different techniques, one taking into account the three-dimensional nature of the particles, yielding values between 1.67 and 1.83, the other taking into account only the two-dimensional orientation, yielding values between 1.68 and 1.74. The textural fractal dimension that describes the roughness of the boundary of the two-dimensional projection of the particle was between 1.10 and 1.19. The maximum length of agglomerates was proportional to a power a of their diameter and the proportionality constant and the three shape descriptors were parameterized as function of the exponent a.

A GCM parameterization for bimodal size spectra and ice mass removal rates in mid-latitude cirrus clouds

This study describes a parameterization for bimodal size spectra in mid-latitude cirrus, based on 996 size distributions (SD) taken from 17 flights in non-convective cirrus during ARM and FIRE intensive observation periods (IOPs). Based on recent work and results given here, the Forward Scattering Spectrometer Probe (FSSP) appears to be a viable instrument for approximating the concentration and sizes of small ice crystals for the cirrus studied here. This, in combination with new methodologies presented, allows the small particle mode of the SD (D≲100 μm) to be characterized. The large mode was characterized from laser imaging 2DC probe measurements. Recent work indicates that the thermal single scattering properties of ice clouds are not adequately determined by effective diameter (Deff) and ice water content (IWC) alone, and that information on SD dispersion (e.g. degree of bimodality) is also required. This parameterization satisfies this need, providing three gamma SD parameters for each mode of the bimodal distribution. Three of these six parameters are approximated as constant, while the other three are expressed in terms of cloud IWC and/or temperature (T). These simple inputs make the parameterization convenient for large scale models, such as Global Climate Models (GCMs). In addition, this parameterization provides a physically rigorous means for parameterizing the mass sedimentation rates from ice clouds in a microphysical sense. Accurate knowledge of mass removal rates is critical for predicting cirrus IWCs and radiative properties. Finally, the data in this study was used to parameterize Deff as a function of T for use in schemes parameterizing bulk short-wave single scattering properties. Uncertainties in estimating Deff drop considerably if most mid-latitude cirrus crystals are irregular, as recent studies suggest.

Nitrogen dioxide and kerosene-flame soot calibration of photoacoustic instruments for measurement of light absorption by aerosols

A nitrogen dioxide calibration method is developed to evaluate the theoretical calibration for a photoacoustic instrument used to measure light absorption by atmospheric aerosols at a laser wavelength of 532.0 nm. This method uses high concentrations of nitrogen dioxide so that both a simple extinction and the photoacoustically obtained absorption measurement may be performed simultaneously. Since Rayleigh scattering is much less than absorption for the gas, the agreement between the extinction and absorption coefficients can be used to evaluate the theoretical calibration, so that the laser gas spectra are not needed. Photoacoustic theory is developed to account for strong absorption of the laser beam power in passage through the resonator. Findings are that the photoacoustic absorption based on heat-balance theory for the instrument compares well with absorption inferred from the extinction measurement, and that both are well within values represented by published spectra of nitrogen dioxide. Photodisso...

Role of small ice crystals in radiative properties of cirrus : a case study, FIRE II, November 22, 1991

Aircraft observations of cirrus cloud were made near Coffeyville, Kansas, during November 1991 as part of the FIRE II project. Cloud ice particle spectra measurements were made using both a PMS 2DC probe and an ice particle replicator. Particles larger than 200 μm were column rosettes. The replicator shows the presence of large numbers of ice crystals smaller than 66 μm (two PMS size bins) that are not recorded by the PMS 2DC probe. Calculations based on the replicator data of the geometrical blocked area and absorption cross section of the cloud per unit volume show that small particles can contribute significantly to and sometimes dominate both the solar extinction and the infrared emission. Intercomparison is made of the ice particle size, area, and mass distributions determined by these different instruments. Power law relationships for area occluded by a crystal as a function of crystal maximum dimension were computed from the PMS 2DC data. The wavelength-dependent infrared absorption cross section per volume was computed using a simple model based on anomalous diffraction and area and mass dimensional relationships for the ice crystals.

Variations in Speciated Emissions from Spark-Ignition and Compression-Ignition Motor Vehicles in California's South Coast Air Basin

Abstract The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Cavity Ring-Down and Cavity-Enhanced Detection Techniques for the Measurement of Aerosol Extinction

An instrument employing cavity ring-down (CRD) and cavity-enhanced detection (CED) for the local measurement of aerosol extinction is described and demonstrated. CRD measures the lifetime of photons in a high-quality optical cavity and thereby determines the sum of sample extinction between the cavity mirrors and that due to mirror losses. CRD systems can be calibrated with a single gas for the determination of extinction. A green laser emitting subnanosecond pulses is used as a light source, facilitating measurements free from optical interference in the cavity. The addition of a low-frequency chopper allows for the determination of extinction coefficients with simple linear fitting procedures and also facilitates CED measurements by providing laser power modulation for phase-sensitive detection. CED measures the average power transmitted by the optical cavity. After calibration with two gases, CED allows for the independent measurement of extinction with very high dynamic range and for an independent comparison with CRD measurements, thereby increasing confidence in the measurements.