Rajan K. Chakrabarty

An Inter-Comparison of Instruments Measuring Black Carbon Content of Soot Particles

Inter-comparison studies of well-characterized fractal soot particles were conducted using the following four instruments: Aerosol Mass Spectrometer-Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Multi-Angle Absorption Photometer (MAAP), and Photoacoustic Spectrometer (PAS). These instruments provided measurements of the refractory mass (AMS-SMPS), incandescent mass (SP2) and optically absorbing mass (MAAP and PAS). The particles studied were in the mobility diameter range from 150 nm to 460 nm and were generated by controlled flames with fuel equivalence ratios ranging between 2.3 and 3.5. The effect of organic coatings (oleic acid and anthracene) on the instrument measurements was determined. For uncoated soot particles, the mass measurements by the AMS-SMPS, SP2, and PAS instruments were in agreement to within 15%, while the MAAP measurement of optically-absorbing mass was higher by ∼ 50%. Thin organic coatings (∼ 10 nm) did not affect the instrument readings. A thicker (∼ 50 nm) oleic acid coating likewise did not affect the instrument readings. The thicker (∼60 nm) anthracene coating did not affect the readings provided by the AMS-SMPS or SP2 instruments but increased the reading of the MAAP instrument by ∼ 20% and the reading of the PAS by ∼ 65%. The response of each instrument to the different particle types is discussed in terms of particle morphology and coating material.

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.

Characterizing elemental, equivalent black, and refractory black carbon aerosol particles: a review of techniques, their limitations and uncertainties

Elemental-, equivalent black- and refractory black-carbon are terms that have been defined in order to dissect the more general term, black carbon, into its component parts related to its specific chemical and optical properties and its impact on climate and health. Recent publications have attempted to clarify the meaning of these terms with respect to their environmental impact, particularly on climate. Here, we focus on the measurement aspects, reviewing the most commonly implemented techniques for the direct and indirect derivation of black carbon properties, their strengths, limitations, and uncertainties, and provide a non-exhaustive bibliography where the reader can find more detailed information. This review paper is designed as a guide for those wishing to learn about the current state of black carbon measurement instrumentation, how calibration is carried out, when one instrument may have the advantage over another, and where new techniques are needed to fill important knowledge gaps.

Light scattering and absorption by fractal-like carbonaceous chain aggregates: comparison of theories and experiment.

This study compares the optical coefficients of size-selected soot particles measured at a wavelength of 870 nm with those predicted by three theories, namely, Rayleigh-Debye-Gans (RDG) approximation, volume-equivalent Mie theory, and integral equation formulation for scattering (IEFS). Soot particles, produced by a premixed ethene flame, were size-selected using two differential mobility analyzers in series, and their scattering and absorption coefficients were measured with nephelometry and photoacoustic spectroscopy. Scanning electron microscopy and image processing techniques were used for the parameterization of the structural properties of the fractal-like soot aggregates. The aggregate structural parameters were used to evaluate the predictions of the optical coefficients based on the three light-scattering and absorption theories. Our results show that the RDG approximation agrees within 10% with the experimental results and the exact electromagnetic calculations of the IEFS theory. Volume-equivalent Mie theory overpredicts the experimental scattering coefficient by a factor of approximately 3.2. The optical coefficients predicted by the RDG approximation showed pronounced sensitivity to changes in monomer mean diameter, the count median diameter of the aggregates, and the geometric standard deviation of the aggregate number size distribution.

Soot superaggregates from flaming wildfires and their direct radiative forcing

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension Df ≈ 1.8 mobility diameter Dm ≤ 1 μm, and aerodynamic diameter Da ≤ 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic Df ≈ 2.6, Dm > 1 μm, and Da ≤ 300 nm that form via the cluster-dense aggregation mechanism. We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. We estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (Df ≈ 1.8) aggregates, and ≈90% more warming than the volume-equivalent spherical soot particles simulated in climate models.

Polycyclic aromatic hydrocarbons in biomass-burning emissions and their contribution to light absorption and aerosol toxicity.

In recent years, brown carbon (BrC) has been shown to be an important contributor to light absorption by biomass-burning atmospheric aerosols in the blue and near-ultraviolet (UV) part of the solar spectrum. Emission factors and optical properties of 113 polycyclic aromatic hydrocarbons (PAHs) were determined for combustion of five globally important fuels: Alaskan, Siberian, and Florida swamp peat, cheatgrass (Bromus tectorum), and ponderosa pine (Pinus ponderosa) needles. The emission factors of total analyzed PAHs were between 1.9±0.43.0±0.6 and 9.6±1.2-42.2±5.4mgPAHkg(-1)fuel for particle- and gas phase, respectively. Spectrophotometric analysis of the identified PAHs showed that perinaphthenone, methylpyrenes, and pyrene contributed the most to the total PAH light absorption with 17.2%, 3.3 to 10.5%, and 7.6% of the total particle-phase PAH absorptivity averaged over analyzed emissions from the fuels. In the gas phase, the top three PAH contributors to BrC were acenaphthylene (32.6%), anthracene (8.2%), and 2,4,5-trimethylnaphthalene (8.0%). Overall, the identified PAHs were responsible for 0.087-0.16% (0.13% on average) and 0.033-0.15% (0.11% on average) of the total light absorption by dichloromethane-acetone extracts of particle and gas emissions, respectively. Toxic equivalency factor (TEF) analysis of 16 PAHs prioritized by the United States Environmental Protection Agency (EPA) showed that benzo(a)pyrene contributed the most to the PAH carcinogenic potency of particle phase emissions (61.8-67.4% to the total carcinogenic potency of Σ16EPA PAHs), while naphthalene played the major role in carcinogenicity of the gas phase PAHs in the biomass-burning emission analyzed here (35.4-46.0% to the total carcinogenic potency of Σ16EPA PAHs). The 16 EPA-prioritized PAHs contributed only 22.1±6.2% to total particle and 23.4±11% to total gas phase PAH mass, thus toxic properties of biomass-burning PAH emissions are most likely underestimated.

Strong radiative heating due to wintertime black carbon aerosols in the Brahmaputra River Valley

values of BC mass concentration were 9–41 mgm � 3 , with maxima over 50 mgm � 3 during evenings and early mornings. Median BC concentrations were higher than in mega cities of India and China, and significantly higher than in urban locations of Europe and USA. The corresponding mean cloud-free aerosol radiative forcing is � 63.4 Wm � 2 at the surface and +11.1 Wm � 2 at the top of the atmosphere with the difference giving the net atmospheric BC solar absorption, which translates to a lower atmospheric heating rate of � 2 K/d. Potential regional climatic impacts associated with large surface cooling and high lower-atmospheric heating are discussed. Citation: Chakrabarty, R. K., M. A. Garro, E. M. Wilcox, and H. Moosmuller (2012), Strong radiative heating due to wintertime black carbon aerosols in the Brahmaputra River Valley, Geophys. Res. Lett., 39, L09804, doi:10.1029/2012GL051148.

Technical Note: Simple analytical relationships between Ångström coefficients of aerosol extinction, scattering, absorption, and single scattering albedo

Abstract. Angstrom coefficients are commonly used to parameterize the slow wavelength dependence of aerosol scattering, absorption, and extinction coefficients and single scattering albedo. Here we introduce simple analytical relationships between these coefficients that establish a framework for intercomparison between theory and experimental results from different instruments and platforms and allow for closure studies and improved physical understanding.

Observation of Superaggregates from a Reversed Gravity Low-Sooting Flame

Copyright 2012 American Association for Aerosol Research

Simulation of Aggregates with Point-Contacting Monomers in the Cluster–Dilute Regime. Part 1: Determining the Most Reliable Technique for Obtaining Three-Dimensional Fractal Dimension from Two-Dimensional Images

Analysis of electron microscopy images of fractal-like aggregates involves extraction of three-dimensional (3-d) structural and geometrical properties of aggregates, which are commonly unknown, from their two-dimensional (2-d) projected images. The fractal dimension Df of an aggregate is considered to be the key property for characterizing fractal-like aggregates. The nested squares method (NSM) (also known as the cumulative-intersection method and concentric circles method), the perimeter grid method (PGM), and the ensemble method (EM) have found wide use as techniques for determination of Df of both individual and ensemble aggregates in the cluster-dilute regime. However, no study has so far compared the validity and accuracy of these three most commonly used analysis methods. In this article, using the fractal simulation package FracMAP, these methods were individually tested by applying them to a statistically significant (∼2500 per fractal dimension) number of projected images of all stable orientations of computer-generated 3-d fractal aggregates with Df ranging between 1.0 and 3.0 in increments of 0.1. Results show that of the three methods, the only method that can be used to reliably determine Df from 2-d images is the EM. Both the NSM and the PGM yield many overlapping values of 2-d Df for differing values of 3-d Df resulting in a non-one-to-one relationship and large margins of error. A correction factor has been formulated as a piece-wise function of linear functions for calibrating EM measured values of 2-d Df to actual 3-d Df values.