Color of brown carbon: A model for ultraviolet and visible light absorption by organic carbon aerosol

We recommend ultraviolet and visible absorption spectra to represent particular types of atmospheric organic particles. Spectra of liquids and particles can be compared using the absorption coefficient of bulk material divided by material density. Reported absorption by absorbing organic aerosol from combustion is greater than that of organic material isolated by humic acid extraction. We examine ultraviolet and visible spectra of 200 organic compounds, concluding that visible absorption may be attributable to n → π* electronic transitions in a small fraction of oxygenated compounds. Absorption spectra can be communicated using the band‐gap and Urbach relationships instead of the absorption Angstrom exponent. Water‐soluble atmospheric aerosol has a band‐gap of about 2.5 eV; insoluble aerosol may have a lower band‐gap and higher absorption. Although different types of organic carbon may exhibit a continuum in absorption, there is a sharp distinction between the most‐absorbing organic carbon and black carbon.

[1]  E. Knapp Lineshapes of molecular aggregates, exchange narrowing and intersite correlation , 1984 .

[2]  A. Duarte,et al.  Spectroscopic characteristics of ultrafiltration fractions of fulvic and humic acids isolated from an eucalyptus bleached Kraft pulp mill effluent. , 2003, Water research.

[3]  Tami C Bond,et al.  Emission factors and real-time optical properties of particles emitted from traditional wood burning cookstoves. , 2006, Environmental science & technology.

[4]  M. Ewald,et al.  UV-visible absorption and fluorescence properties of fulvic acids of microbial origin as functions of their molecular weights , 1988 .

[5]  R. L. Wal Soot Precursor Material: Visualization Via Simultaneous LIF-LII and Characterization Via TEM , 1996 .

[6]  T. Bond Spectral dependence of visible light absorption by carbonaceous particles emitted from coal combustion , 2001 .

[7]  P. Minutolo,et al.  The optical band gap model in the interpretation of the UV-visible absorption spectra of rich premixed flames , 1996 .

[8]  G. Amaratunga,et al.  Evolution of sp2 bonding with deposition temperature in tetrahedral amorphous carbon studied by Raman spectroscopy , 2000 .

[9]  Heinz-Helmut Perkampus,et al.  UV-VIS atlas of organic compounds , 1992 .

[10]  M. Andreae,et al.  Black carbon or brown carbon? The nature of light-absorbing carbonaceous aerosols , 2006 .

[11]  C. Linke,et al.  Strong spectral dependence of light absorption by organic carbon particles formed by propane combustion , 2006 .

[12]  E. LeBoeuf,et al.  Macromolecular characteristics of natural organic matter. 2. Sorption and desorption behavior. , 2000 .

[13]  R. Kurdi,et al.  In-situ Formation of Light-Absorbing Organic Matter in Cloud Water , 2003 .

[14]  G. Kiss,et al.  Isolation of water-soluble organic matter from atmospheric aerosol. , 2001, Talanta.

[15]  Thomas A. Milne,et al.  Molecular characterization of the pyrolysis of biomass , 1987 .

[16]  E. LeBoeuf,et al.  Macromolecular Characteristics of Natural Organic Matter. 1. Insights from Glass Transition and Enthalpic Relaxation Behavior , 2000 .

[17]  P. Barber Absorption and scattering of light by small particles , 1984 .

[18]  J. Robertson Electronic and atomic structure of diamond-like carbon , 2003 .

[19]  D. Klockow,et al.  Spectroscopic Characterization of Humic-Like Substances in Airborne Particulate Matter , 1998 .

[20]  M. Jacobson Isolating nitrated and aromatic aerosols and nitrated aromatic gases as sources of ultraviolet light absorption , 1999 .

[21]  O. Mullins,et al.  The Electronic Absorption Edge of Petroleum , 1992 .

[22]  S. Kinoshita,et al.  Urbach tail of organic dyes in solution , 1987 .

[23]  A. Limbeck,et al.  Carbon-specific analysis of humic-like substances in atmospheric aerosol and precipitation samples. , 2005, Analytical chemistry.

[24]  Tami C. Bond,et al.  Calibration and Intercomparison of Filter-Based Measurements of Visible Light Absorption by Aerosols , 1999 .

[25]  Thomas W. Kirchstetter,et al.  Evidence that the spectral dependence of light absorption by aerosols is affected by organic carbon , 2004 .

[26]  Meinrat O. Andreae,et al.  Optical properties of humic-like substances (HULIS) in biomass-burning aerosols , 2005 .

[27]  F. Urbach The Long-Wavelength Edge of Photographic Sensitivity and of the Electronic Absorption of Solids , 1953 .

[28]  A. Ciajolo,et al.  Aromatic structures of carbonaceous materials and soot inferred by spectroscopic analysis , 2004 .

[29]  T. Bond,et al.  Yellow Beads and Missing Particles: Trouble Ahead for Filter-Based Absorption Measurements , 2007 .

[30]  R. Woodward,et al.  Structure and Absorption Spectra. III. Normal Conjugated Dienes , 1942 .

[31]  Patrick J. Medvecz,et al.  The occurrence and light induced formation of ortho-quinonoid lignin structures in white spruce refiner mechanical pulp , 1988 .

[32]  Yinon Rudich,et al.  Atmospheric HULIS : how humic-like are they ? A comprehensive and critical review , 2005 .

[33]  T. Bond,et al.  Light Absorption by Carbonaceous Particles: An Investigative Review , 2006 .

[34]  B. Simoneit,et al.  Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 1. Temperate climate conifers , 2001 .

[35]  K. Pihlaja,et al.  Molecular size distribution and spectroscopic properties of aquatic humic substances , 1997 .

[36]  N. Blough,et al.  On the origin of the optical properties of humic substances. , 2004, Environmental science & technology.