Abstract. Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While black carbon (BC) is highly absorbing, some organic carbon (OC) also has significant absorption, especially at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to positive direct aerosol radiative forcing. Quantification of that absorption is necessary so that radiative-transfer models can evaluate the net radiative effect of OC. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble OC contributes to light absorption at both ultraviolet and visible wavelengths. However, a larger portion of the absorption comes from OC that is extractable only by methanol. Absorption spectra of water-soluble OC are similar to literature reports. We compare spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating OC with higher absorption; changing wood temperature from a devolatilizing state of 210 °C to a near-flaming state of 360 °C causes about a factor of four increase in mass-normalized absorption at visible wavelengths. A clear-sky radiative transfer model suggests that, despite the absorption, both high-temperature and low-temperature OC result in negative top-of-atmosphere radiative forcing over a surface with an albedo of 0.19 and positive radiative forcing over bright surfaces. Unless absorption by real ambient aerosol is higher than that measured here, it probably affects global average clear-sky forcing very little, but could be important in energy balances over bright surfaces.

Light Absorption by Organic Carbon From Wood Combustion

Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/Vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene

. Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional–global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Nino event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs; grams of a compound per kilogram biomass burned) for up to  ∼  90 gases, including CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n  =  35), indicating essentially pure smoldering combustion, and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g kg−1) were carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision of the EFs for CO2 (−8 %), CH4 (−55 %), NH3 (−86 %), CO (+39 %), and other gases compared with widely used recommendations for tropical peat fires based on a lab study of a single sample published in 2003. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) are important air toxics and aerosol precursors and were emitted in total at 1.5 ± 0.6 g kg−1. Formaldehyde is probably the air toxic gas most likely to cause local exposures that exceed recommended levels. The field results from Kalimantan were in reasonable agreement with recent lab measurements of smoldering Kalimantan peat for “overlap species,” lending importance to the lab finding that burning peat produces large emissions of acetamide, acrolein, methylglyoxal, etc., which were not measurable in the field with the deployed equipment and implying value in continued similar efforts. The aerosol optical data measured include EFs for the scattering and absorption coefficients (EF Bscat and EF Babs, m2 kg−1 fuel burned) and the single scattering albedo (SSA) at 870 and 405 nm, as well as the absorption Angstrom exponents (AAE). By coupling the absorption and co-located trace gas and filter data we estimated black carbon (BC) EFs (g kg−1) and the mass absorption coefficient (MAC, m2 g−1) for the bulk organic carbon (OC) due to brown carbon (BrC). Consistent with the minimal flaming, the emissions of BC were negligible (0.0055 ± 0.0016 g kg−1). Aerosol absorption at 405 nm was  ∼  52 times larger than at 870 nm and BrC contributed  ∼  96 % of the absorption at 405 nm. Average AAE was 4.97 ± 0.65 (range, 4.29–6.23). The average SSA at 405 nm (0.974 ± 0.016) was marginally lower than the average SSA at 870 nm (0.998 ± 0.001). These data facilitate modeling climate-relevant aerosol optical properties across much of the UV/visible spectrum and the high AAE and lower SSA at 405 nm demonstrate the dominance of absorption by the organic aerosol. Comparing the Babs at 405 nm to the simultaneously measured OC mass on filters suggests a low MAC ( ∼  0.1) for the bulk OC, as expected for the low BC/OC ratio in the aerosol. The importance of pyrolysis (at lower MCE), as opposed to glowing (at higher MCE), in producing BrC is seen in the increase of AAE with lower MCE (r2 =  0.65).

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Field measurements of trace gases and aerosols emitted by peat fires in Central Kalimantan, Indonesia, during the 2015 El Niño

This study presents the first measurement of Hg stable isotope fractionation during gas-phase oxidation of Hg0 vapor by halogen atoms (Cl•, Br•) in the laboratory at 750 ± 1 Torr and 298 ± 3 K. Using a relative rate technique, the rate coefficients for Hg0+Cl• and Hg0+Br• reactions are determined to be (1.8 ± 0.5) × 10–11 and (1.6 ± 0.8) × 10–12 cm3 molecule–1 s–1, respectively. Results show that heavier isotopes are preferentially enriched in the remaining Hg0 during Cl• initiated oxidation, whereas being enriched in the product during oxidation by Br•. The fractionation factors for 202Hg/198Hg during the Cl• and Br• initiated oxidations are α202/198 = 0.99941 ± 0.00006 (2σ) and 1.00074 ± 0.00014 (2σ), respectively. A Δ199Hg/Δ201Hg ratio of 1.64 ± 0.30 (2σ) during oxidation of Hg0 by Br atoms suggests that Hg-MIF is introduced by the nuclear volume effect (NVE). In contrast, the Hg0 + Cl• reaction produces a Δ199Hg/Δ201Hg-slope of 1.89 ± 0.18 (2σ), which in addition to a high degree of odd-mass-number is...

Mass-Dependent and -Independent Fractionation of Mercury Isotope during Gas-Phase Oxidation of Elemental Mercury Vapor by Atomic Cl and Br.

. Secondary organic material (SOM) produced by the oxidation of anthropogenic volatile organic compounds can be light-absorbing (i.e., brown carbon). Spectral data of the optical properties, however, are scarce. The present study obtained the continuous spectra of the real and imaginary refractive indices (m = n-i k) in the ultraviolet (UV)-to-visible region using spectroscopic ellipsometry for n and UV–visible spectrometry for k. Several different types of SOM were produced in an oxidation flow reactor by photooxidation of toluene and m-xylene for variable concentrations of nitrogen oxides (NOx). The results show that the k values of the anthropogenically derived material were at least 10 times greater than those of the biogenically derived material. The presence of NOx was associated with the production of organonitrogen compounds, such as nitro-aromatics and organonitrates, which enhanced light absorption. Compared with the SOM derived from m-xylene, the toluene-derived SOM had larger k values, as well as a greater NOx-induced enhancement, suggesting different brown-carbon-forming potentials of different aromatic precursor compounds. The results imply that anthropogenic SOM produced around urban environments can have an important influence on ultraviolet irradiance, which might consequently influence photochemical cycles of urban pollution.

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Ultraviolet and visible complex refractive indices of secondary organic material produced by photooxidation of the aromatic compounds toluene and m -xylene

Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons

/pdf/optical-properties-of-secondary-organic-aerosols-generated-4iie8ivc2g.pdf

Secondary organic aerosol (SOA) plays a pivotal role in visibility and radiative forcing, both of which are intrinsically linked to the refractive index (RI). While previous studies have focused on the RI of SOA from traditional formation processes, the effect of multiphase reactions on the RI has not been considered. Here, we investigate the effects of multiphase processes on the RI and light-extinction of m-xylene-derived SOA, a common type of anthropogenic SOA. We find that multiphase reactions in the presence of liquid water lead to the formation of oligomers from intermediate products such as glyoxal and methylglyoxal, resulting in a large enhancement in the RI and light-scattering of this SOA. These reactions will result in increases in light-scattering efficiency and direct radiative forcing of approximately 20%–90%. These findings improve our understanding of SOA optical properties and have significant implications for evaluating the impacts of SOA on the rapid formation of regional haze, global r...

Enhanced Light Scattering of Secondary Organic Aerosols by Multiphase Reactions

The formation of secondary organic aerosols (SOAs) contains partitioning processes of the oxidation products between the gas and particle phases, which could change the particle-phase composition when particles grow. However, the effects of these processes on the optical properties of SOA remain poorly understood. In this study, we performed smog chamber experiments to investigate the effects of gas-particle partitioning (GPP) on the refractive index (RI) and chemical composition of the m-xylene SOA. Here, we show that the GPP processes, as organic mass increases, can increase the proportions of semivolatile and intermediate-volatility organic compounds (SVOCs and IVOCs) in the particle phase and result in the decrease of SOA RI real part for 0.09 ± 0.02 (without seeds) and 0.15 ± 0.02 (with seeds). This indicates that the SOA optical properties are closely related to the total organic mass and molecular-level composition. In addition, the presence of inorganic seeds promotes the GPP to the particle phase...

Jiangjun Li

Papers

Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons

Enhanced Light Scattering of Secondary Organic Aerosols by Multiphase Reactions

Effects of Gas-Particle Partitioning on Refractive Index and Chemical Composition of m-Xylene Secondary Organic Aerosol