Development of a liquid chromatographic method based on ultraviolet–visible and electrospray ionization mass spectrometric detection for the identification of nitrocatechols and related tracers in biomass burning atmospheric organic aerosol

Kitanovski, Zoran; Grgić, Irena; Yasmeen, Farhat; Claeys, Magda; Čusak, Alen

doi:10.1002/rcm.6170

Cited by 74 publications

(84 citation statements)

References 37 publications

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“…Thus, the BrC chromophore at RT = 15 min is most likely 4-nitrocatechol. 52 We note that more detailed structural characterization of BrC chromophores using, for example, tandem mass spectrometry and comparison with reference standards, 37 could be possible but is outside the scope of this study.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

Lin

Aiona

Liu

et al. 2016

Environ. Sci. Technol.

290

372

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Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly emitted biomass burning organic aerosol (BBOA) samples collected during test burns of sawgrass, peat, ponderosa pine, and black spruce. We demonstrate that both the BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as source-specific markers of BrC. On average, ∼50% of the light absorption in the solvent-extractable fraction of BBOA can be attributed to a limited number of strong BrC chromophores. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of ∼16 h. A “molecular corridor” analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low saturation mass concentration (<1 μg m–3) and will be retained in the particle phase under atmospherically relevant conditions.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

Lin

Aiona

Liu

et al. 2016

Environ. Sci. Technol.

290

372

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“…S2). The presence of NO x may lead to the formation of nitrogen-containing aromatic compounds during aerosol aging (Kahnt et al, 2013;Kitanovski et al, 2012). These compounds can absorb in the 450-550 nm range (J. and, therefore, can cause an absorbance increase in this spectral range.…”

Section: Absorbance Of Polar and Non-polar Fractionsmentioning

confidence: 99%

Light absorption by polar and non-polar aerosol compounds from laboratory biomass combustion

et al. 2018

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Abstract. Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly lightabsorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction -brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while the non-polar BrC fraction has been largely ignored. In the present study, the light absorption properties of polar and non-polar fractions of fresh and aged BB emissions were examined to estimate the contribution of differentpolarity organic compounds to the light absorption properties of BB aerosols.In our experiments, four globally and regionally important fuels were burned under flaming and smoldering conditions in the Desert Research Institute (DRI) combustion chamber. To mimic atmospheric oxidation processes (5-7 days), BB emissions were aged using an oxidation flow reactor (OFR). Fresh and OFR-aged BB aerosols were collected on filters and extracted with water and hexane to study absorption properties of polar and non-polar organic species. Results of spectrophotometric measurements (absorption weighted by the solar spectrum and normalized to mass of fuel consumed) over the 190 to 900 nm wavelength range showed that the non-polar (hexane-soluble) fraction is 2-3 times more absorbing than the polar (water-soluble) fraction. However, for emissions from fuels that undergo flaming combustion, an increased absorbance was observed for the water extracts of oxidized/aged emissions while the absorption of the hexane extracts was lower for the aged emissions for the same type of fuels. Absorption Ångström exponent (AAE) values, computed based on absorbance values from spectrophotometer measurements, were changed with aging and the nature of this change was fuel dependent. The light absorption by humic-like substances (HULIS) was found to be higher in fuels characteristic of the southwestern USA. The absorption of the HULIS fraction was lower for OFR-aged BB emissions. Comparison of the light absorption properties of different-polarity extracts (water, hexane, HULIS) provides insight into the chemical nature of BB BrC and its transformation during oxidation processes.

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“…2). The presence of NO x may lead to the formation of nitrogen-containing aromatic compounds during aerosol aging (Kahnt et al, 2013;Kitanovski et al, 2012). These compounds can absorb in the 450 -550 nm range (Liu et al, 2016b) and therefore, can cause an absorbance increase in this spectral range.…”

Section: Absorbance Of Polar and Non-polar Fractionsmentioning

confidence: 99%

Light absorption by polar and non-polar aerosol compounds from laboratory biomass combustion

Sengupta¹,

Samburova²,

Bhattarai³

et al. 2018

Preprint

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Abstract. Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of black carbon (BC) and organic carbon (OC) with its light-absorbing fraction -brown carbon (BrC). 10There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while the non-polar BrC fraction has been largely ignored. In the present study, 15 the light absorption properties of polar and non-polar fractions of fresh and aged BB emissions were examined to estimate the contribution of different-polarity organic compounds to the light absorption properties of BB aerosols.In our experiments, four globally and regionally important fuels were burned under flaming and smoldering conditions in DRI's combustion chamber. To mimic atmospheric oxidation processes (5-7 20 days), BB emissions were aged using an oxidation flow reactor (OFR). Fresh and OFR-aged BB aerosols were collected on filters and extracted with water and hexane to study absorption properties of polar and non-polar organic species. Spectrophotometric measurements over the 190 to 900 nm wavelength range showed that the non-polar (hexane-soluble) fraction is 2-3 times more absorbing than the polar (water-soluble) fraction. However, an increased absorbance was observed for the water 25 extracts of oxidized/aged emissions while the absorption of the hexane extracts was lower for the aged emissions. Comparing the absorption Ångström Exponent (AAE) values, we observed changes in the light absorption properties of BB aerosols with aging that was dependent on the fuel types. The light Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2018-161 Manuscript under review for journal Atmos. Chem. Phys.

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Development of a liquid chromatographic method based on ultraviolet–visible and electrospray ionization mass spectrometric detection for the identification of nitrocatechols and related tracers in biomass burning atmospheric organic aerosol

Cited by 74 publications

References 37 publications

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

Light absorption by polar and non-polar aerosol compounds from laboratory biomass combustion

Light absorption by polar and non-polar aerosol compounds from laboratory biomass combustion

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