Abstract. To better understand the effects of wildfires on air quality andclimate, it is important to assess the occurrence of chromophoric compoundsin smoke and characterize their optical properties. This study explores themolecular composition of light-absorbing organic aerosol, or brown carbon(BrC), sampled at the Missoula Fire Sciences laboratory as a part of theFIREX Fall 2016 lab intensive. A total of 12 biomass fuels from different planttypes were tested, including gymnosperm (coniferous) and angiosperm(flowering) plants and different ecosystem components such as duff, litter,and canopy. Emitted biomass burning organic aerosol (BBOA) particles werecollected onto Teflon filters and analyzed offline using high-performanceliquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer(HPLC–PDA–HRMS). Separated BrC chromophores were classified by theirretention times, absorption spectra, integrated absorbance in the near-UVand visible spectral range (300–700 nm), and chemical formulas from theaccurate m∕z measurements. BrC chromophores were grouped into the followingclasses and subclasses: lignin-derived products, which include lignin pyrolysisproducts; distillation products, which include coumarins and flavonoids;nitroaromatics; and polycyclic aromatic hydrocarbons (PAHs). The observedclasses and subclasses were common across most fuel types, although specific BrCchromophores varied based on plant type (gymnosperm or angiosperm) andecosystem component(s) burned. To study the stability of the observed BrCcompounds with respect to photodegradation, BBOA particle samples wereirradiated directly on filters with near UV (300–400 nm) radiation, followedby extraction and HPLC–PDA–HRMS analysis. Lifetimes of individual BrCchromophores depended on the fuel type and the corresponding combustioncondition. Lignin-derived and flavonoid classes of BrC generally hadthe longest lifetimes with respect to UV photodegradation. Moreover,lifetimes for the same type of BrC chromophores varied depending on biomassfuel and combustion conditions. While individual BrC chromophoresdisappeared on a timescale of several days, the overall light absorption bythe sample persisted longer, presumably because the condensed-phasephotochemical processes converted one set of chromophores into anotherwithout complete photobleaching or from undetected BrC chromophores thatphotobleached more slowly. To model the effect of BrC on climate, it isimportant to understand the change in the overall absorption coefficientwith time. We measured the equivalent atmospheric lifetimes of the overallBrC absorption coefficient, which ranged from 10 to 41 d, with subalpinefir having the shortest lifetime and conifer canopies, i.e., juniper, havingthe longest lifetime. BrC emitted from biomass fuel loads encompassingmultiple ecosystem components (litter, shrub, canopy) had absorptionlifetimes on the lower end of the range. These results indicate thatphotobleaching of BBOA by condensed-phase photochemistry isrelatively slow. Competing chemical aging mechanisms, such as heterogeneousoxidation by OH, may be more important for controlling the rate of BrCphotobleaching in BBOA.
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Effects of the sample matrix on the photobleaching and photodegradation of toluene-derived secondary organic aerosol compounds
Abstract. Secondary organic aerosol (SOA) generated from the photooxidationof aromatic compounds in the presence of oxides of nitrogen (NOx) isknown to efficiently absorb ultraviolet and visible radiation. With exposureto sunlight, the photodegradation of chromophoric compounds in the SOAcauses this type of SOA to slowly photobleach. These photodegradationreactions may occur in cloud droplets, which are characterized by lowconcentrations of solutes, or in aerosol particles, which can have highlyviscous organic phases and aqueous phases with high concentrations ofinorganic salts. To investigate the effects of the surrounding matrix on therates and mechanisms of photodegradation of SOA compounds, SOA was preparedin a smog chamber by photooxidation of toluene in the presence of NOx.The collected SOA was photolyzed for up to 24 h using near-UV radiation(300–400 nm) from a xenon arc lamp under different conditions: directly onthe filter, dissolved in pure water, and dissolved in 1 M ammonium sulfate.The SOA mass absorption coefficient was measured as a function ofirradiation time to determine photobleaching rates. Electrospray ionizationhigh-resolution mass spectrometry coupled to liquid chromatographyseparation was used to observe changes in SOA composition resulting from theirradiation. The rate of decrease in SOA mass absorption coefficient due tophotobleaching was the fastest in water, with the presence of 1 M ammoniumsulfate modestly slowing down the photobleaching. By contrast,photobleaching directly on the filter was slower. The high-resolutionmass spectrometry analysis revealed an efficient photodegradation ofnitrophenol compounds on the filter but not in the aqueous phases, withrelatively little change observed in the composition of the SOA irradiatedin water or 1 M ammonium sulfate despite faster photobleaching than in theon-filter samples. This suggests that photodegradation of nitrophenolscontributes much more significantly to photobleaching in the organic phasethan in the aqueous phase. We conclude that the SOA absorption coefficientlifetime with respect to photobleaching and lifetimes of individualchromophores in SOA with respect to photodegradation will depend strongly onthe sample matrix in which SOA compounds are exposed to sunlight.
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- NSF-PAR ID:
- 10355000
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 22
- Issue:
- 15
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 10155 to 10171
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/acp-22-10155-2022
