Biomass burning organic aerosol (BBOA) is one of the largest sources of organics in the atmosphere. Mineral dust and biomass burning smoke frequently co-exist in the same atmospheric environment. Common biomass burning compounds, such as dihydroxybenzenes and their derivatives, are known to produce light-absorbing, water-insoluble polymeric particles upon reaction with soluble Fe( iii ) under conditions characteristic of aerosol liquid water. However, such reactions have not been tested in realistic mixtures of BBOA compounds. In this study, model organic aerosol (OA), meant to replicate BBOA from smoldering fires, was generated through the pyrolysis of Canary Island pine needles in a tube furnace at 300, 400, 500, 600, 700, and 800 °C in nitrogen gas, and the water-soluble fractions were reacted with iron chloride under dark, acidic conditions. We utilized spectrophotometry to monitor the reaction progress. For OA samples produced at lower temperatures (300 and 400 °C), particles (P300 and P400) formed in solution, were syringe filtered, and extracted in organic solvents. Analysis was conducted with ultrahigh pressure liquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer (UHPLC-PDA-HRMS). For OA samples formed at higher pyrolysis temperatures (500–800 °C), water-insoluble, black particles (P500–800) formed in solution. In contrast to P300 and P400, P500–800 were not soluble in common solvents. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM) were used to image P600 and determine bulk elemental composition. Electron microscopy revealed that P600 had fractal morphology, reminiscent of soot particles, and contained no detectable iron. These results suggest that light-absorbing aerosol particles can be produced from Fe( iii )-catalyzed reactions in aging BBOA plumes produced from smoldering combustion in the absence of any photochemistry. This result has important implications for understanding the direct and indirect effects of aged BBOA on climate.
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Relationship between the molecular composition, visible light absorption, and health-related properties of smoldering woodsmoke aerosols
Abstract. Organic aerosols generated from the smoldering combustion of woodcritically impact air quality and health for billions of people worldwide;yet, the links between the chemical components and the optical or biologicaleffects of woodsmoke aerosol (WSA) are still poorly understood. In thiswork, an untargeted analysis of the molecular composition of smoldering WSA,generated in a controlled environment from nine types of heartwood fuels(African mahogany, birch, cherry, maple, pine, poplar, red oak, redwood, andwalnut), identified several hundred compounds using gas chromatography massspectrometry (GC-MS) and nano-electrospray high-resolution mass spectrometry(HRMS) with tandem multistage mass spectrometry (MSn). The effects ofWSA on cell toxicity as well as gene expression dependent on the aryl hydrocarbon receptor (AhR) and estrogen receptor(ER) were characterized with cellular assays, andthe visible mass absorption coefficients (MACvis) of WSA were measuredwith ultraviolet–visible spectroscopy. The WSAs studied in this work have significantlevels of biological and toxicological activity, with exposure levels inboth an outdoor and indoor environment similar to or greater than those ofother toxicants. A correlation between the HRMS molecular composition andaerosol properties found that phenolic compounds from the oxidativedecomposition of lignin are the main drivers of aerosol effects, while thecellulose decomposition products play a secondary role; e.g., levoglucosanis anticorrelated with multiple effects. Polycyclic aromatic hydrocarbons(PAHs) are not expected to form at the combustion temperature in this work,nor were they observed above the detection limit; thus, biological and opticalproperties of the smoldering WSA are not attributed to PAHs. Syringylcompounds tend to correlate with cell toxicity, while the more conjugatedmolecules (including several compounds assigned to dimers) have higher AhRactivity and MACvis. The negative correlation between cell toxicity andAhR activity suggests that the toxicity of smoldering WSA to cells is notmediated by the AhR. Both mass-normalized biological outcomes have astatistically significant dependence on the degree of combustion of thewood. In addition, our observations support the fact that the visible lightabsorption of WSA is at least partially due to charge transfer effects inaerosols, as previously suggested. Finally, MACvis has no correlationwith toxicity or receptor signaling, suggesting that key chromophores inthis work are not biologically active on the endpoints tested.
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- Award ID(s):
- 1656889
- NSF-PAR ID:
- 10152048
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 20
- Issue:
- 1
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 539 to 559
- 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-20-539-2020
