skip to main content

Title: Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels
Abstract. The chemical complexity of biomass burning organic aerosol (BBOA) greatlyincreases with photochemical aging in the atmosphere, necessitatingcontrolled laboratory studies to inform field observations. In theseexperiments, BBOA from American white oak (Quercus alba) leaf andheartwood samples was generated in a custom-built emissions and combustionchamber and photochemically aged in a potential aerosol mass (PAM) flowreactor. A thermal desorption aerosol gas chromatograph (TAG) was used inparallel with a high-resolution time-of-flight aerosol mass spectrometer(AMS) to analyze BBOA chemical composition at different levels ofphotochemical aging. Individual compounds were identified and integrated toobtain relative decay rates for key molecules. A recently developedchromatogram binning positive matrix factorization (PMF) technique was usedto obtain mass spectral profiles for factors in TAG BBOA chromatograms,improving analysis efficiency and providing a more complete determination ofunresolved complex mixture (UCM) components. Additionally, the recentlycharacterized TAG decomposition window was used to track molecular fragmentscreated by the decomposition of thermally labile BBOA during sampledesorption. We demonstrate that although most primary (freshly emitted) BBOAcompounds deplete with photochemical aging, certain components eluting withinthe TAG thermal decomposition window are instead enhanced. Specifically, theincreasing trend in the decomposition m∕z 44 signal (CO2+)indicates formation of secondary organic aerosol (SOA) in the PAM reactor.Sources of m∕z 60 (C2H4O2+), typically attributed tofreshly emitted BBOA in AMS field measurements, were also investigated. Fromthe TAG chemical speciation and decomposition window data, we observed adecrease in m∕z 60 with photochemical aging due to the decay ofanhydrosugars (including levoglucosan) and other compounds, as well as anincrease in m∕z 60 due to the formation of thermally labile organic acidswithin the PAM reactor, which decompose during TAG sample desorption. Whenaging both types of BBOA (leaf and heartwood), the AMS data exhibit acombination of these two contributing effects, causing limited change to theoverall m∕z 60 signal. Our observations demonstrate the importance ofchemically speciated data in fully understanding bulk aerosol measurementsprovided by the AMS in both laboratory and field studies.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ;
Date Published:
Journal Name:
Atmospheric Chemistry and Physics
Page Range / eLocation ID:
2199 to 2224
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. null (Ed.)
    Abstract. An accurate measurement of the optical properties of aerosol is critical for quantifying the effect of aerosol on climate. Uncertainties persist and results of measurements vary significantly. Biomass burning (BB) aerosol has been extensively studied through both field and laboratory environments for North American fuels to understand the changes in opticaland chemical properties as a function of aging. There is a need for a widersampling of fuels from different regions of the world for laboratory studies. This work represents the first such study of the optical andchemical properties of wood fuel samples commonly used for domestic purposes ineast Africa. In general, combustion temperature or modified combustionefficiency (MCE) plays a major role in the optical properties of the emitted aerosol. For fuels combusted with MCE of 0.974±0.015, which is referred to as flaming-dominated combustion, the single-scattering albedo (SSA) values were in the range of 0.287 to 0.439, while for fuels combusted with MCE of 0.878±0.008, which is referred to as smoldering-dominated combustion, the SSA values were in the range of 0.66 to 0.769. There is a clear but very small dependence of SSA on fuel type. A significant increase in the scattering and extinction cross section (with no significant change inabsorption cross section) was observed, indicating the occurrence of chemistry, even during dark aging for smoldering-dominated combustion. Thisfact cannot be explained by heterogeneous oxidation in the particle phase,and we hypothesize that secondary organic aerosol formation is potentiallyhappening during dark aging. After 12 h of photochemical aging, BB aerosolbecomes highly scattering with SSA values above 0.9, which can be attributedto oxidation in the chamber. Aging studies of aerosol from flaming-dominatedcombustion were inconclusive due to the very low aerosol number concentration. We also attempted to simulate polluted urban environments byinjecting volatile organic compounds (VOCs) and BB aerosol into the chamber, but no distinct difference was observed when compared to photochemical aging in the absence of VOCs. 
    more » « less
  3. null (Ed.)
    Abstract. We present a rapid method for apportioning the sources of atmospheric organic aerosol composition measured by gas chromatography–mass spectrometry methods. Here, we specifically apply this new analysis method to data acquired on a thermal desorption aerosol gas chromatograph (TAG) system. Gas chromatograms are divided by retention time into evenly spaced bins, within which the mass spectra are summed. A previous chromatogram binning method was introduced for the purpose of chromatogram structure deconvolution (e.g., major compound classes) (Zhang et al., 2014). Here we extend the method development for the specific purpose of determining aerosol samples' sources. Chromatogram bins are arranged into an input data matrix for positive matrix factorization (PMF), where the sample number is the row dimension and the mass-spectra-resolved eluting time intervals (bins) are the column dimension. Then two-dimensional PMF can effectively do three-dimensional factorization on the three-dimensional TAG mass spectra data. The retention time shift of the chromatogram is corrected by applying the median values of the different peaks' shifts. Bin width affects chemical resolution but does not affect PMF retrieval of the sources' time variations for low-factor solutions. A bin width smaller than the maximum retention shift among all samples requires retention time shift correction. A six-factor PMF comparison among aerosol mass spectrometry (AMS), TAG binning, and conventional TAG compound integration methods shows that the TAG binning method performs similarly to the integration method. However, the new binning method incorporates the entirety of the data set and requires significantly less pre-processing of the data than conventional single compound identification and integration. In addition, while a fraction of the most oxygenated aerosol does not elute through an underivatized TAG analysis, the TAG binning method does have the ability to achieve molecular level resolution on other bulk aerosol components commonly observed by the AMS. 
    more » « less
  4. null (Ed.)
    Guaiacyl acetone (GA) is a phenolic carbonyl emitted in significant quantities by wood combustion that undergoes rapid aqueous-phase oxidation to produce aqueous secondary organic aerosol (aqSOA). We investigate the photosensitized oxidation of GA by an organic triplet excited state (3C*) and the formation and aging of the resulting aqSOA in wood smoke-influenced fog/cloud water. The chemical transformations of the aqSOA were characterized in situ using a high-resolution time-of-flight aerosol mass spectrometer. Additionally, aqSOA samples collected over different time periods were analyzed using high-performance liquid chromatography coupled with a photodiode array detector and a high-resolution Orbitrap mass spectrometer (HPLC-PDA-HRMS) to provide details on the molecular composition and optical properties of brown carbon (BrC) chromophores. Our results show efficient formation of aqSOA from GA, with an average mass yield around 80%. The composition and BrC properties of the aqSOA changed significantly over the course of reaction. Three generations of aqSOA products were identified via Positive Matrix Factorization analysis of the AMS data. Oligomerization and functionalization dominated the production of the first-generation aqSOA, whereas fragmentation and ring-opening reactions controlled the formation of more oxidized second- and third-generation products. Significant formation of BrC was observed in the early stages of the photoreaction, while organic acids were produced throughout the experiment. High-molecular-weight molecules (m/z > 180) with high aromaticity were identified via HPLC-PDA-HRMS and were found to account for a majority of the UV-vis absorption of the aqSOA. 
    more » « less
  5. Isoprene (C5H8) is the largest non-methane volatile organic compound emitted into the atmosphere. Isoprene reacts rapidly with ambient hydroxyl radicals (OH) and subsequent addition of O2 results in the formation alkyl peroxy (RO2) radicals. The fate of the initially formed RO2 radicals has been the focus of continuing theoretical and experimental research. Under pristine conditions where bimolecular reactions of RO2 are limited, the thermodynamically favored RO2 undergoes an intramolecular H-shift followed by reaction with O2 and elimination of HO2 to yield 4-hydroperoxy aldehyde (4-HPALD, C5H8O3), predicted to account for up to 13% of first-generation isoprene photochemical oxidation products. Mass spectrometric evidence has been reported for 4-HPALD, but lack of an authentic standard has precluded definitive confirmation of both the structure of 4-HPALD and its origin as a first-generation product of OH oxidation of isoprene. We report the synthesis and characterization of 4-HPALD and establish that it is a major product of isoprene oxidation. Synthetic 4-HPALD is isolated as the peroxyhemiacetal. As expected for the 4-hydroperoxy aldehyde, 1H NMR spectra show no evidence for equilibration with the carbonyl form, even in protic solvents, and gas-phase chemical analysis by CIMS also shows only a single form. OH oxidation of isoprene in an oxidation flow reactor coupled to an ion mobility source with an HR-CIMS detector unequivocally demonstrates 4-HPALD (and likely also 1-HPALD) as isoprene oxidation products. Although HPALDs have been discounted as significant contributors to SOA, oxidation of 4-HPALD in a potential aerosol mass (PAM) reactor in the presence of ozone and OH indicates 4-HPALD rapidly undergoes autooxidation reactions forming low-volatility particulate products. We have confirmed highly oxygenated compounds with compositions C5H8O6 and C5H10O6 likely from OH oxidation, and C5H10O7 and C5H10O8 compounds likely products of ozonolysis. The PAM oxidation experiment further demonstrates that the highly oxygenated, low-volatility products efficiently nucleate particles. 
    more » « less