scholarly journals Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

2013 ◽  
Vol 13 (2) ◽  
pp. 3485-3532 ◽  
Author(s):  
L. D. Yee ◽  
K. E. Kautzman ◽  
C. L. Loza ◽  
K. A. Schilling ◽  
M. M. Coggon ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Semivolatile Organic Compounds ◽  
Aerosol Formation ◽  
Aerosol Mass Spectrometer ◽  
Chemical Mechanisms ◽  
Aerosol Mass ◽  
Volatile Products

Abstract. The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (<10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O:C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

scholarly journals Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

2013 ◽  
Vol 13 (16) ◽  
pp. 8019-8043 ◽  
Author(s):  
L. D. Yee ◽  
K. E. Kautzman ◽  
C. L. Loza ◽  
K. A. Schilling ◽  
M. M. Coggon ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Semivolatile Organic Compounds ◽  
Aerosol Formation ◽  
Aerosol Mass Spectrometer ◽  
Chemical Mechanisms ◽  
Aerosol Mass ◽  
Volatile Products

Abstract. The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (< 10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

scholarly journals Secondary organic aerosol formation from biomass burning emissions

2019 ◽  
Author(s):  
Christopher Y. Lim ◽  
David H. Hagan ◽  
Matthew M. Coggon ◽  
Abigail R. Koss ◽  
Kanako Sekimoto ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Total Concentration ◽  
Organic Aerosol ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Atmospheric Aging ◽  
Aerosol Mass ◽  
Photochemical Aging ◽  
Organic Gases

Abstract. Biomass burning is an important source of aerosol and trace gases to the atmosphere, but how these emissions change chemically during their lifetimes is not fully understood. As part of the Fire Influence on Regional and Global Environments Experiment (FIREX 2016), we investigated the effect of photochemical aging on biomass burning organic aerosol (BBOA), with a focus on fuels from the western United States. Emissions were sampled into a small (150 L) environmental chamber and photochemically aged via the addition of ozone and irradiation by 254 nm light. While some fraction of species undergoes photolysis, the vast majority of aging occurs via reaction with OH radicals, with total OH exposures corresponding to the equivalent of up to 10 days of atmospheric oxidation. For all fuels burned, large and rapid changes are seen in the ensemble chemical composition of BBOA, as measured by an aerosol mass spectrometer (AMS). Secondary organic aerosol (SOA) formation is seen for all aging experiments and continues to grow with increasing OH exposure, but the magnitude of the SOA formation is highly variable between experiments. This variability can be explained well by a combination of experiment-to-experiment differences in OH exposure and the total concentration of non-methane organic gases (NMOGs) in the chamber before oxidation, measured by PTR-ToF-MS (r2 values from 0.64 to 0.83). From this relationship, we calculate the fraction of carbon from biomass burning NMOGs that is converted to SOA as a function of equivalent atmospheric aging time, with carbon yields ranging from 24 ± 4 % after 6 hours to 56 ± 9 % after 4 days.

scholarly journals Secondary organic aerosol formation from reaction of tertiary amines with nitrate radical

2008 ◽  
Vol 8 (4) ◽  
pp. 16585-16608 ◽  
Author(s):  
M. E. Erupe ◽  
D. J. Price ◽  
P. J. Silva ◽  
Q. G. J. Malloy ◽  
L. Qi ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Nitrate Radical ◽  
Tertiary Amines ◽  
Aerosol Formation ◽  
Night Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Secondary Organic Aerosol Formation

Abstract. Secondary organic aerosol formation from the reaction of tertiary amines with nitrate radical was investigated in an indoor environmental chamber. Particle chemistry was monitored using a high resolution aerosol mass spectrometer while gas-phase species were detected using a proton transfer reaction mass spectrometer. Trimethylamine, triethylamine and tributylamine were studied. Results indicate that tributylamine forms the most aerosol mass followed by trimethylamine and triethylamine respectively. Spectra from the aerosol mass spectrometer indicate the formation of complex non-salt aerosol products. We propose a reaction mechanism that proceeds via abstraction of a proton by nitrate radical followed by RO2 chemistry. Rearrangement of the aminyl alkoxy radical through hydrogen shift leads to the formation of hydroxylated amides, which explain most of the higher mass ions in the mass spectra. These experiments show that oxidation of tertiary amines by nitrate radical may be an important night-time source of secondary organic aerosol.

scholarly journals Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

2015 ◽  
Vol 15 (20) ◽  
pp. 11807-11833 ◽  
Author(s):  
W. W. Hu ◽  
P. Campuzano-Jost ◽  
B. B. Palm ◽  
D. A. Day ◽  
A. M. Ortega ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Chemical Transport Model ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Multiple Field

Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

scholarly journals Secondary organic aerosol formation and primary organic aerosol oxidation from biomass-burning smoke in a flow reactor during FLAME-3

2013 ◽  
Vol 13 (22) ◽  
pp. 11551-11571 ◽  
Author(s):  
A. M. Ortega ◽  
D. A. Day ◽  
M. J. Cubison ◽  
W. H. Brune ◽  
D. Bon ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Biomass Burning ◽  
Flow Reactor ◽  
Organic Aerosol ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
Chemical Transformations ◽  
Aerosol Formation ◽  
Aerosol Mass ◽  
Smog Chambers

Abstract. We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp~3.9 × 1011 molecules cm−3 s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeded the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility species, and possibly of unidentified VOCs as SOA precursors in biomass burning smoke. Chemical transformations continued even after mass concentration stabilized. Changes in the biomass-burning tracer f60 ranged from substantially decreasing to remaining constant with increased aging. With increased OHexp, oxidation was always detected (as indicated by f44 and O/C). POA O/C ranged from 0.15 to 0.5, while aged OA O/C reached up to 0.87. The rate of oxidation and maximum O/C achieved differs for each biomass, and appears to increase with the initial O/C of the POA.

scholarly journals Aging of aerosols emitted from biomass burning in northern Australia

2016 ◽  
Author(s):  
Andelija Milic ◽  
Marc D. Mallet ◽  
Luke T. Cravigan ◽  
Joel Alroe ◽  
Zoran D. Ristovski ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Northern Territory ◽  
Dry Season ◽  
Research Station ◽  
Aerosol Formation ◽  
Chemical Signature ◽  
Aerosol Mass ◽  
Wide Range

Abstract. There is a lack of knowledge of how biomass burning aerosols in the tropics age, including those in the fire-prone Northern Territory in Australia. This paper reports chemical characterization and aging of aerosols monitored during the one month long SAFIRED (Savannah Fires in the Early Dry Season) field study, with an emphasis on chemical signature and aging of organic aerosols. The campaign took place in June 2014 during the early dry season when the surface measurement site, the Australian Tropical Atmospheric Research Station (ATARS), located in the Northern Territory, was heavily influenced by thousands of wild and prescribed bushfires. ATARS was equipped with a wide suite of instrumentation for gaseous and aerosol characterization. A compact time-of-flight aerosol mass spectrometer was deployed to monitor aerosol chemical composition. Approximately 80 % of submicron carbonaceous mass and 90 % of submicron non-refractory mass was composed of organic material. Ozone enhancement in biomass burning plumes indicated increased air mass photochemistry and increased organic aerosol and particle diameter with the aging parameter (f44) suggested secondary organic aerosol formation. Diversity of biomass burning emissions was illustrated through variability in chemical signature (e.g. wide range in f44, from 0.06 to 0.13) for five intense fire events. The background particulate loading was characterized using Positive Matrix Factorization (PMF). A PMF-resolved BBOA (biomass burning organic aerosol) factor comprised 24 % of the submicron non-refractory organic aerosol mass, confirming the significance of fire sources. A dominant PMF factor, OOA (oxygenated organic aerosol), made up 47 % of sampled aerosol fraction, illustrating the importance of aerosol aging in the Northern Territory. Biogenic IEPOX-SOA (isoprene epoxydiols-related secondary organic aerosol) was the third significant fraction of the background aerosol (28 %).

scholarly journals Secondary organic aerosol formation from idling gasoline passenger vehicle emissions investigated in a smog chamber

2013 ◽  
Vol 13 (12) ◽  
pp. 6101-6116 ◽  
Author(s):  
E. Z. Nordin ◽  
A. C. Eriksson ◽  
P. Roldin ◽  
P. T. Nilsson ◽  
J. E. Carlsson ◽  
...  
Keyword(s):  
Mass Spectrum ◽  
Mass Spectrometer ◽  
Urban Areas ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Smog Chamber ◽  
Aerosol Formation ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Gasoline Vehicles

Abstract. Gasoline vehicles have recently been pointed out as potentially the main source of anthropogenic secondary organic aerosol (SOA) in megacities. However, there is a lack of laboratory studies to systematically investigate SOA formation in real-world exhaust. In this study, SOA formation from pure aromatic precursors, idling and cold start gasoline exhaust from three passenger vehicles (EURO2–EURO4) were investigated with photo-oxidation experiments in a 6 m3 smog chamber. The experiments were carried out down to atmospherically relevant organic aerosol mass concentrations. The characterization instruments included a high-resolution aerosol mass spectrometer and a proton transfer mass spectrometer. It was found that gasoline exhaust readily forms SOA with a signature aerosol mass spectrum similar to the oxidized organic aerosol that commonly dominates the organic aerosol mass spectra downwind of urban areas. After a cumulative OH exposure of ~5 × 106 cm−3 h, the formed SOA was 1–2 orders of magnitude higher than the primary OA emissions. The SOA mass spectrum from a relevant mixture of traditional light aromatic precursors gave f43 (mass fraction at m/z = 43), approximately two times higher than to the gasoline SOA. However O : C and H : C ratios were similar for the two cases. Classical C6–C9 light aromatic precursors were responsible for up to 60% of the formed SOA, which is significantly higher than for diesel exhaust. Important candidates for additional precursors are higher-order aromatic compounds such as C10 and C11 light aromatics, naphthalene and methyl-naphthalenes. We conclude that approaches using only light aromatic precursors give an incomplete picture of the magnitude of SOA formation and the SOA composition from gasoline exhaust.

scholarly journals Effect of chemical structure on secondary organic aerosol formation from C<sub>12</sub> alkanes

2013 ◽  
Vol 13 (21) ◽  
pp. 11121-11140 ◽  
Author(s):  
L. D. Yee ◽  
J. S. Craven ◽  
C. L. Loza ◽  
K. A. Schilling ◽  
N. L. Ng ◽  
...  
Keyword(s):  
Chemical Structure ◽  
Secondary Organic Aerosol ◽  
Peroxy Radical ◽  
Organic Aerosol ◽  
Particle Phase ◽  
Aerosol Formation ◽  
Phase Measurements ◽  
Chemical Mechanisms ◽  
Volatile Products ◽  
Growth Reaction

Abstract. The secondary organic aerosol (SOA) formation from four C12 alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane) is studied in the Caltech Environmental Chamber under low-NOx conditions, in which the principal fate of the peroxy radical formed in the initial OH reaction is reaction with HO2. Simultaneous gas- and particle-phase measurements elucidate the effect of alkane structure on the chemical mechanisms underlying SOA growth. Reaction of branched structures leads to fragmentation and more volatile products, while cyclic structures are subject to faster oxidation and lead to less volatile products. Product identifications reveal that particle-phase reactions involving peroxyhemiacetal formation from several multifunctional hydroperoxide species are key components of initial SOA growth in all four systems. The continued chemical evolution of the particle-phase is structure-dependent, with 2-methylundecane SOA formation exhibiting the least extent of chemical processing and cyclododecane SOA achieving sustained growth with the greatest variety of chemical pathways. The extent of chemical development is not necessarily reflected in the oxygen to carbon (O : C) ratio of the aerosol as cyclododecane achieves the lowest O : C, just above 0.2, by the end of the experiment and hexylcyclohexane the highest, approaching 0.35.

scholarly journals Aerosol mass spectrometer constraint on the global secondary organic aerosol budget

2011 ◽  
Vol 11 (2) ◽  
pp. 5699-5755 ◽  
Author(s):  
D. V. Spracklen ◽  
J. L. Jimenez ◽  
K. S. Carslaw ◽  
D. R. Worsnop ◽  
M. J. Evans ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Anthropogenic Pollution ◽  
Organic Aerosol ◽  
Chemical Transport Model ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Global Mean

Abstract. The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a−1. We used a dataset of aerosol mass spectrometer (AMS) observations and a global chemical transport model including aerosol microphysics to produce top-down constraints on the SOA budget. We treated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. Organic aerosol observations from the IMPROVE network were used as an independent check of our optimised sources. The optimised model has a global SOA source of 140 ± 90 Tg (SOA) a−1 comprised of 13 ± 8 Tg (SOA) a−1 from biogenic, 100 ± 60 Tg (SOA) a−1 from anthropogenically controlled SOA, 23 ± 15 Tg (SOA) a−1 from conversion of primary organic aerosol (mostly from biomass burning) to SOA and an additional 3 ± 3 Tg (SOA) a−1 from biomass burning VOCs. Compared with previous estimates, our optimized model has a substantially larger SOA source in the Northern Hemisphere mid-latitudes. We used a dataset of 14C observations from rural locations to estimate that 10 Tg (SOA) a−1 (10%) of our anthropogenically controlled SOA is of urban/industrial origin, with 90 Tg (SOA) a−1 (90%) most likely due to an anthropogenic pollution enhancement of SOA from biogenic VOCs, almost an order-of-magnitude beyond what can be explained by current understanding. The urban/industrial SOA source is consistent with the 13 Tg a−1 estimated by de Gouw and Jimenez (2009), which was much larger than estimates from previous studies. The anthropogenically controlled SOA source results in a global mean aerosol direct effect of −0.26 ± 0.15 Wm−2 and global mean indirect (cloud albedo) effect of −0.6+0.24−0.14 Wm−2. The biogenic and biomass SOA sources are not well constrained due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional observations are needed in the tropics and the Southern Hemisphere.

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