scholarly journals Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

2010 ◽  
Vol 10 (2) ◽  
pp. 2915-2943 ◽  
Author(s):  
Y. Sun ◽  
Q. Zhang ◽  
C. Anastasio ◽  
J. Sun
Keyword(s):  
Phenolic Compounds ◽  
High Resolution ◽  
Aromatic Ring ◽  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Photochemical Reactions ◽  
Oxidation Products ◽  
Formation Mechanisms

Abstract. Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) – can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatograph (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C–H/C) between −0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21–2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4–5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an ·OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C–C and C–O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or ·OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, ·OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C16H18O6+) and m/z 246 (C14H14O4+), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog processing. Our results indicate that cloud and fog processing of phenolic compounds, especially in areas with active biomass burning, might represent an important pathway for the formation of low-volatility and highly oxygenated organic species, which would remain in particle phase after fog/cloud evaporation and affect the hygroscopicity and radiative impacts of ambient OA.

scholarly journals Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

2010 ◽  
Vol 10 (10) ◽  
pp. 4809-4822 ◽  
Author(s):  
Y. L. Sun ◽  
Q. Zhang ◽  
C. Anastasio ◽  
J. Sun
Keyword(s):  
Phenolic Compounds ◽  
High Resolution ◽  
Aromatic Ring ◽  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Photochemical Reactions ◽  
Oxidation Products ◽  
Formation Mechanisms

Abstract. Recent work has shown that aqueous-phase reactions of phenolic compounds – phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) – can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatography system (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80–1.06 and carbon oxidation states (=2×O/C-H/C) between −0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21–2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4−5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C-C and C-O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C16H18O6+) and m/z 246 (C14H14O4+), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog processing. Our results indicate that cloud and fog processing of phenolic compounds, especially in areas with active biomass burning, might represent an important pathway for the formation of low-volatility and highly oxygenated organic species, which would remain in the particle phase after fog/cloud evaporation and affect the chemical and optical properties of atmospheric particles.

scholarly journals Secondary Organic Aerosol from Atmospheric Photooxidation of Indole

2017 ◽  
Author(s):  
Julia Montoya ◽  
Jeremy R. Horne ◽  
Mallory L. Hinks ◽  
Lauren T. Fleming ◽  
Veronique Perraud ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Air Quality ◽  
Chemical Composition ◽  
High Resolution ◽  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Scanning Mobility Particle Sizer ◽  
High Resolution Mass ◽  
Resolution Mass

Abstract. Indole is a heterocyclic compound emitted by various plant species under stressed conditions or during flowering events. The formation, optical properties, and chemical composition of secondary organic aerosol (SOA) formed by low-NOx photooxidation of indole were investigated. The SOA yield (1.1 ± 0.3) was estimated from measuring the particle mass concentration with a scanning mobility particle sizer (SMPS) and correcting it for the wall loss effects. The SOA particles were collected on filters and analysed offline with UV-Vis spectrophotometry to measure the mass absorption coefficient (MAC) of the bulk sample. The samples were visibly brown and had MAC values of ~7 m2/g at λ = 300 nm and ~2 m2/g at λ = 400 nm, comparable to strongly absorbing brown carbon emitted from biomass burning. The chemical composition of SOA was examined with several mass spectrometry methods. The direct analysis in real time mass spectrometry (DART-MS) and nanospray desorption electrospray high resolution mass spectrometry (nano-DESI-HRMS) were used to provide information about the overall distribution of SOA compounds. High performance liquid chromatography, coupled to photodiode array spectrophotometry and high resolution mass spectrometry (HPLC-PDA-HRMS) was used to identify chromophoric compounds. Indole derivatives, such as tryptanthrin, indirubin, indigo dye, and indoxyl red were found to contribute significantly to the visible absorption spectrum of indole SOA. The potential effect of indole SOA on air quality was explored with the airshed model, which found elevated concentrations of indole SOA during the afternoon hours contributing considerably to the total organic aerosol under selected scenarios. Because of its high MAC values, indole SOA can contribute to decreased visibility and poor air quality.

scholarly journals Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

2013 ◽  
Vol 13 (17) ◽  
pp. 8651-8667 ◽  
Author(s):  
Y. B. Lim ◽  
Y. Tan ◽  
B. J. Turpin
Keyword(s):  
Acetic Acid ◽  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Oxidation Products ◽  
Radical Reactions ◽  
Organic Radical ◽  
Oh Radical ◽  
Radical Oxidation

Abstract. Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10−6 − ~ 10−3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical–radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.

scholarly journals Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

2013 ◽  
Vol 13 (7) ◽  
pp. 18113-18141
Author(s):  
J. F. Hamilton ◽  
M. R. Alfarra ◽  
N. Robinson ◽  
M. W. Ward ◽  
A. C. Lewis ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Tropical Rainforest ◽  
Ion Trap ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ion Cyclotron Resonance ◽  
Aerosol Formation ◽  
Chemical Structures

Abstract. Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding the process of these transformations has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a South East Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high resolution aerosol mass spectrometry and fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyltetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products

2015 ◽  
Vol 120 (9) ◽  
pp. 1395-1407 ◽  
Author(s):  
Dana Aljawhary ◽  
Ran Zhao ◽  
Alex K.Y. Lee ◽  
Chen Wang ◽  
Jonathan P.D. Abbatt
Keyword(s):  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Photo Oxidation

scholarly journals Impact of anthropogenic and biogenic sources on the seasonal variation of the molecular composition of urban organic aerosols: a field and laboratory study using ultra-high resolution mass spectrometry

2018 ◽  
Author(s):  
Kaspar R. Daellenbach ◽  
Ivan Kourtchev ◽  
Alexander L. Vogel ◽  
Emily A. Bruns ◽  
Jianhui Jiang ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Molecular Composition ◽  
Wood Burning ◽  
High Resolution Mass ◽  
Alpine Valleys ◽  
Resolution Mass

Abstract. This study presents the molecular composition of OA using ultra-high resolution mass spectrometry (Orbitrap) at an urban site in Central Europe (Zurich, Switzerland). Specific source spectra were also analysed, including samples representative of wood burning emissions from Alpine valleys during wood burning pollution episodes and chamber investigations of wood smoke as well as samples from Hyytiälä strongly influenced by biogenic secondary organic aerosol. While samples collected during winter in Alpine valleys have a molecular composition remarkably similar to fresh laboratory wood burning emissions, winter samples from Zurich are influenced by more aged wood burning emissions. In addition, other organic aerosol emission or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiälä, predominantly impacted by oxygenated compounds with an H / C ratio of 1.5, indicating the importance of biogenic precursors for SOA formation at this location. We could explain the strong seasonality of the molecular composition at a typical European site by primary and aged wood burning emissions and biogenic secondary organic aerosol formation during winter and summer, respectively. Results presented here likely explain the seasonally rather constant predominance of non-fossil organic carbon at European locations.

scholarly journals Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

2013 ◽  
Vol 13 (22) ◽  
pp. 11295-11305 ◽  
Author(s):  
J. F. Hamilton ◽  
M. R. Alfarra ◽  
N. Robinson ◽  
M. W. Ward ◽  
A. C. Lewis ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Tropical Rainforest ◽  
Ion Trap ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ion Cyclotron Resonance ◽  
Aerosol Formation ◽  
Chemical Structures

Abstract. Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding these transformation processes has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a Southeast Asian tropical rainforest in Borneo were characterised using liquid chromatography–ion trap mass spectrometry, high-resolution aerosol mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyl tetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

scholarly journals Secondary organic aerosol in the global aerosol – chemical transport model Oslo CTM2

2007 ◽  
Vol 7 (21) ◽  
pp. 5675-5694 ◽  
Author(s):  
C. R. Hoyle ◽  
T. Berntsen ◽  
G. Myhre ◽  
I. S. A. Isaksen
Keyword(s):  
Ammonium Sulphate ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Chemical Transport ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Formation Mechanisms ◽  
Total Production ◽  
Chemical Transport Model ◽  
Sulphate Aerosol

Abstract. The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 69 Tg yr−1 by allowing semi-volatile species to partition to ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated. Allowing SOA to partition into ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to 9.4% of the total production. Total modelled organic aerosol (OA) values are found to represent a lower fraction of the measured values in winter (when primary organic aerosol (POA) is the dominant OA component) than in summer, which may be an indication that estimates of POA emissions are too low. Additionally, for measurement stations where the summer OA values are higher than in winter, the model generally underestimates the increase in summertime OA. In order to correctly model the observed increase in OA in summer, additional SOA sources or formation mechanisms may be necessary. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas, if the yield of condensible oxidation products for β-pinene is used for NO3 oxidation of all terpenes. Reducing the yield for α-pinene and limonene oxidation in line with recent measurements reduces the global fraction of SOA formed from NO3 oxidation products from 27% to about 21%. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.

scholarly journals Impact of anthropogenic and biogenic sources on the seasonal variation in the molecular composition of urban organic aerosols: a field and laboratory study using ultra-high-resolution mass spectrometry

2019 ◽  
Vol 19 (9) ◽  
pp. 5973-5991 ◽  
Author(s):  
Kaspar R. Daellenbach ◽  
Ivan Kourtchev ◽  
Alexander L. Vogel ◽  
Emily A. Bruns ◽  
Jianhui Jiang ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Carbon Number ◽  
Organic Aerosol ◽  
Molecular Composition ◽  
Wood Burning ◽  
Alpine Valleys ◽  
Resolution Mass

Abstract. This study presents the molecular composition of organic aerosol (OA) using ultra-high-resolution mass spectrometry (Orbitrap) at an urban site in Central Europe (Zurich, Switzerland). Specific source spectra were also analysed, including samples representative of wood-burning emissions from Alpine valleys during wood-burning pollution episodes and smog chamber investigations of woodsmoke, as well as samples from Hyytiälä, which were strongly influenced by biogenic secondary organic aerosol. While samples collected during winter in Alpine valleys have a molecular composition remarkably similar to fresh laboratory wood-burning emissions, winter samples from Zurich are influenced by more aged wood-burning emissions. In addition, other organic aerosol emissions or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiälä and are predominantly impacted by oxygenated compounds with an H∕C ratio of 1.5, indicating the importance of biogenic precursors for secondary organic aerosol (SOA) formation at this location (summertime Zurich – carbon number 7.6, O:C 0.7; Hyytiälä – carbon number 10.5, O:C 0.57). We could explain the strong seasonality of the molecular composition at a typical European site by primary and aged wood-burning emissions and biogenic secondary organic aerosol formation during winter and summer, respectively. Results presented here likely explain the rather constant seasonal predominance of non-fossil organic carbon at European locations.

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