scholarly journals Polar organic compounds in rural PM<sub>2.5</sub> aerosols from K-puszta, Hungary, during a 2003 summer field campaign: Sources and diel variations

2005 ◽  
Vol 5 (7) ◽  
pp. 1805-1814 ◽  
Author(s):  
A. C. Ion ◽  
R. Vermeylen ◽  
I. Kourtchev ◽  
J. Cafmeyer ◽  
X. Chi ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Malic Acid ◽  
Sampling Site ◽  
Photochemical Reactions ◽  
Oxidation Products ◽  
Forest Site ◽  
Supporting Evidence ◽  
Diel Pattern ◽  
Field Campaign ◽  
Photo Oxidation

Abstract. In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June-10 July 2003), a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. The major components detected at significant atmospheric concentrations were: (a) photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and 2-methylglyceric acid, (b) levoglucosan, a marker for biomass burning, (c) malic acid, an intermediate in the oxidation of unsaturated fatty acids, and (d) the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diel patterns with highest concentrations during day-time were observed for the 2-methyltetrols, which can be regarded as supporting evidence for their fast photochemical formation from locally emitted isoprene. In addition, a diel pattern with highest concentrations during day-time was observed for the fungal markers, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diel pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products during day-time, it can be concluded that rapid photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol (SOA) formation at K-puszta during summer.

scholarly journals Polar organic compounds in rural PM<sub>2.5</sub> aerosols from K-puszta, Hungary, during a 2003 summer field campaign: sources and diurnal variations

2005 ◽  
Vol 5 (2) ◽  
pp. 1863-1889 ◽  
Author(s):  
A. C. Ion ◽  
R. Vermeylen ◽  
I. Kourtchev ◽  
J. Cafmeyer ◽  
X. Chi ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Malic Acid ◽  
Photochemical Reactions ◽  
Oxidation Products ◽  
Forest Site ◽  
Diurnal Pattern ◽  
Field Campaign ◽  
Photo Oxidation ◽  
Isoprene Oxidation ◽  
Isoprene Oxidation Products

Abstract. In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June–10 July 2003), a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. Analysis was performed using gas chromatography/mass spectrometry (GC/MS) after suitable sample workup consisting of extraction with methanol and derivatisation into trimethylsilyl (TMS) derivatives. The major components detected at significant atmospheric concentrations were: (a) photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and 2-methylglyceric acid, (b) levoglucosan, a marker for biomass burning, (c) malic acid, an end-oxidation product of unsaturated fatty acids, and (d) the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diurnal patterns with highest concentrations during day-time were observed for the isoprene oxidation products, i.e., the 2-methyltetrols and 2-methylglyceric acid, which can be regarded as supporting evidence for their fast photochemical formation from their locally emitted precursor. In addition, a diurnal pattern with highest concentrations during day-time was observed for the fungal markers, arabitol and mannitol, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diurnal pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products, i.e., the 2-methyltetrols (28.5 ng m-3) and 2-methylglyceric acid (7.6 ng m-3), it can be concluded that rapid photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol (SOA) formation at K-puszta during summer.

scholarly journals OH reactivity and concentrations of Biogenic Volatile Organic Compounds in a Mediterranean forest of downy oak trees

2015 ◽  
Vol 15 (16) ◽  
pp. 22047-22095 ◽  
Author(s):  
N. Zannoni ◽  
V. Gros ◽  
M. Lanza ◽  
R. Sarda ◽  
B. Bonsang ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Degradation Products ◽  
Ambient Air ◽  
Oxidation Products ◽  
Deciduous Tree ◽  
Forest Site ◽  
Mediterranean Forests ◽  
Oak Trees ◽  
Volatile Organic

Abstract. Understanding the processes between the biosphere and the atmosphere is challenged by the difficulty to determine with enough accuracy the composition of the atmosphere. Total OH reactivity, which is defined as the total loss of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify indirectly the important reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites. Such results demonstrated the importance of OH reactivity for characterizing two of the major unknowns currently present associated to forests: the set of primary emissions from the canopy to the atmosphere and biogenic compounds oxidation pathways. Previous studies also highlighted the need to quantify OH reactivity and missing OH reactivity at more forested sites. Our study presents results of a field experiment conducted during late spring 2014 at the forest site at the Observatoire de Haute Provence, OHP, France. The forest is mainly composed of downy oak trees, a deciduous tree species characteristic of the Mediterranean region. We deployed the Comparative Reactivity Method and a set of state-of-the-art techniques such as Proton Transfer Reaction-Mass Spectrometry and Gas Chromatography to measure the total OH reactivity, the concentration of volatile organic compounds and main atmospheric constituents at the site. We sampled the air masses at two heights: 2 m, i.e. inside the canopy, and 10 m, i.e. above the canopy, where the mean canopy height is 5 m. We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long lived atmospheric compounds (up to 26 % during daytime). We determined that the daytime total measured reactivity equaled the calculated reactivity obtained from the concentrations of the compounds measured at the site. Hence, no significant missing reactivity is reported in this specific site, neither inside, nor above the canopy. However, during two nights we reported a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. Our results confirm the weak intra canopy oxidation, already suggested in a previous study focused on isoprene fluxes. They also demonstrate how helpful can be the OH reactivity as a tool to clearly characterize the suite of species present in the atmosphere. We show that our result of reactivity is among the highest reported in forests worldwide and stress the importance to quantify OH reactivity at more and diverse Mediterranean forests.

scholarly journals Biogenic and biomass burning organic aerosol in a boreal forest at Hyytiälä, Finland, during HUMPPA-COPEC 2010

2013 ◽  
Vol 13 (24) ◽  
pp. 12233-12256 ◽  
Author(s):  
A. L. Corrigan ◽  
L. M. Russell ◽  
S. Takahama ◽  
M. Äijälä ◽  
M. Ehn ◽  
...  
Keyword(s):  
Factor Analysis ◽  
Boreal Forest ◽  
Biomass Burning ◽  
Sampling Site ◽  
Organic Aerosol ◽  
Ftir Spectra ◽  
Oxidation Products ◽  
Forest Site ◽  
Submicron Aerosol ◽  
Aerosol Mass

Abstract. Submicron aerosol particles were collected during July and August 2010 in Hyytiälä, Finland, to determine the composition and sources of aerosol at that boreal forest site. Submicron particles were collected on Teflon filters and analyzed by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFGs). Positive matrix factorization (PMF) was applied to aerosol mass spectrometry (AMS) measurements and FTIR spectra to identify summertime sources of submicron aerosol mass at the sampling site. The two largest sources of organic mass (OM) in particles identified at Hyytiälä were (1) biogenic aerosol from surrounding local forest and (2) biomass burning aerosol, transported 4–5 days from large wildfires burning near Moscow, Russia, and northern Ukraine. The robustness of this apportionment is supported by the agreement of two independent analytical methods for organic measurements with three statistical techniques. FTIR factor analysis was more sensitive to the chemical differences between biogenic and biomass burning organic components, while AMS factor analysis had a higher time resolution that more clearly linked the temporal behavior of separate OM factors to that of different source tracers even though their fragment mass spectrum were similar. The greater chemical sensitivity of the FTIR is attributed to the nondestructive preparation and the functional group specificity of spectroscopy. The FTIR spectra show strong similarities among biogenic and biomass burning factors from different regions as well as with reference OM (namely olive tree burning organic aerosol and α-pinene chamber secondary organic aerosol (SOA)). The biogenic factor correlated strongly with temperature and oxidation products of biogenic volatile organic compounds (BVOCs), included more than half of the oxygenated OFGs (carbonyl groups at 29% and carboxylic acid groups at 22%), and represented 35% of the submicron OM. Compared to previous studies at Hyytiälä, the summertime biogenic OM is 1.5 to 3 times larger than springtime biogenic OM (0.64 μg m−3 and 0.4 μg m−3, measured in 2005 and 2007, respectively), even though it contributed only 35% of OM. The biomass burning factor contributed 25% of OM on average and up to 62% of OM during three periods of transported biomass burning emissions: 26–28 July, 29–30 July, and 8–9 August, with OFG consisting mostly of carbonyl (41%) and alcohol (25%) groups. The high summertime terrestrial biogenic OM (1.7 μg m−3) and the high biomass burning contributions (1.2 μg m−3) were likely due to the abnormally high temperatures that resulted in both stressed boreal forest conditions with high regional BVOC emissions and numerous wildfires in upwind regions.

scholarly journals Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project

2005 ◽  
Vol 5 (5) ◽  
pp. 8851-8877
Author(s):  
F. Cavalli ◽  
M. C. Facchini ◽  
S. Decesari ◽  
L. Emblico ◽  
M. Mircea ◽  
...  
Keyword(s):  
Total Mass ◽  
Chemical Properties ◽  
Particle Formation ◽  
Water Soluble ◽  
Oxidation Products ◽  
Forest Site ◽  
New Particle Formation ◽  
Anthropogenic Aerosol ◽  
Photo Oxidation ◽  
Mass Concentrations

Abstract. Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiälä, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred. A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 μg m−3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 μg m−3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto accumulation mode particles are responsible also for the growth of newly formed thermodynamically stable clusters, our finding allows one to postulate that, at the site, α-pinene photo-oxidation products (and probably also photo-oxidation products from other terpenes) are the most likely species to contribute to the growth of nanometer-sized particles.

scholarly journals Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

2014 ◽  
Vol 14 (23) ◽  
pp. 12781-12801 ◽  
Author(s):  
K. P. Wyche ◽  
A. C. Ryan ◽  
C. N. Hewitt ◽  
M. R. Alfarra ◽  
G. McFiggans ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Organic Aerosol ◽  
Reaction Chamber ◽  
Oxidation Products ◽  
Photo Oxidation ◽  
Tropical Plant ◽  
Aerosol Mass ◽  
Volatile Organic ◽  
Seed Aerosol

Abstract. Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65–89%, volatile organic compound-to-NOx or VOC / NOx ~3–9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques. Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26–39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast Asia. Moreover, in general the amount of aerosol mass produced from the emissions of the principally isoprene-emitting plants was less than would be expected from published single-VOC experiments, if co-emitted species were solely responsible for the final SOA mass. Interpretation of the results obtained from the fig data sets leaves room for a potential role for isoprene in inhibiting SOA formation under certain ambient atmospheric conditions, although instrumental and experimental constraints impose a level of caution in the interpretation of the results. Concomitant gas- and aerosol-phase composition measurements also provide a detailed overview of numerous key oxidation mechanisms at work within the systems studied, and their combined analysis provides insight into the nature of the SOA formed.

scholarly journals Aqueous-Phase Production of Secondary Organic Aerosols from Oxidation of Dibenzothiophene (DBT)

Atmosphere ◽  
2020 ◽  
Vol 11 (2) ◽  
pp. 151 ◽  
Author(s):  
Yu Liu ◽  
Junchen Lu ◽  
Yanfang Chen ◽  
Yue Liu ◽  
Zhaolian Ye ◽  
...  
Keyword(s):  
Hydroxyl Radical ◽  
Aqueous Phase ◽  
Reaction Pathway ◽  
Photochemical Reactions ◽  
Oxidation Products ◽  
Gas Phase Reactions ◽  
Photo Oxidation ◽  
Oxygenated Compounds ◽  
Direct Light ◽  
Triplet Excited States

Intermediate-volatility organic compounds (IVOCs) have been recognized as an important contributor to the secondary organic aerosol (SOA) formation via gas-phase reactions. However, it is unclear whether or not IVOCs-SOA can be produced in the aqueous phase. This work investigated aqueous oxidation of one model compound of IVOCs, dibenzothiophene (DBT). Results show that DBT can be degraded by both hydroxyl radical and the triplet excited states of organic light chromophores (3C*). Aqueous dark oxidation of DBT was also possible. SOA yields of 32% and 15% were found for hydroxyl radical (OH)-mediated photo-oxidation and dark oxidation, respectively. A continuous and significant increase of oxidation degree of SOA was observed during OH photo-oxidation, but not during the dark oxidation. Factor analyses revealed that there was a persistent production of highly oxygenated compounds from the less oxygenated species. OH-initiated photochemical reactions can also produce species with a relatively large light-absorbing ability, while such photo-enhancement due to direct light irradiation and 3C*-initiated oxidation could occur, but is much less important. In the future, studies on the second-order rate constants, molecular characterization of the oxidation products from this and other IVOCs precursors are needed to better understand the role of this reaction pathway in SOA budget, air quality and climate change.

scholarly journals Size-segregated aerosol chemical composition at a boreal site in southern Finland, during the QUEST project

2006 ◽  
Vol 6 (4) ◽  
pp. 993-1002 ◽  
Author(s):  
F. Cavalli ◽  
M. C. Facchini ◽  
S. Decesari ◽  
L. Emblico ◽  
M. Mircea ◽  
...  
Keyword(s):  
Total Mass ◽  
Chemical Properties ◽  
Particle Formation ◽  
Water Soluble ◽  
Oxidation Products ◽  
Forest Site ◽  
New Particle Formation ◽  
Anthropogenic Aerosol ◽  
Photo Oxidation ◽  
Mass Concentrations

Abstract. Size-segregated aerosol samples were collected during the QUEST field campaign at Hyytiälä, a boreal forest site in Southern Finland, during spring 2003. Aerosol samples were selectively collected during both particle formation events and periods in which no particle formation occurred. A comprehensive characterisation of the aerosol chemical properties (water-soluble inorganic and organic fraction) and an analysis of the relevant meteorological parameters revealed how aerosol chemistry and meteorology combine to determine a favorable "environment" for new particle formation. The results indicated that all events, typically favored during northerly air mass advection, were background aerosols (total mass concentrations range between 1.97 and 4.31 µg m-3), with an increasingly pronounced marine character as the northerly air flow arrived progressively from the west and, in contrast, with a moderate SO2-pollution influence as the air arrived from more easterly directions. Conversely, the non-event aerosol, transported from the south, exhibited the chemical features of European continental sites, with a marked increase in the concentrations of all major anthropogenic aerosol constituents. The higher non-event mass concentration (total mass concentrations range between 6.88 and 16.30 µg m-3) and, thus, a larger surface area, tended to suppress new particle formation, more efficiently depleting potential gaseous precursors for nucleation. The analysis of water-soluble organic compounds showed that clean nucleation episodes were dominated by aliphatic biogenic species, while non-events were characterised by a large abundance of anthropogenic oxygenated species. Interestingly, a significant content of α-pinene photo-oxidation products was observed in the events aerosol, accounting for, on average, 72% of their WSOC; while only moderate amounts of these species were found in the non-event aerosol. If the organic vapors condensing onto accumulation mode particles are responsible also for the growth of newly formed thermodynamically stable clusters, our finding allows one to postulate that, at the site, α-pinene photo-oxidation products (and probably also photo-oxidation products from other terpenes) are the most likely species to contribute to the growth of nanometer-sized particles.

scholarly journals Low-level isoprene observed during summertime at a forested mountaintop site in southern China: implications for strong regional atmospheric oxidative capacity

2018 ◽  
Author(s):  
Daocheng Gong ◽  
Hao Wang ◽  
Shenyang Zhang ◽  
Yu Wang ◽  
Shaw Liu ◽  
...  
Keyword(s):  
Air Pollution ◽  
Southern China ◽  
Sampling Site ◽  
Reaction Times ◽  
Oxidative Capacity ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Atmospheric Environment ◽  
Mountain Forest ◽  
Forest Site

Abstract. To investigate the atmospheric oxidizing capacity in certain polluted isoprene-rich environments, such as the forests surrounding megacities. Here we present online observations of isoprene and its first-stage oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) in summer 2016 at a remote, high-altitude mountain forest site (1690 m a.s.l.) to the north of the air-polluted Pearl River Delta (PRD) region in southern China. The observed isoprene level was found to be significantly lower in comparison with other forest sites either in China or around the world, although the sampling site was surrounded with subtropical evergreen broad-leaved trees which are strong isoprene emitters. Also, high (MVK+MACR)/isoprene ratio was observed. Based on the observations, we hypothesized that the lower isoprene levels in the study forest might be attributable to a strong atmospheric oxidative capacity in relation to the elevated regional complex air pollution. High daytime OH and nighttime NO3 radical concentrations estimated by using a photochemical box model incorporating Master Chemical Mechanism (PBM-MCM), as well as calculated short atmospheric reaction times of isoprene and long photochemical age, indicated that the isoprene was rapidly and fully oxidized at this aged atmospheric environment, which confirmed our hypothesis. The study suggests that the complex air pollution in the PRD region has significantly elevated the background atmospheric oxidative capacity of the adjacent forests, and most likely does would probably affect the regional air quality and ecological environment in the long term. The feedback of forest ecosystems to the increasing atmospheric oxidation capacity warrants further studies.

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