scholarly journals Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-<i>E</i>-pentenal, 2-<i>E</i>-hexenal, and 3-<i>Z</i>-hexenal

2015 ◽  
Vol 15 (20) ◽  
pp. 29555-29590 ◽  
Author(s):  
M. S. Shalamzari ◽  
R. Vermeylen ◽  
F. Blockhuys ◽  
T. E. Kleindienst ◽  
M. Lewandowski ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Epoxy Group ◽  
Organic Aerosol ◽  
Green Leaf Volatiles ◽  
Green Leaf ◽  
Hydroxyl Group ◽  
Mechanical Wounding ◽  
Acid Sulfate ◽  
Chemical Structures ◽  
Unsaturated Aldehydes

Abstract. We show in the present study that the unsaturated aldehydes, 2-E-pentenal, 2-E-hexenal and 3-Z-hexenal, are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack), and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS) and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements) to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfoxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α, β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013). The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl group at the C-4 position. Evidence is also presented that the MW 214 positional isomer, 2-sulfooxy-3-hydroxypentanoic acid is unstable and decarboxylates, giving rise to 1-sulfooxy-2-hydroxybutane, a MW 170 organosulfate. Furthermore, evidence is obtained that lactic acid sulfate is generated from 2-E-pentenal.

scholarly journals Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-<i>E</i>-pentenal, 2-<i>E</i>-hexenal, and 3-<i>Z</i>-hexenal

2016 ◽  
Vol 16 (11) ◽  
pp. 7135-7148 ◽  
Author(s):  
Mohammad Safi Shalamzari ◽  
Reinhilde Vermeylen ◽  
Frank Blockhuys ◽  
Tadeusz E. Kleindienst ◽  
Michael Lewandowski ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Epoxy Group ◽  
Organic Aerosol ◽  
Green Leaf Volatiles ◽  
Green Leaf ◽  
Hydroxyl Group ◽  
Mechanical Wounding ◽  
Acid Sulfate ◽  
Chemical Structures ◽  
Unsaturated Aldehydes

Abstract. We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles (GLVs) 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack), and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS) and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements) to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfooxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α,β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013). The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl group at the C-4 position. Evidence is also presented that the MW 214 positional isomer, 2-sulfooxy-3-hydroxypentanoic acid, is unstable and decarboxylates, giving rise to 1-sulfooxy-2-hydroxybutane, a MW 170 organosulfate. Furthermore, evidence is obtained that lactic acid sulfate is generated from 2-E-pentenal. This chemistry could be important on a regional and local scale where GLV emissions such as from grasses and cereal crops are substantial.

scholarly journals Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

2009 ◽  
Vol 9 (1) ◽  
pp. 3921-3943
Author(s):  
J. F. Hamilton ◽  
A. C. Lewis ◽  
T. J. Carey ◽  
J. C. Wenger ◽  
E. Borrás i Garcia ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Chemical Species ◽  
Organic Aerosol ◽  
Green Leaf Volatiles ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
Green Leaf ◽  
Aerosol Formation ◽  
Leaf Volatiles

Abstract. Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr−1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

scholarly journals Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

2009 ◽  
Vol 9 (11) ◽  
pp. 3815-3823 ◽  
Author(s):  
J. F. Hamilton ◽  
A. C. Lewis ◽  
T. J. Carey ◽  
J. C. Wenger ◽  
E. Borrás i Garcia ◽  
...  
Keyword(s):  
First Generation ◽  
Secondary Organic Aerosol ◽  
Chemical Species ◽  
Organic Aerosol ◽  
Green Leaf Volatiles ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
Green Leaf ◽  
Aerosol Formation ◽  
Leaf Volatiles

Abstract. Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1–5 TgC yr−1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

Characterization of Polar Organosulfates in Secondary Organic Aerosol from the Green Leaf Volatile 3-Z-Hexenal

2014 ◽  
Vol 48 (21) ◽  
pp. 12671-12678 ◽  
Author(s):  
Mohammad Safi Shalamzari ◽  
Ariane Kahnt ◽  
Reinhilde Vermeylen ◽  
Tadeusz E. Kleindienst ◽  
Michael Lewandowski ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Green Leaf ◽  
Green Leaf Volatile

scholarly journals Role of aldehyde chemistry and NO<sub>x</sub> concentrations in secondary organic aerosol formation

2010 ◽  
Vol 10 (15) ◽  
pp. 7169-7188 ◽  
Author(s):  
A. W. H. Chan ◽  
M. N. Chan ◽  
J. D. Surratt ◽  
P. S. Chhabra ◽  
C. L. Loza ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Peroxyl Radicals ◽  
Unsaturated Aldehyde ◽  
Aerosol Formation ◽  
Unsaturated Aldehydes ◽  
Oxidation Of Hydrocarbons ◽  
Important Intermediate

Abstract. Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3–8), the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

scholarly journals Role of aldehyde chemistry and NO<sub>x</sub> concentrations in secondary organic aerosol formation

2010 ◽  
Vol 10 (4) ◽  
pp. 10219-10269 ◽  
Author(s):  
A. W. H. Chan ◽  
M. N. Chan ◽  
J. D. Surratt ◽  
P. S. Chhabra ◽  
C. L. Loza ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Peroxyl Radicals ◽  
Unsaturated Aldehyde ◽  
Aerosol Formation ◽  
Unsaturated Aldehydes ◽  
Oxidation Of Hydrocarbons ◽  
Important Intermediate

Abstract. Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios, the SOA yields from isoprene high-NOxphotooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

scholarly journals The Costs of Green Leaf Volatile-Induced Defense Priming: Temporal Diversity in Growth Responses to Mechanical Wounding and Insect Herbivory

Plants ◽  
2019 ◽  
Vol 8 (1) ◽  
pp. 23 ◽  
Author(s):  
Jurgen Engelberth ◽  
Marie Engelberth
Keyword(s):  
Biological Activities ◽  
Induced Defense ◽  
Insect Herbivory ◽  
Defense Responses ◽  
Green Leaf Volatiles ◽  
Green Leaf ◽  
Growth Responses ◽  
Maize Seedlings ◽  
Mechanical Wounding ◽  
Differential Growth

Green leaf volatiles (GLVs) have long been associated with plant defense responses against insect herbivory. Although some of their biological activities appear to directly affect the attacking herbivore, one of the major functions of GLVs seems to be the priming of these defense responses. This priming is generally considered to impose low costs on the plant should no direct attack happen. Here, we demonstrate that priming of maize seedlings with GLVs is costly for the plants as it results in significantly reduced growth. We further demonstrate that priming very selectively affects growth responses after insect elicitor treatment and mechanical wounding depending on the age and/or the developmental stage of the treated plant. The differential growth response of maize seedlings to treatment with GLVs and subsequent herbivory-related damage sheds new light on the biological activity of these important plant volatile compounds and indicates consequences that go beyond defense.

Review of recent advances on the production and eco-physiological roles of green leaf volatiles

2013 ◽  
Vol 37 (3) ◽  
pp. 268-275
Author(s):  
Hai-Feng SUN ◽  
Zhen-Yu LI ◽  
Bin WU ◽  
Xue-Mei QIN
Keyword(s):  
Green Leaf Volatiles ◽  
Green Leaf ◽  
Leaf Volatiles ◽  
Recent Advances
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