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Primary and secondary organics in biogenic atmospheric aerosol: The chiral study of 2-methyltetrols from method development to application
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM). (Atmospheric Science)
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Distinguishing between the primary and secondary origin of the organic components in atmospheric aerosols is one of the key parameters in assessing the relevance and role of different chemical species in the overall chemistry of the atmosphere. Currently available methods used in field measurements are not able to fully discriminate between the primary or secondary origin of compounds detected in atmospheric aerosols. This thesis presents a new analytical method for examining the primary and secondary origin of certain organic constituents, 2-methyltetrols, in biogenic atmospheric aerosol based on chirality. Chirality is a molecular structure property that makes a pair of compounds to be mirror images of each other. Consequently, compounds with chirality represent challenges for their study as individual species. This is of importance because 2-methyltetrols have been studied so far solely as two diastereomeric constituents, 2-methylerythritol and 2-methylthreitol, when in reality they are four different compounds: (2R,3S)-methylerythritol, (2S,3R)-methylerythritol, (2S,3S)-methylthreitol and (2R,3R)-mehtylthreitol. Furthermore, 2-methylerythritol and 2-methylthreitol are currently used as the main tracers for the contribution of isoprene to the formation of secondary organic aerosols in the atmosphere. Therefore, a new method directed to the chiral analysis of 2-methyltetrols was developed and applied to atmospheric samples collected at Aspvreten, Sweden, the Amazon, Brazil, and Hyytiälä, Finland. The results indicate that 2-methyltetrols in samples from the three sites have both primary and secondary origins with variability among sites as well as seasons. The estimates of the minimum primary origin contribution represent a significant fraction of the total mass of 2-methyltetrols in the samples. In some samples the contribution was as high as 30% of the total mass of these compounds. Even though 2-methyltetrols have secondary origin, their use as tracers for the atmospheric oxidation of isoprene should be discouraged, unless relative primary contributions are considered, as this study has demonstrated that they have primary origin as well. Moreover, the development and application of chiral analytical methods should be prioritized in order to improve the prevailing understanding of the real chemical composition and origin of chiral compounds in atmospheric aerosols.

Place, publisher, year, edition, pages
Stockholm: Department of Applied Environmental Science (ITM), Stockholm Univeristy , 2013. , 63 p.
Keyword [en]
atmospheric organic aerosols, 2-methyltetrols, isoprene, chiral GC-MS, enantiomeric composition
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
URN: urn:nbn:se:su:diva-89233ISBN: 978-91-7447-683-5 (print)OAI: oai:DiVA.org:su-89233DiVA: diva2:616525
Public defence
2013-05-31, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrehnius 12, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Submitted.

Available from: 2013-05-09 Created: 2013-04-17 Last updated: 2013-04-19Bibliographically approved
List of papers
1. New method for resolving the enantiomeric composition of 2-methyltetrols in atmospheric organic aerosols
Open this publication in new window or tab >>New method for resolving the enantiomeric composition of 2-methyltetrols in atmospheric organic aerosols
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2011 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1218, no 51, 9288-9294 p.Article in journal (Refereed) Published
Abstract [en]

In order to facilitate the determination of the primary and secondary origin of atmospheric organic aerosols, a novel method involving chiral capillary gas chromatography coupled with mass spectrometry has been developed and validated. The method was focused on the analysis of 2-methylerythritol and 2-methylthreitol, considered to be tracers of secondary organic aerosols from the oxidation of atmospheric isoprene. The method was validated by performing various tests using authentic standards, including pure enantiomeric standards. The result showed that the analytical method itself does not affect the enantiomeric composition of the samples analyzed. The method was applied on atmospheric aerosols from a boreal forest collected in Aspvreten, Sweden and on laboratory samples obtained from liquid phase oxidation of isoprene and smog chamber experiments. Aerosol samples contained one enantiomer of 2-methylerythritol in significantly larger quantities than the others. In contrast, the liquid-phase oxidation of isoprene and its gas-phase oxidation in the smog chamber produced all enantiomers in equal quantities. The results obtained where the enantiomer fraction, EF, is larger than 0.50 suggest that 2-methyltetrols in atmospheric aerosols may also have biological origin. Information about the differences between enantiomer fractions obtained using this method brings new insights in the area of atmospheric aerosols.

Keyword
Secondary Organic Aerosols, 2-Methylerythritol, 2-Methylthreitol, Chiral GC-MS, Isoprene
National Category
Natural Sciences
Identifiers
urn:nbn:se:su:diva-71152 (URN)10.1016/j.chroma.2011.10.069 (DOI)000298530000021 ()
Note

authorCount :8

Available from: 2012-01-26 Created: 2012-01-26 Last updated: 2017-12-08Bibliographically approved
2. Atmospheric chemistry in stereo: A new look at secondary organic aerosols from isoprene
Open this publication in new window or tab >>Atmospheric chemistry in stereo: A new look at secondary organic aerosols from isoprene
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2011 (English)In: Geophysical Research Letters, ISSN 0094-8276, E-ISSN 1944-8007, Vol. 38, L11807- p.Article in journal (Refereed) Published
Abstract [en]

Isoprene, a compound emitted by vegetation, could be a major contributor to secondary organic aerosols (SOA) in the atmosphere. The main evidence for this contribution were the 2-methylbutane-1,2,3,4-tetraols, or 2-methyltetrols (2-methylerythritol and 2-methylthreitol) present in ambient aerosols. In this work, the four stereoisomers of these tetraols were analyzed in aerosols from Aspvreten, Sweden. 2-C-methyl-D-erythritol was found in excess over its enantiomer in the Spring/Summer, by up to 29% in July. This clearly indicated some biological origins for this enantiomer, consistent with its well-documented production by plants and other living organisms. In addition, a minimum of 20 to 60% of the mass of racemic tetraols appeared from biological origin. Thus, the SOA mass produced by isoprene in the atmosphere is less than what indicated by the 2-methyltetrols in aerosols. Our results also demonstrate that stereochemical speciation can distinguish primary and secondary organic material in atmospheric aerosols.

National Category
Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-67582 (URN)10.1029/2011GL047323 (DOI)000291813300002 ()
Note
authorCount :9Available from: 2011-12-29 Created: 2011-12-29 Last updated: 2017-12-08Bibliographically approved
3. Primary and secondary organics in tropical rainforest aerosols: Quantitative and qualitative analysis of 2-methyltetrols in the Amazon
Open this publication in new window or tab >>Primary and secondary organics in tropical rainforest aerosols: Quantitative and qualitative analysis of 2-methyltetrols in the Amazon
(English)In: Atmospheric Chemistry and Physics Discussions, ISSN 1680-7367, E-ISSN 1680-7375Article in journal (Refereed) Submitted
Abstract [en]

Ambient aerosol samples from central Amazonia were analyzed for the presence of (2R,3S)- and (2S,3R)- methylerythritol and (2S,3S)- and (2R,3R)- methylthreitol, four stereoisomers that may have primary and secondary origins from the biosynthesis and oxidation processes of isoprene within plants and also in the atmosphere. The 2-methyltetrols were detected in aerosol samples collected at a measurement site near Manaus, Brazil in a remote tropical rainforest environment between June 2008 and June 2009. Average concentrations of 78.2 and 72.8 ng m-3 were observed for (2R,3S)- and (2S,3R)- methylerythritol and 3.1 and 3.3 ng m-3 for (2S,3S)- and (2R,3R)- methylthreitol during the dry season. In the wet season, the average concentrations were 7.1, 6.5, 2.0, and 2.2 ng m-3, respectively. The enantiomer fractions (Ef) were on average 0.52: 0.48 for (2R,3S)- and (2S,3R)- methylerythritol and 0.46: 0.54 for (2S,3S)- and (2R,3R)- methylthreitol. The concentration of these isoprene oxidation products attributed to primary origin ranged between 0.8 and 53.8 ng m-3 for the 2-methylerythritols and between 0.3 and 2.1 ng m-3 for the 2-methylthreitols. The 2-methylerythritols show no correlation with isoprene emission estimates whereas 2-methylthreitol displays a negative correlation. The present study reinforces the importance of the analysis of chiral organic compounds to correctly assess the relative contribution of primary biogenic emissions and isoprene oxidation products to biogenic secondary organic aerosol.

Keyword
2-methyltetrols, isoprene, enantiomeric composition
National Category
Environmental Sciences
Research subject
Atmospheric Sciences
Identifiers
urn:nbn:se:su:diva-89302 (URN)
Available from: 2013-04-19 Created: 2013-04-19 Last updated: 2017-12-06Bibliographically approved
4. Enantiomeric composition of 2-methyltetrols in atmospheric aerosol from boreal forest environment in Hyytiälä, Finland
Open this publication in new window or tab >>Enantiomeric composition of 2-methyltetrols in atmospheric aerosol from boreal forest environment in Hyytiälä, Finland
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Ambient aerosol samples collected in a boreal forest environment in Hyytiälä, Finland were analyzed for the presence of (2R,3S)- and (2S,3R)- methylerythritol and (2S,3S)- and (2R,3R)- methylthreitol. These four stereoisomers can have primary and secondary origins from the biosynthesis and oxidation processes of isoprene in plants and in the atmosphere. Only 2-methylerythritols were detected in the aerosol samples collected between June 2009 and January 2010. Average observed concentrations were 3.16 and 2.83 ng m-3 for (2R,3S)- and (2S,3R)- methylerythritol, respectively. The enantiomer fractions for (2R,3S)- and (2S,3R)- methylerythritol (Ef) were on average 0.53:0.47. The concentrations of these isoprene oxidation products of primary origin ranged between 0.8 and 53.8 ng m-3 for the 2-methylerythritols. The primary origin contribution was up to 100% of the total mass of the 2-methylerythritols in some of these samples. The present study reinforces the importance of the analysis of chiral organic compounds to correctly assess the relative contribution of primary biogenic emissions and atmospheric isoprene oxidation products to biogenic secondary organic aerosol.

Keyword
isoprene, 2-methyltetrols, chiral GC-MS, enantiomeric composition
National Category
Environmental Sciences
Research subject
Atmospheric Sciences
Identifiers
urn:nbn:se:su:diva-89300 (URN)
Available from: 2013-04-19 Created: 2013-04-19 Last updated: 2013-04-19Bibliographically approved

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