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Determination of OPAHs and PAHs in Particulate Matter from Ambient Air and Engine Emissions: Multidimensional Chromatography
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Particulate matter (PM) is an air pollutant that seriously impacts human health. Epidemiological studies have shown associations between human exposure to urban air PM and lung cancer, respiratory and cardiovascular diseases. Polycyclic aromatic hydrocarbons (PAHs) and oxygenated polycyclic aromatic hydrocarbons (OPAHs) are two groups of compounds associated with PM in ambient air. These compounds are generated from the incomplete combustion of organic material of both natural and anthropogenic origin. PAHs are thought to play an important role in the adverse health outcomes from exposure to PM in air. OPAHs contain one or more carbonyl groups and could be more toxic to humans compared to their corresponding parent PAH. Measurement of these compounds at trace levels in complex matrices requires analytical methods with high selectivity and precision and low quantification limits.

This thesis describes the development and application of analytical methods for the determination of PAHs and OPAHs in ambient air and engine exhaust PM. Extraction was performed using pressurized liquid extraction, and two different setups for liquid chromatography–gas chromatography (LC-GC) were employed for automated sample clean-up, separation and detection. The developed methods were validated using standard reference materials issued by the National Institute of Standards and Technology. The first methodology developed used off-line solid-phase extraction and on-line LC-GC/mass spectrometry (LC-GC/MS). This method provided low limits of quantification and high selectivity and was successfully applied to the determination of OPAHs and PAHs in PM from the urban atmosphere of Sulaymaniyah city in the Kurdistan region of Iraq. The concentration of benzo[a]pyrene in Sulaymaniyah city was three times higher than the legislated EU target value (1 ng/m3). Furthermore the analytical method was applied on exhaust PM of vehicles fuelled with various gasoline/ethanol blends. The emissions factors for PAHs and OPAHs were highest when using70% ethanol/gasoline blends at -7 °C.

The second method developed provided fully automated clean-up, separation and detection of PAHs in PM extracts using a multidimensional 2D-LC/2D-GC system. Polar, mono/di-aromatic and alkane compounds were successively removed by the two-dimensional LC part of the system. Heart-cutting segments from the first GC column (first dimension) to the second GC column (second dimension) increased the resolution of poorly separated or co-eluted PAHs. The results were in good agreement with the certified values from NIST (±25%).

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University , 2015. , 58 p.
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-122046ISBN: 978-91-7649-242-0 (print)OAI: oai:DiVA.org:su-122046DiVA: diva2:862360
Public defence
2015-11-27, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2015-11-05 Created: 2015-10-21 Last updated: 2015-10-26Bibliographically approved
List of papers
1. Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC-GC/MS
Open this publication in new window or tab >>Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC-GC/MS
2015 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 407, no 2, 427-438 p.Article in journal (Refereed) Published
Abstract [en]

The objective of this study was to develop a novel analytical chemistry method, comprised of a coupled high-performance liquid chromatography-gas chromatography/mass spectrometry system (LC-GC/MS) with low detection limits and high selectivity, for the identification and determination of oxygenated polycyclic aromatic hydrocarbons (OPAHs) and polycyclic aromatic hydrocarbons (PAHs) in urban air and diesel particulate matter. The linear range of the four OPAHs, which include 9,10-anthraquinone, 4H-cyclopenta[def]phenanthrene-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, was 0.7 pg-43.3 ng with limits of detection (LODs) and limits of quantification (LOQs) on the order of 0.2-0.8 and 0.7-1.3 pg, respectively. The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection. The recoveries of the OPAHs spiked onto glass fiber filters using two different pressurized liquid extraction (PLE) methods were in the ranges of 84-107 and 67-110 %, respectively. The analytical protocols were validated using the following National Institute of Standards and Technology standard reference materials: SRM 1649a (Urban Dust), SRM 1650b (Diesel Particulate Matter), and SRM 2975 (Diesel Particulate Matter, Industrial Forklift). The measured mass fractions of the OPAHs in the standard reference materials (SRMs) in this present study are higher than the values from the literature, except for benzanthrone in SRM 1649a (Urban Dust). In addition to the OPAHs, 44 PAHs could be detected and quantified from the same particulate extract used in this protocol. Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs. However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature.

Keyword
OPAHs, PAHs, PLE, SRM1649a, SRM2975, SRM1650b
National Category
Chemical Sciences
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-114258 (URN)10.1007/s00216-014-8304-8 (DOI)000348207200007 ()25395203 (PubMedID)
Note

AuthorCount:4;

Available from: 2015-03-26 Created: 2015-02-25 Last updated: 2017-12-04Bibliographically approved
2. Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
Open this publication in new window or tab >>Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
Show others...
2015 (English)In: Atmospheric Environment, ISSN 1352-2310, E-ISSN 1873-2844, Vol. 116, 44-50 p.Article in journal (Refereed) Published
Abstract [en]

The concentrations of 43 polycyclic aromatic hydrocarbons (PAHs) and 4 oxygenated PAHs (OPAHs) are reported for the first time in particulate matter (PM10) sampled in the air of the city of Sulaimaniyah in Iraq. The total PAH concentration at the different sampling sites varied between 9.3 and 114 ng/m(3). The corresponding values of the human carcinogen benzotalpyrene were between 0.3 and 6.9 ng/m(3), with most samples exceeding the EU annual target value of 1 ng/m(3). The highly carcinogenic dibenzopyrene isomers dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene constituted 0.1-0.4% of the total PAH concentration. However, when scaling for relative cancer potencies using toxic equivalency factors, a benzo[a]pyrene equivalent concentration of dibenzo[a,l]pyrene equal to that of benzo[a]pyrene was obtained, indicating that the contribution of dibenzo[a,l]pyrene to the carcinogenicity of the PAHs could be similar to that of benzo[a]pyrene. A high correlation between the determined concentrations of the dibenzopyrene isomers and benzo[a]pyrene was found, which supported the use of benzo[a]pyrene as an indicator for the carcinogenicity of PAHs in ambient air. The total concentrations of the four OPAHs, 9,10-anthraquinone, 4H-cyclopenta[def]phenanthren-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, varied between 0.6 and 8.1 ng/m(3), with 9,10-anthraquinone being the most abundant OPAH in all of the samples.

Keyword
Ambient air, Particulates, Oxygenated polycyclic aromatic hydrocarbons, Polycyclic aromatic hydrocarbons, Benzo[a]pyrene, Dibenzopyrenes, Anthraquinone
National Category
Earth and Related Environmental Sciences Chemical Sciences
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-120178 (URN)10.1016/j.atmosenv.2015.06.020 (DOI)000358469300005 ()
Available from: 2015-09-07 Created: 2015-09-02 Last updated: 2017-12-04Bibliographically approved
3. Emissions of particulate associated oxygenated and native polycyclic aromatic hydrocarbons from vehicles powered by ethanol/gasoline fuel blends
Open this publication in new window or tab >>Emissions of particulate associated oxygenated and native polycyclic aromatic hydrocarbons from vehicles powered by ethanol/gasoline fuel blends
(English)Manuscript (preprint) (Other academic)
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-122045 (URN)
Available from: 2015-10-21 Created: 2015-10-21 Last updated: 2016-01-29Bibliographically approved
4. Automated clean-up, separation and detection of polycyclic aromatic hydrocarbons in particulate matter extracts from urban dust and diesel standard reference materials using a 2D-LC/2D-GC system
Open this publication in new window or tab >>Automated clean-up, separation and detection of polycyclic aromatic hydrocarbons in particulate matter extracts from urban dust and diesel standard reference materials using a 2D-LC/2D-GC system
2013 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 405, no 25, 8215-8222 p.Article in journal (Refereed) Published
Abstract [en]

A multidimensional, on-line coupled liquid chromatographic/gas chromatographic system was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs). A two-dimensional liquid chromatographic system (2D-liquid chromatography (LC)), with three columns having different selectivities, was connected on-line to a two-dimensional gas chromatographic system (2D-gas chromatography (GC)). Samples were cleaned up by combining normal elution and column back-flush of the LC columns to selectively remove matrix constituents and isolate well-defined, PAH enriched fractions. Using this system, the sequential removal of polar, mono/diaromatic, olefinic and alkane compounds from crude extracts was achieved. The LC/GC coupling was performed using a fused silica transfer line into a programmable temperature vaporizer (PTV) GC injector. Using the PTV in the solvent vent mode, excess solvent was removed and the enriched PAH sample extract was injected into the GC. The 2D-GC setup consisted of two capillary columns with different stationary phase selectivities. Heart-cutting of selected PAH compounds in the first GC column (first dimension) and transfer of these to the second GC column (second dimension) increased the baseline resolutions of closely eluting PAHs. The on-line system was validated using the standard reference materials SRM 1649a (urban dust) and SRM 1975 (diesel particulate extract). The PAH concentrations measured were comparable to the certified values and the fully automated LC/GC system performed the clean-up, separation and detection of PAHs in 16 extracts in less than 24 h. The multidimensional, on-line 2D-LC/2D-GC system eliminated manual handling of the sample extracts and minimised the risk of sample loss and contamination, while increasing accuracy and precision.

Keyword
2D-GC, 2D-LC, Benzo[a]pyrene, Heart cut, PAH, SRM1649a, SRM1975
National Category
Chemical Sciences
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-95076 (URN)10.1007/s00216-013-7222-5 (DOI)000324587400027 ()
Note

AuthorCount:4;

Available from: 2013-10-22 Created: 2013-10-21 Last updated: 2017-12-06Bibliographically approved

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