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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
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2013 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 405, no 25, p. 8215-8222Article 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.

Place, publisher, year, edition, pages
2013. Vol. 405, no 25, p. 8215-8222
Keywords [en]
2D-GC, 2D-LC, Benzo[a]pyrene, Heart cut, PAH, SRM1649a, SRM1975
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-95076DOI: 10.1007/s00216-013-7222-5ISI: 000324587400027OAI: oai:DiVA.org:su-95076DiVA, id: diva2:658705
Note

AuthorCount:4;

Available from: 2013-10-22 Created: 2013-10-21 Last updated: 2018-09-13Bibliographically approved
In thesis
1. Determination of OPAHs and PAHs in Particulate Matter from Ambient Air and Engine Emissions: Multidimensional Chromatography
Open this publication in new window or tab >>Determination of OPAHs and PAHs in Particulate Matter from Ambient Air and Engine Emissions: Multidimensional Chromatography
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. p. 58
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-122046 (URN)978-91-7649-242-0 (ISBN)
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
2. Automation, hyphenation and multidimensional chromatography for PAH analysis: Analytical techniques to simplify sample complexity
Open this publication in new window or tab >>Automation, hyphenation and multidimensional chromatography for PAH analysis: Analytical techniques to simplify sample complexity
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

One group of organic environmental pollutants which are potentially hazardous to human health is polycyclic aromatic hydrocarbons (PAHs). These compounds consist of two or more benzene rings in their structure among which benzo[a]pyrene (B[a]P) is classified as a human carcinogen. In order to generate accurate data for PAHs, reliable analytical methods are a prerequisite for PAH monitoring in the environment and cancer risk assessments. However, there are several analytical challenges in PAH analysis because they are a large number of compounds with different physical and chemical properties and occur at varying concentration levels, often in complex matrices. Thus, this thesis aimed at tackling these difficulties in PAH analysis using various analytical techniques such as automation, hyphenation and multidimensional chromatography, particularly to increase the detectability and separation efficiency of PAHs in complex matrices. Furthermore, analytical methods were also presented as a tool for toxicological studies.

A fully automated two-dimensional (2D)-liquid chromatography (LC)/2D-gas chromatography system was developed to enable the online sample clean-up, separation and detection, initially with two flame ionization detectors (FIDs) (Paper I). The introduction of mass selective detectors (MSDs) instead of two FIDs further advanced the original 2D system, improving the detectability and selectivity in PAH analysis (Paper II). The PAH levels were determined in two standard reference materials (SRMs) from the National Institute of Standards and Technology (NIST), i.e. urban dust (SRM 1649a) and diesel particulate extract (SRM 1975). The measured PAH levels were in good agreement with those obtained from FID- and MSD-based systems and reported by NIST (Paper I and II). Additionally, the PAH determination was done in particulates from wood burning, which also showed comparable results between FID and MSD systems (Paper II). The FID-based system showed slightly better separation efficiency owing to the use of hydrogen as carrier gas instead of helium and similar detectability to that of MSD (Paper I). However, the MSD-based system was advantageous to detecting late-eluting PAHs and separating interfering peaks in complex matrices (Paper II).

Paper III presented an online LC system for B[a]P-selective fractionation as a tool for studying biological interactions. Fractions could be obtained from Stockholm air particulate matter (PM) extract with or without B[a]P. The selective fractionation was achieved using serial LC columns of two pyrenyl phases, resulting in more than 90% of B[a]P in the B[a]P-containing fraction. An analytical method for identification and quantification of benz[j]aceanthrylene (B[j]A) in air PM was developed and described in paper IV. B[j]A is rarely measured due to its low abundance but is known to have high carcinogenic potential. The determination of B[j]A in air PM from Stockholm (Sweden) and Limeira (Brazil), was done together with a series of toxicological studies. The measurement and toxicological data showed an increased number of estimated cancer cases from air PM exposure when levels of B[j]A were taken into account.

In conclusion, this thesis presents various analytical approaches to obtain more accurate PAH data as well as the possibilities of using them in toxicological research.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University, 2018. p. 88
Keywords
polycyclic aromatic hydrocarbon, PAH, benzo[a]pyrene, B[a]P, carcinogenicity, cancer risk assessment, complex matrix, automation, hyphenation, multidimensional chromatography, two-dimensional, method translation, online fractionation, benz[j]aceanthrylene, B[j]A, relative potency factor
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-159716 (URN)978-91-7797-336-2 (ISBN)978-91-7797-337-9 (ISBN)
Public defence
2018-10-19, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2018-09-26 Created: 2018-09-04 Last updated: 2018-10-22Bibliographically approved

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