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Automation, hyphenation and multidimensional chromatography for PAH analysis: Analytical techniques to simplify sample complexity
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.ORCID iD: 0000-0003-4309-8282
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 [en]
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: urn:nbn:se:su:diva-159716ISBN: 978-91-7797-336-2 (print)ISBN: 978-91-7797-337-9 (electronic)OAI: oai:DiVA.org:su-159716DiVA, id: diva2:1245084
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
List of papers
1. 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, 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.

Keywords
2D-GC, 2D-LC, Benzo[a]pyrene, Heart cut, PAH, SRM1649a, SRM1975
National Category
Analytical Chemistry
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: 2018-09-13Bibliographically approved
2. Automated clean-up, separation and detection of polycyclic aromatic hydrocarbons in particulate matter extracts using a 2D-LC/2D-GC system: a method translation from two FIDs to two MS detectors
Open this publication in new window or tab >>Automated clean-up, separation and detection of polycyclic aromatic hydrocarbons in particulate matter extracts using a 2D-LC/2D-GC system: a method translation from two FIDs to two MS detectors
2017 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 409, no 24, p. 5619-5629Article in journal (Refereed) Published
Abstract [en]

An online two-dimensional (2D) liquid chromatography/2D gas chromatography system with two mass-selective detectors has been developed on the basis of a previous system with two flame ionization detectors. The method translation involved the change of carrier gas from hydrogen to helium, column dimension and detectors. The 2D system with two mass-selective detectors was validated with use of polycyclic aromatic hydrocarbon (PAH) standards and two standard reference materials from air and diesel exhaust. Furthermore, the system was applied to a real sample, wood smoke particulates. The PAH values determined correlated well with the previous data and those from the National Institute of Standards and Technology. The system enhanced the benefits of the previous system, which were limited by the low detectability and lack of mass selectivity. This study shows an automated 2D system that is valid for PAH analysis of complex environmental samples directly from crude extracts.

Keywords
Polycyclic aromatic hydrocarbon, Multidimensional gas chromatography, Standard reference material, Wood smoke particulates, Long-term stability
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-147893 (URN)10.1007/s00216-017-0509-1 (DOI)000409295300002 ()
Available from: 2017-10-23 Created: 2017-10-23 Last updated: 2018-09-04Bibliographically approved
3. Benzo[a]pyrene-specific online high-performance liquid chromatography fractionation of air particulate extracts–A tool for evaluating biological interactions
Open this publication in new window or tab >>Benzo[a]pyrene-specific online high-performance liquid chromatography fractionation of air particulate extracts–A tool for evaluating biological interactions
Show others...
2014 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1355, p. 100-106Article in journal (Refereed) Published
Abstract [en]

Benzo[a]pyrene (B[a]P) is a known human carcinogen and is commonly used as a surrogate for assessing the carcinogenic risk posed by complex mixtures of polycyclic aromatic hydrocarbons (PAHs) present in air particulate matter (PM). However, studies have shown that using B[a]P as a surrogate may underestimate the carcinogenic potential of PAH mixtures, as the risk assessment approach does not consider interaction effects. Thus, toxicological studies using B[a]P to assess its carcinogenic potential in environmentally derived complex mixtures, as opposed to single compound experiments, could improve risk assessment. The intention of the present study was to develop an online HPLC fractionation system for the selective removal of B[a]P from air PM extracts. Two serial pyrenylethyl (PYE) columns enabled selective separation of B[a]P from its isomers and other PAHs as well as a short fractionation cycle of 30 minutes. One run consisted of three collection steps: the first fraction contained PAHs eluting earlier than B[a]P, the second contained B[a]P and the last contained later-eluting PAHs. The selectivity and recovery of the system was investigated using extracts of Stockholm air PM samples. The overall recovery for all PAHs was approximately 80%, and the system proved to be selective, as it removed 94% of B[a]P and less than 3% of benzo[b]fluoranthene from the complex PAH mixture. Exposing human cells to blanks generated by the fractionation system did not induce cytotoxicity or DNA damage signalling. In conclusion, the online HPLC system was selective for B[a]P fractionation whilst minimising run-to-run variation and allowing repeated fractionations for larger samples due to its relatively short run time

National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-104502 (URN)10.1016/j.chroma.2014.05.082 (DOI)000340302500011 ()
Available from: 2014-06-08 Created: 2014-06-11 Last updated: 2018-09-04Bibliographically approved
4. Detection of Benz[j]aceanthrylene in Urban Air and Evaluation of Its Genotoxic Potential
Open this publication in new window or tab >>Detection of Benz[j]aceanthrylene in Urban Air and Evaluation of Its Genotoxic Potential
Show others...
2015 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 49, no 5, p. 3101-3109Article in journal (Refereed) Published
Abstract [en]

Benz[j]aceanthrylene (B[j]A) is a cyclopenta-fused polycyclic aromatic hydrocarbon with strong mutagenic and carcinogenic effects. We have identified B[j]A in air particulate matter (PM) in samples collected in Stockholm, Sweden and in Limeira, Brazil using LC-GC/MS analysis. Determined concentrations ranged between 1.57 and 12.7 and 19.6-30.2 pg/m(3) in Stockholm and Limeira, respectively, which was 11-30 times less than benzo[a]pyrene (B[a]P) concentrations. Activation of the DNA damage response was evaluated after exposure to B[j]A in HepG2 cells in comparison to B[a]P. We found that significantly lower concentrations of B[j]A were needed for an effect on cell viability compared to B[a]P, and equimolar exposure resulted in significant more DNA damage with B[j]A. Additionally, levels of gamma H2AX, pChk1, p53, pp53, and p21 proteins were higher in response to B[j]A than B[a]P. On the basis of dose response induction of pChk1 and gamma H2AX, B[j]A potency was 12.5- and 33.3-fold higher than B[a]P, respectively. Although B[j]A levels in air were low, including B[j]A in the estimation of excess lifetime cancer risk increased the risk up to 2-fold depending on which potency factor for B[j]A was applied. Together, our results show that B[j]A could be an important contributor to the cancer risk of air PM.

National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-116630 (URN)10.1021/es505458g (DOI)000350611100065 ()25625372 (PubMedID)
Note

AuthorCount:11;

Available from: 2015-04-27 Created: 2015-04-22 Last updated: 2018-09-04Bibliographically approved

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