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Trace analysis of dioxins and dioxin-like PCBs using comprehensive two-dimensional gas chromatography with electron capture detection
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), two groups of struc-turally related chlorinated aromatic hydrocarbons, generally referred to as “dioxins” are of great concern due to their extreme toxicity and presence in all compartments of the environment. Since they occur at very low levels, their analysis is complex and challenging, and there is a need for cost-efficient, reliable and rapid analytical alternatives to the expensive methods in-volving use of gas chromatography high-resolution mass spectrometry (GC-HRMS). It is im-portant to routinely monitor food and feed items to detect contaminations at an early stage. For the regulation of dioxins and dioxin-like PCBs in food and feed according to current legis-lation, large numbers of samples have to be analysed. Furthermore, soils at many industrial sites are also contaminated with dioxins and need remediation. In order to optimize the cost-efficiency of reclamation activities it is important to acquire information about the levels and distribution of dioxins in the contaminated areas.

The aim of the studies underlying this thesis was to investigate the potential of comprehen-sive two-dimensional gas chromatography with a micro-electron capture detector (GC × GC-µECD) as a cost-effective method for analysing dioxins and dioxin-like PCBs in food, feed, fly ash and contaminated soils. Quantification studies of dioxins and dioxin-like PCBs were con-ducted and results were compared with GC-HRMS reference data. Generally, there was good agreement between both the congener-specific results and data expressed as total toxic equiva-lents (TEQs). The developed GC × GC-µECD method meets the European Community (EC) requirements for screening methods for control of dioxins and dioxin-like PCBs in food and feed. The presented results also indicate that GC × GC-µECD has potential to be used as a routine method for the congener-specific analysis of 2,3,7,8-PCDD/Fs and dioxin-like PCBs in matrices such as food and feed, fly ash and soil.

However, to fully exploit the potential of the GC × GC-µECD technique, it should be combined with a fast and cost-efficient sample preparation procedure. Therefore, a number of certified reference materials (CRMs) were extracted using a new shape-selective pressurized liquid extraction technique with integrated carbon fractionation (PLE-C), and the purified extracts were analysed for PCDD/Fs using GC × GC-µECD. The results compared well with the certified values of a fly ash and a sandy soil CRM, but they were much too high for a com-plex clay soil CRM. It was concluded that this combination of techniques was very promising for screening ash and highly permeable soils.

Further assessments and method revisions are still required before GC × GC-µECD can be used on a routine basis, and available software packages need to be refined in order to accelerate the data-handling procedures, which currently restrict the sample throughput.

Place, publisher, year, edition, pages
Umeå: Kemi , 2006. , 43 p.
Keyword [en]
Comprehensive two-dimensional gas chromatography, GC × GC, µECD, PCDDs, PCDFs, dioxins, dioxin-like PCBs, Pressurized liquid extraction, PLE, PLE-C, food, feed, fly ash, soil
National Category
Environmental Sciences
Identifiers
URN: urn:nbn:se:umu:diva-963ISBN: 91-7264-234-3 (print)OAI: oai:DiVA.org:umu-963DiVA: diva2:145208
Public defence
2007-01-19, KB3B1, KBC, Umeå Universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2006-12-29 Created: 2006-12-29 Last updated: 2012-06-07Bibliographically approved
List of papers
1. Comprehensive two-dimensional gas chromatography of the 209 polychlorinated biphenyls
Open this publication in new window or tab >>Comprehensive two-dimensional gas chromatography of the 209 polychlorinated biphenyls
2003 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1019, no 1-2, 111-126 p.Article in journal (Refereed) Published
Abstract [en]

Comprehensive two-dimensional gas chromatography (GC×GC) of the 209 polychlorinated biphenyls (CBs) was carried out using a longitudinally modulated cryogenic system (LMCS) and liquid carbon dioxide as cryogen. The effluent from a non-polar column was modulated and further separated on either a polar or a shape-selective second-dimension column. Five GC×GC column combinations were evaluated, with DB-XLB as the first column in each case. DB-XLB separates more congeners than any other GC column currently available. When combined with a biscyanopropyl siloxane (SP-2340 or BPX70) or smectic liquid crystal (LC-50) second-dimension column in a GC×GC system many additional CBs can be separated. In total, 176 and 181 of the 209 congeners were separated (Rs=0.5) on the column combinations DB-XLB/SP-2340 and DB-XLB/LC-50, respectively. Of the 136 CBs present in any Aroclor mixture at concentrations greater than 0.05% (w/w), 126 were resolved using either of these two column combinations. The seven frequently measured CBs 28, 52, 101, 118, 138, 153, 180, and the WHO-PCBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169 and 189 were all separated from Aroclor CBs on the DB-XLB/LC-50 column set, whereas CBs 118 and 131 coeluted on the DB-XLB/SP-2340 column set. In addition, three technical CB formulations (Aroclors 1232, 1248 and 1260) and a seal blubber sample (Halichoerus grypus) from the Baltic Sea were analyzed. Similar peak patterns were found for Aroclor 1260 and the CBs in the seal blubber, facilitating use of this technical CB formulation to identify the CBs in the blubber by GC×GC. Individual CBs in environmental samples, such as seal blubber, may be identified semi-automatically by matching the samples GC×GC profiles to a template generated using a standard containing all 209 CBs. Using such a template, 64 CBs were identified in the grey seal blubber sample.

Keyword
Gas chromatography, comprehensive two-dimensional, Baltic grey seal, Polychlorinated biphenyls, Aroclors
Identifiers
urn:nbn:se:umu:diva-9222 (URN)10.1016/j.chroma.2003.08.100 (DOI)14650609 (PubMedID)
Available from: 2008-03-12 Created: 2008-03-12 Last updated: 2017-12-14Bibliographically approved
2. Evaluation of modulators and electron-capture detectors for comprehensive two-dimensional GC of halogenated organic compounds
Open this publication in new window or tab >>Evaluation of modulators and electron-capture detectors for comprehensive two-dimensional GC of halogenated organic compounds
Show others...
2003 (English)In: Journal of Chromatography A, Vol. 1019, no 1-2, 65-77 p.Article in journal (Refereed) Published
Abstract [en]

Abstract

Different cryogenic and a heated GC×GC modulator(s) were evaluated and compared for the analysis of high-boiling halogenated compounds. The cryogenic modulators investigated were: (i) the longitudinally modulated cryogenic system; (ii) the liquid-nitrogen-cooled jet modulator (KT2001); (iii) a dual-jet CO2 modulator (made in-house); (iv) a semi-rotating cryogenic modulator (made in-house) and (v) a CO2 loop modulator (KT2003); the heated modulator was the slotted heater system (sweeper). Each modulator was optimised with respect to analyte peak widths at half height in the second-dimension. n-Alkanes, chlorinated alkanes, polychlorinated biphenyls (PCBs) and fluorinated polycyclic aromatic hydrocarbons (F-PAHs) were used as test analytes. The flow rate of the coolant was found to be an important parameter, i.e. the flow rate of the gaseous nitrogen in the KT2001, and of the liquid CO2 in the other cryogenic modulators. For the slotted heater the stroke velocity and pause time were important parameters. This modulator had a limited application range in terms of temperature due to a necessary 100 °C difference between sweeper and oven temperature. All cryogenic modulators were found to be suitable for the GC×GC analysis of high-boiling compounds, but the CO2 modulators are to be preferred to the KT2001 due to a wider application range and slightly narrower peaks. As regards the performance of three commercially available electron-capture detectors (ECDs), the aim was to obtain narrow peak widths in GC×GC, i.e. to avoid band broadening caused by the cell volume. The most important parameters were the flow rate of the make-up gas and the detector temperature which both should be as high as possible. Comparison of analyte peak widths obtained with ECD mode and flame ionisation detection (FID) showed that all ECDs exhibited band broadening compared to the FID. The narrowest peaks were obtained with the Agilent micro-ECD, which has a cell volume of only 150 μl.

Keyword
Modulators, Electron-capture detector, Gas chromatography, comprehensive two-dimensional
Identifiers
urn:nbn:se:umu:diva-9214 (URN)doi:10.1016/S0021-9673(03)01237-8 (DOI)
Note
First International Symposium on Comprehensive Multidimensional Gas ChromatographyAvailable from: 2008-03-11 Created: 2008-03-11 Last updated: 2012-06-07Bibliographically approved
3. Separation of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans and 12 dioxin-like polychlorinated biphenyls by comprehensive two-dimensional gas chromatography with electron-capture detection
Open this publication in new window or tab >>Separation of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans and 12 dioxin-like polychlorinated biphenyls by comprehensive two-dimensional gas chromatography with electron-capture detection
Show others...
2004 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1038, no 1-2, 189-199 p.Article in journal (Refereed) Published
Abstract [en]

Comprehensive two-dimensional gas chromatography (GC×GC) with electron-capture detection (ECD) has been optimized for the separation of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans and 12 dioxin-like polychlorinated biphenyls, with emphasis on the selection of the first- and second-dimension, commercially available, columns. When eight second-dimension columns were subsequently combined with a 100% methylpolysiloxane stationary phase (DB-1) in the first dimension to create orthogonal conditions, a complete separation of all congeners with different TEF values was obtained with two column combinations, DB-1 × VF-23 and DB-1 × LC-50. When other types of first-dimension columns were used (and orthogonality was partly sacrificed), a DB-XLB column combined with 007-65HT, VF-23 and LC-50 was found to provide a complete separation of all 29 priority congeners. Next, the potential of these three column combinations for real-life analysis was preliminarily studied. With a spiked and fractionated milk extract, DB-XLB × LC-50 was found to be the most powerful column combination, because of the good separation of the 29 priority congeners from each other as well as from the matrix constituents. Quantitative performance (close to three-order linearity; LODs, 30–150 fg injected; R.S.D.s, 1.5–6.5% (n=10)) was satisfactory.

Place, publisher, year, edition, pages
Amsterdam: Elsevier, 2004
Keyword
Gas chromatography, comprehensive two-dimensional, Polychlorinated dibenzo-p-dioxins, Polychlorinated dibenzofurans, Dioxin-like polychlorinated biphenyls
Identifiers
urn:nbn:se:umu:diva-14324 (URN)10.1016/j.chroma.2004.03.026 (DOI)
Available from: 2007-05-28 Created: 2007-05-28 Last updated: 2017-12-14Bibliographically approved
4. Trace analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans and WHO polychlorinated biphenyls in food using comprehensive two-dimensional gas chromatography with electron-capture detection
Open this publication in new window or tab >>Trace analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans and WHO polychlorinated biphenyls in food using comprehensive two-dimensional gas chromatography with electron-capture detection
Show others...
2005 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1086, no 1-2, 61-70 p.Article in journal (Refereed) Published
Abstract [en]

Trace analysis of 2,3,7,8-polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and the 12 WHO-PCBs (four non-ortho and eight mono-ortho congeners that have been assigned toxic equivalence factors, TEFs, by the World Health Organisation) was conducted by comprehensive two-dimensional gas chromatography with a micro electron-capture detector (GC x GC-mu ECD). Four food matrices (fish oil from herring, spiked cows' milk, vegetable oil and an eel extract) were analysed by two GC x GC laboratories, and four GC-HRMS laboratories generated reference values. The two GC x GC laboratories used different column combinations for separating the target analytes. For the first dimension, non-polar DB-XLB and VF-1 columns were used, and for the second dimension, an LC-50 liquid crystalline column with unique selectivity for planar compounds. The congener-specific and total toxic equivalence (TEQ) data obtained using DB-XLB x LC-50 were in good agreement with results obtained by the GC-HRMS laboratories. The WHO-PCB data obtained with the VF-1 x LC-50 combination was also good, but the PCDD/F concentrations were sometimes overestimated due to matrix interferences. GC x GC-mu ECD using DB-XLB x LC-50 seems to fulfil the European Community requirements of a screening method for PCDD/F and WHO-PCB TEQ in food.

Keyword
comprehensive two-dimensional gas chromatography, GC x GC, mu ECD; PCB, PCDD/F, TEF, TEQ, quantification, food, Dioxins, GC-HRMS
Identifiers
urn:nbn:se:umu:diva-13351 (URN)doi:10.1016/j.chroma.2004.11.071 (DOI)
Available from: 2007-05-08 Created: 2007-05-08 Last updated: 2017-12-14Bibliographically approved
5. Congener-specific analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash using comprehensive two-dimensional gas chromatography with electron cap-ture detection.
Open this publication in new window or tab >>Congener-specific analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in fly ash using comprehensive two-dimensional gas chromatography with electron cap-ture detection.
Manuscript (Other academic)
Identifiers
urn:nbn:se:umu:diva-5627 (URN)
Available from: 2006-12-29 Created: 2006-12-29 Last updated: 2010-01-13Bibliographically approved
6. Analysis of dioxins in soil and fly ash using pressurized liquid extraction with an integrated carbon trap followed by comprehensive two-dimensional gas chromatography with electron capture detection
Open this publication in new window or tab >>Analysis of dioxins in soil and fly ash using pressurized liquid extraction with an integrated carbon trap followed by comprehensive two-dimensional gas chromatography with electron capture detection
(English)Manuscript (preprint) (Other (popular science, discussion, etc.))
Identifiers
urn:nbn:se:umu:diva-3232 (URN)
Available from: 2008-05-19 Created: 2008-05-19 Last updated: 2010-01-14Bibliographically approved

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