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Gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry methods for the determination of environmental contaminants
Örebro University, School of Science and Technology, Örebro University, Sweden.ORCID iD: 0000-0002-8553-8824
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The recent developments and improvements of instrumental methods for the analyses of the environmental contaminants, especially the persistent organic pollutants (POPs), have made it possible to detect and quantify these at very low concentrations in environmental and biotic matrices.

The main objective of this thesis is to demonstrate the capability of the atmospheric pressure chemical ionization technique (APCI), using gas chromatography coupled to tandem mass spectrometry for the determination of a wide range of environmental contaminants, including the POPs regulated by Stockholm Convention, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), but also the derivates of PBDEs and novel brominated flame retardants (NBFRs).

The APCI was operated in charge transfer condition, preferably producing molecular ions. Multiple reaction monitoring (MRM) experiments were optimized by adjusting cone voltage, collision energy and dwell time. Optimization of source parameters, such as gas flows and temperatures was also performed. Low concentration standards were analyzed, achieving a visible chromatographic peak for 2 fg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) demonstrating the excellent sensitivity of the system. Adequate linearity and repeatability were observed for all the studied compounds. The performance of APCI methods was validated against the conventional methods using gas chromatography coupled to high resolution mass spectrometry for chlorinated compounds in a wide range of matrices including environmental, air, human and food matrices.

The GC-APCI-MS/MS method was successfully applied to a set of 75 human serum samples to study the circulating levels of POPs in epidemiologic studies. Moreover the method was utilized to establish temporal trends of POPs in osprey eggs samples collected during the past five decades.

Place, publisher, year, edition, pages
Örebro: Örebro university , 2016. , 83 p.
Series
Örebro Studies in Chemistry, ISSN 1651-4270 ; 17
Keyword [en]
PCDD/Fs, PCBs, OCPs, PBDEs, NBFRs, APCI, MS/MS, HRMS, human serum, osprey egg
National Category
Chemical Sciences Other Chemistry Topics
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:oru:diva-51727ISBN: 978-91-7668-157-4OAI: oai:DiVA.org:oru-51727DiVA: diva2:954365
Public defence
2016-09-30, Örebro universitet, Musikhögskolan, Hörsalen, Fakultetsgatan 1, Örebro, 10:15 (English)
Opponent
Supervisors
Available from: 2016-08-22 Created: 2016-08-22 Last updated: 2016-09-09Bibliographically approved
List of papers
1. Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum
Open this publication in new window or tab >>Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum
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2016 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1453, 88-98 p.Article in journal (Refereed) Published
Abstract [en]

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300 pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r2) >0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4 pg/μL) and CS 3 (4 pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS.

Place, publisher, year, edition, pages
Amsterdam, Netherlands: Elsevier, 2016
Keyword
PCBs, OCPs, atmospheric pressure chemical ionization (APCI), triple quadrupole mass spectrometry (MS/MS), high resolution mass spectrometry (GC/HRMS), human serum
National Category
Chemical Sciences
Research subject
Analytical Chemistry; Environmental Chemistry; Enviromental Science
Identifiers
urn:nbn:se:oru:diva-50854 (URN)10.1016/j.chroma.2016.05.030 (DOI)000378182800010 ()27236485 (PubMedID)2-s2.0-84969722268 (ScopusID)
Note

Funding Agency:

China Scholarship Council (CSC) under the Grant CSC 201206400003

Available from: 2016-06-15 Created: 2016-06-14 Last updated: 2016-09-09Bibliographically approved
2. Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins
Open this publication in new window or tab >>Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins
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2015 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 87, no 17, 9047-9053 p.Article in journal (Refereed) Published
Abstract [en]

The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (El). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 mu m film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/mu L, to 1000 pg/mu L. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HEMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:oru:diva-46035 (URN)10.1021/acs.analchem.5b02264 (DOI)000360773100062 ()26267710 (PubMedID)2-s2.0-84940971553 (ScopusID)
Note

Funding Agencies:

Generalitat Valenciana, as research group of excellence PROMETEO/2009/054

Serveis Centrals d'Instrumentacio Cientifica (SCIC) of the University Jaume I

China Scholarship Council 201206400003

Available from: 2015-10-07 Created: 2015-10-07 Last updated: 2016-09-09Bibliographically approved
3. Analysis of Novel and Legacy Brominated Flame Retardants Including Their Derivates by Atmospheric Pressure Chemical Ionization Using Gas Chromatography Coupled to Triple Quadrupole Mass Spectrometry
Open this publication in new window or tab >>Analysis of Novel and Legacy Brominated Flame Retardants Including Their Derivates by Atmospheric Pressure Chemical Ionization Using Gas Chromatography Coupled to Triple Quadrupole Mass Spectrometry
(English)Manuscript (preprint) (Other academic)
National Category
Other Chemistry Topics
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-52072 (URN)
Available from: 2016-09-09 Created: 2016-09-09 Last updated: 2016-09-09Bibliographically approved
4. Temporal Trends of Polychlorinated Biphenyls, Organochlorine Pesticides and Polybrominated Diphenyl Ethers in Osprey Eggs in Sweden over the Years 1966 – 2013
Open this publication in new window or tab >>Temporal Trends of Polychlorinated Biphenyls, Organochlorine Pesticides and Polybrominated Diphenyl Ethers in Osprey Eggs in Sweden over the Years 1966 – 2013
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(English)Manuscript (preprint) (Other academic)
National Category
Other Chemistry Topics
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-52073 (URN)
Available from: 2016-09-09 Created: 2016-09-09 Last updated: 2016-09-09Bibliographically approved

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