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Analysis and human levels of persistent perfluorinated chemicals
Örebro University, Department of Natural Sciences.
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

An extensive use of perfluorinated chemicals (PFCs) in the last 50 years has resulted in a worldwide spread of these persistent chemicals. Human populations are subjected to a large number of PFCs in ways that are not yet fully explained. The aims of this thesis are to develop and assure the quality of analytical methods in order to collect information on human levels and to facilitate the assessment of human exposure of PFCs.

Solid-phase extraction (SPE) methods for human blood and milk using two sorbents, octadecyl (C18) and a weak anion exchange polymer (WAX), were developed. Perfluorinated alkyl sulfonates (PFSAs) and perfluorinated alkyl carboxylic acids (PFCAs) with carbon chain lengths between four and fourteen together with perfluorooctane sulfonamide (PFOSA) could be extracted from human matrices. These extraction procedures enable selective and sensitive analysis of PFCs in human matrices using single quadrupole mass spectrometry (SQMS). The accuracy and reliability of the methods are discussed in the context of intralaboratory as well as interlaboratory quality assurance. Further improvements of the analysis are discussed including the evaluation of ultra performance liquid chromatography (UPLC).

Human whole blood, plasma and serum from Sweden, Australia and the United Kingdom have been analysed. The blood matrix selection in the assessment and comparisons of human exposure to PFCs is crucial. Human plasma contains a high percentage of PFSAs and PFCAs. On the contrary, only about 20% of the total PFOSA content is present in plasma after removal of the red blood cells. Up to eleven persistent PFCs are detected in human blood, with detection levels between 0.1-0.5 ng/mL. A gender difference with higher serum levels for males is apparent. An age trend was observed for perfluorooctane sulfonate (PFOS) levels in serum from Australia. The levels found in Australian serum indicate that emissions from the PFC production facilities are of less importance for human exposure.

Matched human milk and serum samples from Sweden show that milk levels of PFCs are about 1% of the maternal serum level. Up to five persistent PFCs are found in human milk from Sweden, with detection limits between 0.005-0.1 ng/mL, and the levels in Swedish pooled milk samples have remained constant between 1996 and 2004. A linear relationship between the maternal serum level and milk level was seen for PFOS and its shorter homologue perfluorohexane sulfonate (PFHxS). The daily intake of PFOS for a nursing infant in Sweden is estimated to be 121 ng/day if the maternal serum level is 20 ng/mL. Lactation is therefore a major exposure source for breast-fed infants.

Monomethyl- and dimethyl-branched isomers of PFOS could be separated in human blood using high performance liquid chromatography (HPLC). Human plasma contains a smaller percentage of the linear PFOS compared to commercially available PFOS standard materials, which indicate isomer specific uptake and/or elimination. A difference in the isomer composition is also seen between the countries studied. Human blood from the UK and Australia have significantly lower amount of linear PFOS (59-60%) compared to Swedish blood (68%). This geographical variation suggests different human exposure sources and pathways.

Place, publisher, year, edition, pages
Örebro: Örebro universitetsbibliotek , 2006. , p. 53
Series
Örebro Studies in Chemistry, ISSN 1651-4270 ; 6
Keywords [en]
PFOS, PFOA, SPE, LC-MS, human exposure
National Category
Chemical Sciences
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:oru:diva-628ISBN: 91-7668-493-8 (print)OAI: oai:DiVA.org:oru-628DiVA, id: diva2:137040
Public defence
2006-10-13, HSM, Musikhögskolan, Örebro universitet, Örebro, 10:00
Opponent
Supervisors
Available from: 2006-09-22 Created: 2006-09-20 Last updated: 2017-10-18Bibliographically approved
List of papers
1. Development of a solid-phase extraction-HPLC/Single quadrupole MS method for quantification of perfluorochemicals in whole blood
Open this publication in new window or tab >>Development of a solid-phase extraction-HPLC/Single quadrupole MS method for quantification of perfluorochemicals in whole blood
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2005 (English)In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 77, no 3, p. 864-870Article in journal (Refereed) Published
Abstract [en]

A method for the determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) simultaneously with 10 closely related perfluorochemicals (PFCs) in human whole blood was developed and validated. PFOS and PFOA are used in various applications, for example, as surfactants and plastic additives, and are subject to environmental and health research due to their persistence. The main part of the data on PFCs in human blood is from serum samples, analyzed mainly by ion pair extraction followed by high-performance liquid chromatography (HPLC) and negative electrospray (ESI) tandem mass spectrometry (MS/MS). The analytical method developed here is suitable for human whole blood and involves solid-phase extraction (SPE) and HPLC negative electrospray single quadrupole mass spectrometry (HPLC/ES-MS). A whole blood aliquot was treated with formic acid and extracted on a octadecyl (C18) SPE column. The PFCs were isolated with methanol, and quantification was performed using single quadrupole mass spectrometry and perfluoroheptanoic acid as internal standard. Validation was performed in the range 0.3-194 ng/mL with recovery between 64 and 112% and limit of detection in the 0.1-0.5 ng/mL range for 11 of the 12 PFCs studied. We applied this method to 20 whole blood samples collected in 1997-2000 from the Swedish population in the ages 24-72. Eleven of the 12 PFCs were detected, and they were quantitatively and qualitatively confirmed using triple quadrupole LC/MS/MS analysis. PFOS, perfluorooctanesulfonamide, perfluorohexanesulfonate, PFOA and perfluorononanoic acid were quantified in all samples. In addition, perfluorohexanoic acid, perfluorodecanoic acid, perfluorodecanesulfonate, perfluoroundecanoic acid, perfluorododecanoic acid, and perfluorotetradecanoic acid were detected in some samples. This study shows that SPE and single quadrupole MS can be applied for extraction and quantification of PFCs in human whole blood, resulting in selectivity and low detection limits.

National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3115 (URN)10.1021/ac049023c (DOI)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-12-14Bibliographically approved
2. Struggle for quality in determination of perfluorinated contaminants in environmental and human samples
Open this publication in new window or tab >>Struggle for quality in determination of perfluorinated contaminants in environmental and human samples
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2006 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 40, no 24, p. 7854-7860Article in journal (Refereed) Published
Abstract [en]

The first worldwide interlaboratory study on the analyses of 13 perfluorinated compounds (PFCs) in three environmental and two human samples indicates a varying degree of accuracy in relation to the matrix or analyte determined. The ability of 38 participating laboratories from 13 countries to determine the analytes in the various matrices was evaluated by calculation of z-scores according to the Cofino model. The PFCs which were reported most frequently by the laboratories, and assessed with the most satisfactory agreement, were perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In general, the level of agreement between the participating laboratories decreased in the following order: PFC standard solution (76% satisfactory z-scores of <[2]1 for PFOS) < human blood (67%) < human plasma (63%) < fish liver extract (55%) < water (31%) < fish tissue (17%). This shows that relative good agreement between laboratories was obtained for the study of standard and human matrices. For the fish extract, most laboratories underestimated the actual PFOS concentration due to matrix effects. The results for the fish tissue and water are also poor, indicating that the extraction and cleanup steps require further improvement. It was concluded that the PFC determinations in various matrices are not yet fully mastered.

National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3116 (URN)10.1021/es061052c (DOI)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-12-14Bibliographically approved
3. Perfluorinated chemicals in relation to other persistent organic pollutants in human blood
Open this publication in new window or tab >>Perfluorinated chemicals in relation to other persistent organic pollutants in human blood
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2006 (English)In: Chemosphere, ISSN 0045-6535, E-ISSN 1879-1298, Vol. 64, no 9, p. 1582-1591Article in journal (Refereed) Published
Abstract [en]

In order to evaluate blood levels of some perfluorinated chemicals (PFCs) and compare them to current levels of classical persistent organic pollutants (POPs) whole blood samples from Sweden were analyzed with respect to 12 PFCs, 37 polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (DDE), hexachlorobenzene (HCB), six chlordanes and three polybrominated diphenyl ethers (PBDEs). The median concentration, on whole blood basis, of the sum of PFCs was 20-50 times higher compared to the sum of PCBs and p,p'-DDE, 300-450 times higher than HCB, sum of chlordanes and sum of PBDEs. Estimations of the total body amount of PFCs and lipophilic POPs point at similar body burdens. While levels of for example PCBs and PBDEs are normalized to the lipid content of blood, there is no such general procedure for PFCs in blood. The distributions of a number of perfluorinated compounds between whole blood and plasma were therefore studied. Plasma concentrations were higher than whole blood concentrations for four perfluoroalkylated acids with plasma/whole blood ratios between 1.1 and 1.4, whereas the ratio for perflurooctanesulfonamide (PFOSA) was considerably lower (0.2). This suggests that the comparison of levels of PFCs determined in plasma with levels determined in whole blood should be made with caution. We also conclude that Swedish residents are exposed to a large number of PFCs to the same extent as in USA, Japan, Colombia and the few other countries from which data is available today.

National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3117 (URN)10.1016/j.chemosphere.2005.11.040 (DOI)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-12-14Bibliographically approved
4. Levels of 12 perfluorinated chemicals in pooled Australian serum, collected 2002-2003, in relation to age, gender, and region
Open this publication in new window or tab >>Levels of 12 perfluorinated chemicals in pooled Australian serum, collected 2002-2003, in relation to age, gender, and region
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2006 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 40, no 12, p. 3742-3748Article in journal (Refereed) Published
Abstract [en]

Pooled serum samples from 3802 Australian residents were analyzed for four perfluoroalkylsulfonates, seven perfluoroalkylcarboxylates, and perfluorooctanesulfonamide (PFOSA). Serum was collected from men and women of five different age groups and from rural and urban regions in Australia. The highest mean concentration was obtained for perfluorooctane sulfonate (PFOS, 20.8 ng/mL) followed by perfluorooctanoic acid (PFOA, 7.6 ng/mL), perfluorohexane sulfonate (PFHxS, 6.2 ng/mL), perfluorononanoic acid (PFNA, 1.1 ng/mL), and PFOSA (0.71 ng/mL). Additional four PFCs were detected in 5-18% of the samples at concentrations near the detection limits (0.1-0.5 ng/mL). An increase in PFOS concentration with increasing age in both regions and genders was observed. The male pool levels of some of the age groups compared to females were higherfor PFOS, PFOA, and PFHxS. In contrast, PFNA concentrations were higher in the female pools. No substantial difference was found in levels of PFCs between the urban and rural regions. The levels are equal or higher than previously reported serum levels in Europe and Asia but lower compared to the U.S.A. These results suggest that emissions from production in the Northern Hemisphere are of less importance for human exposure.

National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3118 (URN)10.1021/es060301u (DOI)16830536 (PubMedID)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-12-14Bibliographically approved
5. Analysis of perfluorooctane sulfonate (PFOS) isomers: identification and pattern in human blood from Sweden, the United Kingdom and Australia
Open this publication in new window or tab >>Analysis of perfluorooctane sulfonate (PFOS) isomers: identification and pattern in human blood from Sweden, the United Kingdom and Australia
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3119 (URN)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-10-18Bibliographically approved
6. Exposure of perfluorinated chemicals through lactation: levels of matched human milk and serum and a temporal trend, 1996-2004, in Sweden
Open this publication in new window or tab >>Exposure of perfluorinated chemicals through lactation: levels of matched human milk and serum and a temporal trend, 1996-2004, in Sweden
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2007 (English)In: Environmental Health Perspectives, ISSN 0091-6765, Vol. 115, no 2, p. 226-230Article in journal (Refereed) Published
Abstract [en]

Background Only limited data exist on lactation as an exposure source of persistent perfluorinated chemicals (PFCs) for children.Objectives We studied occurrence and levels of PFCs in human milk in relation to maternal serum together with the temporal trend in milk levels between 1996 and 2004 in Sweden. Matched, individual human milk and serum samples from 12 primiparous women in Sweden were analyzed together with composite milk samples (25–90 women/year) from 1996 to 2004.Results Eight PFCs were detected in the serum samples, and five of them were also above the detection limits in the milk samples. Perfluorooctanesulfonate (PFOS) and perfluorohexanesulfonate (PFHxS) were detected in all milk samples at mean concentrations of 0.201 ng/mL and 0.085 ng/mL, respectively. Perfluorooctanesulfonamide (PFOSA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were detected less frequently.Discussion The total PFC concentration in maternal serum was 32 ng/mL, and the corresponding milk concentration was 0.34 ng/mL. The PFOS milk level was on average 1% of the corresponding serum level. There was a strong association between increasing serum concentration and increasing milk concentration for PFOS (r2 = 0.7) and PFHxS (r2 = 0.8). PFOS and PFHxS levels in composite milk samples were relatively unchanged between 1996 and 2004, with a total variation of 20 and 32% coefficient of variation, respectively.Conclusion The calculated total amount of PFCs transferred by lactation to a breast-fed infant in this study was approximately 200 ng/day. Lactation is a considerable source of exposure for infants, and reference concentrations for hazard assessments are needed.

National Category
Environmental Sciences Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:oru:diva-3120 (URN)10.1289/ehp.9491 (DOI)
Available from: 2006-09-22 Created: 2006-09-22 Last updated: 2017-10-18Bibliographically approved

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Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
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  • en-US
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  • Other locale
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Output format
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  • asciidoc
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