Bavel, B., van

Boer, J., de

Kaerman, A.

Leeuwen, S.P.J., van

Lindstroem, G.

Name not available

Perfluorinated compounds in human plasma and blood - 1st worldwide interlaboratory study

Bavel, van, B.

Leeuwen, van, S.P.J.

Boer, de, J.

NARCIS 

Wageningen Yield 

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Introduction 
Accurate and reproducible analysis of perfluorinated alkyl compounds (PFCs) in human tissue is a challenge in many 
ways1. An interlaboratory study was initiated to survey the current quality and conformity of results of PFC analysis 
performed by different laboratories worldwide. Methods, matrices and reference materials used for PFC analysis 
differ between laboratories. Many factors, such as contamination from laboratory materials, incomplete recoveries 
and contamination from instrumental parts are common problems, and can lead to poor accuracy, sensitivity or 
reproducibility. Due to their physical and chemical properties PFCs also tend to adsorb to surfaces, and can be lost 
at any stage of the sample handling. Today LC-MS electrospray is the most common detection technique used for 
PFC analysis. This technique is sensitive to ion-suppression, both from the matrix or from poorly separated PFCs. 
Branched isomers further challenge separation and reference standards are needed to avoid interferences. In 
addition, new methods for various matrices are continuously being developed. A perfect quality assurance tool to 
standardize results for PFCs is worldwide interlaboratory studies.  
The Netherlands Institute for Fisheries Research and Örebro University organized this interlaboratory study in 
collaboration with the EU Perforce research project. The study covers environmental matrices, a standard solution, 
and human plasma and blood. Here the results from the plasma and blood interlaboratory are reported. 
Method and materials 
Samples
 
The human matrices part of the interlaboratory study consisted of a plasma sample and a whole blood sample. 
Laboratories were asked to use any method they preferred, and to analyze as many PFCs possible. Nineteen 
laboratories signed up for this part, and 17 of these have returned final results. All 17 laboratories reported results for 
the plasma sample and 11 laboratories also analyzed the whole blood sample. Authentic blood samples, without 
addition of PFCs, representing the current levels of PFCs in the Swedish general population were used. The 
samples were administrated by the University Hospital of Örebro (USÖ), Sweden, and were released for medical 
use according to the regulations by the Swedish National Board for Health and Welfare. Before shipment to the 
participants, the materials were homogenized and divided into polypropylene tubes in approximately 3 mL portions 
for whole blood and 7 mL for plasma.  
The stability, including within and between tube homogeneity, of the materials at room temperature as well as at 
elevated (37°) temperature was established. Homogeneity within and between tubes (n=3-8) varied with a coefficient 
of variation (CV) between 1-4 % for PFOS concentration in whole blood and plasma. Whole blood and plasma 
samples stored at 20°C were analyzed at day 0, 2, 9 and resulted in PFOS variation (CV) between 1-14%, 
corresponding variation for storage at 37° and analysis at day 0, 2, 9 was 13-16%. 
PFCs
 
The PFCs mentioned in this report are perfluorobutanesulfonate (PFBuS), perfluorohexanesulfonate (PFHxS), 
perfluorooctanesulfonate (PFOS), perfluorodecanesulfonate (PFDS), perfluorohexanoate (PFHxA), 
perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate 
(PFDA), perfluoroundecanoate (PFUnDA), perfluorododecanoate (PFDoDA), perfluorotetradecanoate (PFTDA) 
and perfluorooctanesulfonamide (PFOSA). 
Methods used by participants
 
Clean-up methods ranged from ion-pair extraction, different types of solid-phase extractions to only protein 
Perfluorinated compounds in human plasma and blood - 1st worldwide interlaboratory 
study
Anna Kärrman, Bert van Bavel, Stefan van Leeuwen, Jacob de Boer, Gunilla Lindström
EMG - Fluorinated Compounds
805Organohalogen Compounds - Volume 67 (2005)
precipitation. Analysis and detection methods were for example LC-ESI-MS/MS (triple quadrupole), LC-ESI-MS 
(single quadrupole), LC-ESI-TOF-MS and GC-MS. Quantification was performed by using extracted or non-extracted 
standard curves with or without matrix or internal standard present. 
Results and discussion  
Of the total 19 laboratories that entered the human matrices part of the study 89% reported results. This must be 
considered a good report frequency. Up to the present the most published PFC data in the scientific literature 
concern plasma or serum levels. This is also reflected in the lower number (58%) of laboratories that analyzed the 
whole blood sample as well.  
In Figure 1 the mean and standard deviation for PFOS determination in plasma based on each laboratory’s reported 
value are given.  
 
Figure 1. Mean (mv), standard deviation limits (SD) and individual results for PFOS concentration in plasma 
reported by 18 laboratories.  
No processing of data or removal of outliers have been performed on the data presented, and consequently no 
consensus value is given here. Tables 1 and 2 show the results for a number of PFCs in the plasma and whole blood 
sample reported from the different laboratories. Mean and variability (CV) are given if sufficient number of 
participants (>50%) reported above the detection limit. Since not all participants reported the exact limit of detection 
all non-detect values were excluded from the calculations. The number of PFCs reported (found values or detection 
limits) varied between laboratories.  
 
 
 
 
 
 
 
 
 
 
 
 
 
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806Organohalogen Compounds - Volume 67 (2005)
  
 
 
 
Table 1. Plasma results in ng/mL or ng/g (given in italic) presented as they were reported from each laboratory. 
NA=not analysed, ND=not detected, NQ=not quantified. 
a Lab 31 reported two results using two different methods. 
 
b
 ng/g results have been used for calculation of the mean without recalculation on a ng/mL basis. 
 
Almost all laboratories reported values for PFOS and PFOA. The CV for PFOS was 30% for plasma and 59% for 
whole blood. Corresponding results for PFOA were 50 and 41%. A lower number of participants reported levels for 
PFNA and PFHxS and the variations were larger compared to PFOS and PFOA. Included in Tables 1 and 2 are low 
concentrations of other PFCs reported within this study. 
Considering that this is the first interlaboratory study on a larger worldwide scale and the number of different methods 
used, the variation between participating laboratories is satisfactory. Concentrations of approximately 10-20 ng/ml 
for PFOS and 2 ng/ml for PFOA in whole blood and plasma can be determined reasonably well by most 
laboratories, and the coefficient of variation will further improve after removing obvious outliers and possible 
erroneous numbers reported. In the next round of PFC interlaboratory studies it would be preferable to use human 
samples with higher concentrations of other PFCs that have frequently been reported in human blood, for instance 
PFOSA. 
 
 
 
 
 
Code PFOS PFOA PFNA PFHxS PFOSA PFBS PFDS PFHpA PFDA PFUnDA
Lab 2 34.9 2.11 0.909 0.616 <0.029 <0.342 NA <0.043 0.281 0.309
Lab 3 31.1 1.19 0.77 NA NA NA NA ND ND ND
Lab 5 21.9 1.5 <0.4 NA <0.7 NA NA NA <0.4 <0.1
Lab 10 7.1 0.5 NA <0.05 <0.05 NA NA NA NA NA
Lab 12 31 2.04 0.52 NA NA 0.29 NA NA NA NA
Lab 16 19.92 1.5 0.38 0.78 <0.01 0.02 NA <0.05 <0.05 0.14
Lab 17 25.3 2.0 0.62 NA ND NA NA NA ND NA
Lab 22 22.2 3.63 1.14 1.38 <0.16 <0.01 0.22 0.09 0.31 0.22
Lab 23 31 2.4 0.72 1.9 0.62 <2.4 1.7 0.68 0.59 0.44
Lab 24 22 1.4 0.5 1.6 0.6 <2 <0.5 NA <0.2 <0.1
Lab 25 24.8 2.03 0.29 1.7 ND ND NA NA 0.63 0.14
Lab 29 11 2 NA 4 NA <0.2 NA 0.55 <0.2 <0.1
Lab 30 NA 5.2 NQ NA NA NA NA NA NQ NQ
Lab 31a 18.8 1.9 NQ 1.1 <0.2 0.5 NA <0.3 <0.3 <0.3
Lab 31a 19.9 1.8 0.4 0.8 0.1 0.5 NA <0.4 0.2 0.2
Lab 32 NA 2.8 NA NA NA NA NA NA NA NA
Lab 34 22.7 2.2 NA 1.3 NA <1.0 NA NA NA NA
Lab 35 22.7 1.8 1.25 NA NA NA NA NA NA NA
MEANb 22.9 2.11 0.68 1.52
SD 7.2 1.02 0.31 0.97
CV 32 % 48 % 46 % 64 %
EMG - Fluorinated Compounds
807Organohalogen Compounds - Volume 67 (2005)
  
 
Table 2. Whole blood results in ng/mL or ng/g (given in italic) presented as they were reported from each laboratory. 
NA=not analysed, ND=not detected, NQ=not quantified. 
a
 ng/g results have been used for calculation of the mean without recalculation on a ng/mL basis. 
 
Acknowledgment 
MD Olle Berséus at the University Hospital of Örebro is acknowledged for supplying the sample material.  
The participants in this study were: Urs Berger, NILU, Norway; Antonia Calafat, CDC, USA; Paul Connolly, Exygen 
Research, USA; David Ehresman, 3M Strategic Toxicology Laboratory, USA; Dale Hoover, AXYS Analytical 
Services Ltd, Canada; Hans-Wolfgang Hoppe, MedLab Bremen, Germany; Ulf Järnberg, ITM, Sweden; Anna 
Kärrman, MTM, Sweden; Josef Müller, Fraunhofer Institute for Molecular Biology and Applied Ecology, Germany; 
Hiroyuki Nakazawa, Hoshi University, Japan; Robert Peter, Ciba Speciality Chemicals Inc, Switzerland; Charles R. 
Powley, DuPont Haskell Laboratories, USA; William Reagen, 3M Environmental Laboratory, USA; Brian F. Scott, 
National Water Research Institute, Canada; Sheryl Tittlemier, Health Canada; Lee Wolf, Columbia Analytical 
Services, USA; Nobuyoshi Yamashita, EMTECHAist Japan.  
References 
1. Martin, J. W.; Kannan, K.; Berger, U.; de Voogt, P.; Field, J.; Franklin, J.; Giesy, J. P.; Harner, T.; Muir, D. C.; Scott, 
B.; Kaiser, M.; Järnberg, U.; Jones, K. C.; Mabury, S. A.; Schroeder, H.; Simcik, M.; Sottani, C.; van Bavel, B.; 
Kärrman, A.; Lindström, G.; van Leeuwen, S. (2004) Environmental Science and Technology. 248A-255A.  
Code PFOS PFOA PFNA PFHxS PFOSA PFBS PFDS PFHpA PFDA PFUnDA
Lab 2 9.09 2.15 0.49 1.63 0.305 <0.006 NA 0.116 0.239 0.275
Lab 5 9.3 1.7 <0.4 NA <0.7 NA NA NA <0.4 <0.1
Lab 12 10.6 2.13 0.19 NA NA <2 NA NA NA NA
Lab 16 7.3 1.62 0.29 0.66 0.24 <0.02 NA <0.1 0.11 <0.2
Lab 17 10.0 1.8 0.53 NA ND NA NA NA ND NA
Lab 22 11.8 4.06 0.87 1.17 0.45 <0.01 0.02 0.22 0.47 0.26
Lab 23 24 1.4 0.5 1.4 1.6 <2.4 <0.5 <0.6 0.5 <0.3
Lab 24 10 2 0.4 1.5 0.5 <2 <0.5 NA <0.1 <0.1
Lab 29 1.8 1.4 NA 0.99 NA <0.2 NA 0.54 <0.2 <0.1
Lab 30 NA 3.6 NQ NA NA NQ NA NA NQ ND
Lab 32 NA 2.62 NA NA NA NA NA NA NA NA
MEANa 10.4 2.23 0.47 1.14
SD 5.85 0.88 0.22 0.34
CV 56 % 39 % 46 % 29 %
EMG - Fluorinated Compounds
808Organohalogen Compounds - Volume 67 (2005)


Perfluorinated compounds in human plasma and blood - 1st worldwide interlaboratory study

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