TY - JOUR
T1 - Trace analysis of total fluorine in human blood using combustion ion chromatography for fluorine
T2 - A mass balance approach for the determination of known and unknown organofluorine compounds
AU - Miyake, Yuichi
AU - Yamashita, Nobuyoshi
AU - So, Man Ka
AU - Rostkowski, Pawel
AU - Taniyasu, Sachi
AU - Lam, Paul K.S.
AU - Kannan, Kurunthachalam
N1 - Funding Information:
We thank Mr. Norio Hayashi and Mr. Masanori Hirai (Dia Instruments Co. Ltd, Japan) for their technical support of CIC. Part of this study was supported by a research grant from New Energy and Industrial Technology Development Organization (NEDO), project number 05A21502d (2006–2008), Japan.
PY - 2007/6/22
Y1 - 2007/6/22
N2 - The number of perfluorochemicals (PFCs) that have been found in biological and environmental matrices is increasing as analytical standards and methods evolve. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) constitute only a fraction of the total suite of PFCs found in environmental and biological matrices. A robust method and approach is needed to evaluate the mass of fluorinated compounds in biological matrices. In this study, we developed a method to measure total fluorine (TF) and organic fluorine (TOF) in human blood matrices using combustion ion chromatography (CIC). Blood matrices (whole blood, serum, and plasma) were analyzed in bulk to determine TF. An aliquot of the blood was also extracted with organic solvents such as methyl-tert-butyl ether (MTBE) and hexane, and organic and aqueous extracts were separated, to fractionate organofluorines from inorganic fluorine. The organic layer was analyzed for TF by CIC, and for known PFCs by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). PFCs measured by HPLC-MS/MS accounted for >80% of the TF in the organic fraction. The aqueous fraction contained inorganic fluorine and other non-extractable organofluorines. However, in the bulk sample, fluoride and non-extractable organofluorines accounted for >70% of the TF in blood samples from the general population. In occupationally exposed individuals, known organofluorines accounted for a major proportion of the TF. These results suggest the existence of yet uncharacterized fluorine fraction in human blood. Further studies are needed to characterize the aqueous fraction that contains inorganic fluorine and non-extractable forms of fluorine.
AB - The number of perfluorochemicals (PFCs) that have been found in biological and environmental matrices is increasing as analytical standards and methods evolve. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) constitute only a fraction of the total suite of PFCs found in environmental and biological matrices. A robust method and approach is needed to evaluate the mass of fluorinated compounds in biological matrices. In this study, we developed a method to measure total fluorine (TF) and organic fluorine (TOF) in human blood matrices using combustion ion chromatography (CIC). Blood matrices (whole blood, serum, and plasma) were analyzed in bulk to determine TF. An aliquot of the blood was also extracted with organic solvents such as methyl-tert-butyl ether (MTBE) and hexane, and organic and aqueous extracts were separated, to fractionate organofluorines from inorganic fluorine. The organic layer was analyzed for TF by CIC, and for known PFCs by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). PFCs measured by HPLC-MS/MS accounted for >80% of the TF in the organic fraction. The aqueous fraction contained inorganic fluorine and other non-extractable organofluorines. However, in the bulk sample, fluoride and non-extractable organofluorines accounted for >70% of the TF in blood samples from the general population. In occupationally exposed individuals, known organofluorines accounted for a major proportion of the TF. These results suggest the existence of yet uncharacterized fluorine fraction in human blood. Further studies are needed to characterize the aqueous fraction that contains inorganic fluorine and non-extractable forms of fluorine.
KW - Fluoride
KW - Human blood
KW - Ion chromatography
KW - PFOA
KW - PFOS
KW - Perfluorochemicals
UR - http://www.scopus.com/inward/record.url?scp=34249717348&partnerID=8YFLogxK
U2 - 10.1016/j.chroma.2007.03.084
DO - 10.1016/j.chroma.2007.03.084
M3 - Article
C2 - 17416376
AN - SCOPUS:34249717348
SN - 0021-9673
VL - 1154
SP - 214
EP - 221
JO - Journal of Chromatography A
JF - Journal of Chromatography A
IS - 1-2
ER -