Journal of Environmental Health Sciences (한국환경보건학회지)

Korean Society of Environmental Health (한국환경보건학회)
권호 표지
DOI QR코드

DOI QR Code

Method Development and Cross Validation of Analysis of Hydroxylated Polycyclic Aromatic Hydrocarbons (OH-PAHs) in Human Urine

소변 중 다환방향족탄화수소 대사체의 분석법 확립 및 교차분석

  • Park, Na-Youn (Department of Health, Environment & Safety, Eulji University) ;
  • Jeon, Jung-Dae (Department of Health, Environment & Safety, Eulji University) ;
  • Koo, Hyeryeong (Institute of Metabolism, Green Cross Laboratories) ;
  • Kim, Jung Hoan (Food Technology & Service, Eulji University) ;
  • Lee, Eun-Hee (Graduate School of Health Science, Far-East University) ;
  • Lee, Kyungmu (Department of Environmental Health, Korea National Open University) ;
  • Mun, Cheoljin (Institute of Metabolism, Green Cross Laboratories) ;
  • Kho, Younglim (Department of Health, Environment & Safety, Eulji University)
  • 박나연 (을지대학교 보건환경안전학과) ;
  • 전중대 (을지대학교 보건환경안전학과) ;
  • 구혜령 (녹십자의료재단 대사의학연구소) ;
  • 김정환 (을지대학교 식품산업외식학과) ;
  • 이은희 (극동대학교 보건과학대학원) ;
  • 이경무 (한국방송통신대학교 환경보건학과) ;
  • 문철진 (녹십자의료재단 대사의학연구소) ;
  • 고영림 (을지대학교 보건환경안전학과)
  • Received : 2015.07.09
  • Accepted : 2015.10.15
  • Published : 2015.10.28
Download PDF
⟨ Previous Next ⟩

Abstract

Objectives: This study was performed to evaluate the analytical method for PAH metabolites in human urine using enzyme hydrolysis and solid-phase extraction coupled with LC-(ESI)-MS/MS technique. Methods: We employed HPLC tandem mass spectrometry techniques with appropriate pre-treatment for analysis of 16 OH-PAHs in human urine. Samples were hydrolysis by ${\beta}$-flucuronidase/Aryl sulfatase, and target compounds were extracted by solid-phase extraction with a strata-x cartridge. Cross-validation was performed between Eulji University and Green Cross laboratories with 200 human urine samples. Results: The accuracies were between 90.3% and 118.8%, and precisions (relative standard deviations) were lower than 10%. The linearity obtained was satisfying for the 16 OH-PAH compounds, with a coefficient of determination ($r^2$) higher than 0.99. The results of cross-validation at the two organizations were compared by ICC (interclass correlation coefficient) values. The cross-validation results were excellent or good for all compounds. Conclusion: An analytical method was validated for low nanogram levels of 16 OH-PAHs in human urine. Also, satisfying results were obtained for method validation such as accuracy, precision and ICC of cross-validation.

Keywords

References

  1. Rengarajan T, Rajendran P, Nandakumar N, Lokeshkumar B, Rajendran P, Nishigaki I. Exposure to polycyclic aromatic hydrocarbons with special focus on cancer. Asian Pacific Journal of Tropical Biomedicine. 2015; 5(3): 182-18. https://doi.org/10.1016/S2221-1691(15)30003-4
  2. Motorykin O, Schrlau J, Jia Y, Harper B, Harris S, Harding A, et al. Determination of parent and hydroxy PAHs in personal PM2.5 and urine samples collected during Native American fish smoking activities. Science of the Total Environment. 2015; 505: 694-703. https://doi.org/10.1016/j.scitotenv.2014.10.051
  3. Levine H, Berman T, Goldsmith R, Goen T, Spungen J, Novack L, et al. Urinary concentrations of polycyclic aromatic hydrocarbons in Israeliadults: Demographic and life-style predictors. International Journal of Hygiene and Environmental Health. 2015; 218: 123-131. https://doi.org/10.1016/j.ijheh.2014.09.004
  4. Serrano M, Bartolomee M, Gallego-Picoo A, Garcinunno RM, Bravo JC, Fernaandez P. Synthesis of a molecularly imprinted polymer for the isolation of 1-hydroxypyrene in human urine. Talanta. 2015; 143: 71-76. https://doi.org/10.1016/j.talanta.2015.04.092
  5. IARC. Polynuclear aromatic compounds: Part 1. Chemical, environmental and experimental data. IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans, 32, 1983. p. 1-453.
  6. Sung T, Lee JS, Lee HG. Benzo(a)pyrene Contents in commercial vegetable oils and changes during processing of vegetable oils. Korean J Food Sci Technol. 2012; 44(3): 269-273. https://doi.org/10.9721/KJFST.2012.44.3.269
  7. Bartolome M, Ramos JJ, Cutanda F, Huetos O, Esteban M, Ruiz-Moraga M, et al. Urinary polycyclic aromatic hydrocarbon metabolites levels in a representative sample of the Spanish adult population: The BIOAMBIENT.ES project. Chemosphere. 2015; 135: 436-446. https://doi.org/10.1016/j.chemosphere.2014.12.008
  8. Hara K, Hanaka T, Yamana Y, Itani T. Urinary 1- hydroxypyrene levels of garbage collectors with low-level exposure to polycyclic aromatic hydrocarbons. The Science of the Total Environment. 1997; 199: 159-164. https://doi.org/10.1016/S0048-9697(97)05491-0
  9. Merlo F, Andreassen A, Weston A, Pan CF, Hauqen A, Valerio F, et al. Urinary excretion of 1- hydroxypyrene as a marker for exposure to urban air levels of polycyclic aromatic hydrocarbons. Cancer Epidmiol Biomarkers Prev. 1998; 7(2): 147-155.
  10. Chetiyanukornkul T, Toriba A, Kameda T, Tang N, Hayakawa K. Simultaneous determination of urinary hydroxylated metabolites of naphthalene, fluorene, phenanthrene, fluoranthene and pyrene as multiple biomarkers of exposure to polycyclic aromatic hydrocarbons. Anal Bioanal Chem. 2006; 386: 712-718. https://doi.org/10.1007/s00216-006-0628-6
  11. Hagedorn HW, Scherer G, Engl J, Riedel K, Cheung F, Errington G, et al. Urinary excretion of phenolic polycyclic aromatic hydrocarbons (OH-PAH) in nonsmokers and in smokers of cigarettes with different ISO tar yields. Journal of Analytical Toxicology. 2009; 33(6): 301-309. https://doi.org/10.1093/jat/33.6.301
  12. Xu X, Zhang J, Zhang L, Liu W, Weisel CP. Selective detection of monohydroxy metabolites of polycyclic aromatic hydrocarbons in urine using liquid chromatography/triple quadrupole tandem mass spectrometry. Rapid Commun Mass Spectrom. 2004; 18(19): 2299-2308. https://doi.org/10.1002/rcm.1625
  13. Fan R, Ramage R, Wang D, Zhou J, She J. Determination of ten monohydroxylated polycyclic aromatic hydrocarbons by liquid-liquid extraction and liquid chromatography/tandem mass spectrometry. Talanta. 2012; 93: 383-391. https://doi.org/10.1016/j.talanta.2012.02.059
  14. Zhao G, Chen Y, Wang S, Yu J, Wang X, Xie F. Simultaneous determination of 11 monohydroxylated PAHs in human urine by stir bar sorptive extraction and liquid chromatography/tandem mass spectrometry. Talanta. 2013; 116: 822-826. https://doi.org/10.1016/j.talanta.2013.07.071
  15. Yu J, Wang S, Zhao G, Wang B, Ding L, Zhang X, et al. Determination of urinary aromatic amines in smokers andnonsmokers using a MIPs-SPE coupled with LC–MS/MS method. Journal of Chromatography B. 2014; 958: 130-135. https://doi.org/10.1016/j.jchromb.2014.03.023
  16. Onyemauwa F, Rappaport SM, Sobus JR, Gajdosova D, Wu R, Waidyanatha S. Using liquid chromatography– tandem mass spectrometry to quantify monohydroxylated metabolites of polycyclic aromatic hydrocarbons in urine. Journal of Chromatography B. 2009; 877(11-12): 1117-1125. https://doi.org/10.1016/j.jchromb.2009.02.067
  17. Luo K, Gao Q, Hu J. Derivatization method for sensitive determination of 3-hydroxybenzo[a]pyrene in human urine by liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography A. 2015; 1379: 51-55. https://doi.org/10.1016/j.chroma.2014.12.043
  18. Zhang X, Hou H, Xiong W, Hu Q. Development of a method to detect three monohydroxylated polycyclic aromatic hydrocarbons in human urine by liquid chromatographic tandem mass spectrometry. Journal of Analytical Methods in Chemistry. 2015; 2015: 1-9.
  19. Amorim LCA, Dimandja JM, Cardeal ZL. Analysis of hydroxylated polycyclic aromatic hydrocarbons in urine using comprehensive two-dimensional gas chromatography with a flame ionization detector. Journal of Chromatography A. 2009; 1216: 2900-2904. https://doi.org/10.1016/j.chroma.2008.11.012
  20. Lia Z, Sandau CD, Romanoff LC, Caudill SP, Sjodin A, Needham LL, et al. Concentration and profile of 22 urinary polycyclic aromatic hydrocarbon metabolites in the US population. Environmental Research. 2008; 107: 320-331. https://doi.org/10.1016/j.envres.2008.01.013
  21. Killip S, Mabfoud Z, Pearce K. What is an intracluster correlation coeffi cient? crucial concepts for primary care researchers. Annals of Family Medicine. 2004: 2(3); 204-208. https://doi.org/10.1370/afm.141
  22. Pinedo M, Villacorta E, Tapia C, Arnold R, Lopez J, Revilla A, et al. Inter- and intra-observer variability in the echocardiographic evaluation of right ventricular function. Rev Esp Cardiol. 2010; 63: 802-809. https://doi.org/10.1016/S0300-8932(10)70183-4