DOI QR코드

DOI QR Code

Determination of 4 Parabens in Human Urine by Online SPE and LC-MS/MS Techniques

온라인 고체상추출과 LC-MS/MS 기술을 이용한 소변 중 파라벤류 분석

  • Kim, Jung Hoan (Department of Food Technology & Service, Eulji University) ;
  • Kho, Young Lim (Department of Health, Environment & Safety, Eulji University) ;
  • Kim, Pan Gyi (Department of Occupational & Environmental Health, Yongin University) ;
  • Jeong, Jee Yeon (Department of Occupational & Environmental Health, Yongin University) ;
  • Lee, Eun Hee (Graduate School of Health Science, Far East University) ;
  • Lee, Seung-Youl (Health Effect Analysis Team, National Institute of Food and Drug Safety Evaluation, Korea Food and Drug Administration) ;
  • Nam, Hye-Seon (Health Effect Analysis Team, National Institute of Food and Drug Safety Evaluation, Korea Food and Drug Administration) ;
  • Rhee, Gyu-Seek (Health Effect Analysis Team, National Institute of Food and Drug Safety Evaluation, Korea Food and Drug Administration)
  • 김정환 (을지대학교 식품산업외식학과) ;
  • 고영림 (을지대학교 보건환경안전학과) ;
  • 김판기 (용인대학교 산업환경보건학과) ;
  • 정지연 (용인대학교 산업환경보건학과) ;
  • 이은희 (극동대학교 보건과학대학원) ;
  • 이승열 (식품의약품안전평가원 위해영향연구팀) ;
  • 남혜선 (식품의약품안전평가원 위해영향연구팀) ;
  • 이규식 (식품의약품안전평가원 위해영향연구팀)
  • Received : 2012.11.13
  • Accepted : 2012.11.27
  • Published : 2012.12.31

Abstract

Objectives: Parabens are widely used as antimicrobial agents in pharmaceuticals and cosmetics as well as by the food industry. Parabens have been reported to show weak estrogenic activity and be related to health effects such as allergic reactions and skin and breast cancer. We evaluated an online solid phase extraction (SPE) method coupled with LC-MS/MS technique using free and conjugated parent parabens in human urine for assessing human exposure to parabens. Methods: We employed LC/MS/MS through online solid phase extraction and column-switching techniques and analyzed free and conjugated parabens as biomarkers of human exposure. Four major parabens, methyl-paraben (MP), ethyl-paraben (EP), propyl-paraben (PP) and butyl-paraben (BP), were analyzed. Method validation was performed by sensitivity, accuracy, precision and comparison of the results of online SPE with offline SPE. Results: The limits of detection (LOD) were in the range of 0.2-2 ng/mL, and actual limits of quantification (LOQ) were in the range of 0.7-6 ng/mL urine, depending upon the compound. Accuracy was in the range of 98.3-106.4%, and precision was in the range of 1.3-8.7% (CV) depending upon the compound. We found a good correlation between the results of analysis by online SPE method and that by off-line SPE method. Conclusions: The online SPE method showed proper LOD and validated accuracy, precision and good correlation with the offline method for analyzing parabens in urine.

Keywords

References

  1. Darbre PD, Aljarrah A, Miller WR, Coldham NG, Sauer MJ, Pope GS. Concentrations of Parabens in Human Breast Tumours, J. Appl. Toxicol. 2004; 24: 5-13. https://doi.org/10.1002/jat.958
  2. Food and Drug Administraion, Available: Selected cosmetics ingredients > Parabens. http://www.fda.gov/Cosmetics/ProductandIngredientSafety/SelectedCosmeticIngredients/ucm128042.htm [accessed 28 October 2012].
  3. Ye X, Bishop AM, Needham LL, Calafat AM, Automated on-line column-switching HPLC-MS/ MS method with peak focusing for measuring parabens, triclosan, and other environmental phenols in human milk, analytica chimica acta. 2008; 622: 150-156. https://doi.org/10.1016/j.aca.2008.05.068
  4. Kohl L, Blondeel A, Song M. Allergic contact dermatitis from cosmetics. Retrospective analysis of 819 patch-tested patients. Dermatology. 2002; 204: 334-337. https://doi.org/10.1159/000063379
  5. Jung JY, Narmandakh J, Hong JS, Eun HC. A study of the patch test results with preservative antigens for patients with suspected cosmetic contact dermatitis, Korean J. Dermatol. 2010; 48(2): 109- 114.
  6. Korea Food and Drug Administraion, Notification of amendments. Available: http://www.kfda.go.kr/index.kfda?mid=95&seq=2482&cmd=v [accessed 28 October 2012].
  7. Korea Food and Drug Administration, Online pharmaceutical Library. Available: http://drug.kfda.go.kr/html/businessB_01.jsp?p_menuId=0502#1 [accessed 20 November 2012].
  8. Danish center on endocrine disrupters, Evaluation of tebuconazole, triclosan, methylparaben and ethylparaben according to the Danish proposal for criteria for endocrine disrupters, 2012.
  9. Lee SY, Lee SH. Effect of methyl paraven on the onset of puberty in immature female rats. Sangmyung Univ. J. Natural Sci. 2009; 20: 1-16.
  10. Oishi S. Effects of butyl paraben on the male reproductive system in mice, Arch Toxicol. 2002; 76(7): 423-429. https://doi.org/10.1007/s00204-002-0360-8
  11. Ye X, Kuklenyik Z, Bishop AM, Needham LL, Calafat AM, Quantification of the urinary concentrations of parabens in humans by on-line solid phase extraction-high performance liquid chromatography- isotope dilution tandem mass spectrometry, Journal of Chromatography B. 2006; 844: 53-59. https://doi.org/10.1016/j.jchromb.2006.06.037
  12. FDA, Validation of analytical procedures: Methodology, recommended for implementation at step 7 of the VICH process on 22 October 1998 by the VICH steering committee(64. guidance for industry), FDA, DHHS, 1998.
  13. Robinson JW, Frame EMS, Frame II GM, undergraaduate instrumental analysis 6th ed., Marcel Dekker; 2005. p.57.
  14. Casas L, Fernndez MF, Llop S, Guxens M, Ballester F, Olea N, Irurzun MB, Rodrguez LSM, Riao I, Tardn A, Vrijheid M, Calafat AM, Sunyer J, Urinary concentrations of phthalates and phenols in a population of Spanish, pregnant women and children, Environment International. 2011; 37: 858-866. https://doi.org/10.1016/j.envint.2011.02.012
  15. Boberg J, Taxvig C, Christiansen S, Hass U, Possible endocrine disrupting effects of parabens and their metabolites, Reproductive Toxicology. 2010; 30: 301-312. https://doi.org/10.1016/j.reprotox.2010.03.011
  16. Ye X, Bishop AM, Reidy JA, Needham LL, and Calafat AM, Parabens as Urinary Biomarkers of Exposure in Humans, Environ Health Perspectives. 2006; 114(12): 1843-1846.
  17. Shirai S, Suzuki Y, Yoshinaga J, Shiraishi H, Mizumoto Y, Urinary excretion of parabens in pregnant Japanese women, Reproductive Toxicology. 2012; in press.

Cited by

  1. Analysis Method of Parabens in Human Breast Milk by LC-MS/MS System vol.60, pp.2, 2016, https://doi.org/10.5012/jkcs.2016.60.2.118