Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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Analysis of Synthetic Fragrances (SFs) in Water Using Stir Bar Sorptive Extraction (SBSE) and GC-MS/MS

교반막대 추출법과 GC-MS/MS를 이용한 수중의 합성 향물질류 분석

  • 서창동 (부산광역시 상수도사업본부 수질연구소) ;
  • 손희종 (부산광역시 상수도사업본부 수질연구소) ;
  • 염훈식 (부산광역시 상수도사업본부 수질연구소) ;
  • 최진택 (부산광역시 상수도사업본부 수질연구소) ;
  • 류동춘 (부산광역시 상수도사업본부 수질연구소) ;
  • 권기원 (부산광역시 상수도사업본부 수질연구소) ;
  • 장성호 (부산대학교 바이오환경에너지학과)
  • Received : 2014.04.11
  • Accepted : 2014.05.30
  • Published : 2014.06.30
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Abstract

A highly sensitive analytical method based on stir bar sorptive extraction (SBSE) technique and gas chromatography/tandem mass spectrometry (GC-MS/MS) has been developed, allowing the simultaneous multi-analyte determination of 11 synthetic fragrances (SFs) in water samples. The stir bar coated with polydimethylsiloxane (PDMS) was added to 40 mL of water sample at pH 3 and stirred at 1,100 rpm for 120 min. Other SBSE parameters (salt effect and presence of organic solvent) were optimised. The method shows good linearity (coefficients > 0.990) and reproducibility (RSD < 10.9%). The extraction efficiencies were above 83% for all the compounds. The limits of detections (LOD) and limits of quantification (LOQ) were 2.1~4.1 ng/L and 6.6~12.9 ng/L, respectively. The developed method offers the ability to detect 11 SFs at ultra-low concentration levels with only 40 mL of sample volume. Matrix effects in tap water, river water, wastewater treatment plant (WWTP) final effluent water and seawater were investigated and it was shown that the method is suitable for the analysis of trace level of 11 SFs. The method developed in the present study has the advantage of being rapid, simple, high-sensitive and both user and environmentally friendly.

본 연구에서는 SBSE 전처리 장치와 GC-MS/MS를 이용하여 합성 향물질 11종을 동시 분석할 수 있는 분석법을 개발하기 위해 흡착 bar의 교반시간, 교반속도, 시료수의 pH, 시료수 용량, 염석제 투입량 및 메탄올 주입량 변화 등 SBSE (stir bar sorptive extraction) 전처리 조건과 GC-MS/MS (gas chromatography/tandem mass spectrometry)의 기기조건을 다양하게 변화시켜 SBSE-GC-MS/MS를 이용한 분석법을 개발하였다. 11종의 합성 향물질들에 대한 검출한계(LOD)는 2.1~4.1 ng/L였으며, 정량한계(LOQ)는 6.6~12.9 ng/L였다. 수돗물, 낙동강 원수, 하수처리장 최종방류수 및 해수를 이용하여 시료수의 matrix 영향을 살펴본 결과, 11종의 합성 향물질들의 회수율 및 RSD의 경우 각각 88%~119% 및 0.8%~7.5%로 양호한 결과를 나타내어 시료수의 matrix 영향을 받지 않는 것으로 나타났다. 본 연구에서 개발된 SBSE-GC-MS/MS 분석법은 40 mL 정도의 적은 시료수량으로도 고감도 분석이 가능하며, 용매류를 사용하지 않기 때문에 분석자의 건강 및 환경친화적인 분석법이라는 장점뿐만 아니라 간편하고, 빠르며 자동화된 방법이라는 장점을 가진다.

Keywords

References

  1. Rimkus, G. G., "Polycyclic musk fragrances in the aquatic environment," Toxicol. Lett., 111, 37-56(1999). https://doi.org/10.1016/S0378-4274(99)00191-5
  2. Gatermann, R., Biselli, S., Hühnerfuss, H., Rimkus, G. G., Hecker, M. and Karbe, L., "Synthetic musks in the environment. Part 1: Species-dependent bioaccumulation of polycyclic and nitro musk fragrances in freshwater fish and mussels," Arch. Environ. Contam. Toxicol., 42, 437-446(2002). https://doi.org/10.1007/s00244-001-0041-2
  3. Hutter, H. P., Wallner, P., Moshammer, H., Hartl, W., Sattelberger, R., Lorbeer, G. and Kundi, M., "Blood concentrations of polycyclic musks in healthy young adults," Chemosphere, 59, 487-492(2005). https://doi.org/10.1016/j.chemosphere.2005.01.070
  4. Schmid, P., Kohler, M., Gujer, E., Zennegg, M. and Lanfranchi, M., "Persistent organic pollutants, brominated flame retardants and synthetic musks in fish from remote alpine lakes in Switzerland," Chemosphere, 67, S16-S21(2007). https://doi.org/10.1016/j.chemosphere.2006.05.080
  5. Raab, U., Preiss, U., Albrecht, M., Shahin, N., Parlar, H. and Fromme, H., "Concentrations of polybrominated diphenyl ethers, organochlorine compounds and nitro musks in mother's milk from Germany (Bavaria)," 72, 87-95(2008). https://doi.org/10.1016/j.chemosphere.2008.01.053
  6. Lee, I. S., Lee, S. H. and Oh, J. E., "Occurrence and fate of synthetic musk compounds in water environment," Water Res., 44, 214-222(2010). https://doi.org/10.1016/j.watres.2009.08.049
  7. Tanabe, S., "Synthetic musks-arising new environmental menace?," Mar. Pollut. Bull., 50, 1025-1026(2005). https://doi.org/10.1016/j.marpolbul.2005.07.005
  8. Nakata, H., "Occurrence of synthetic musk fragrances in marine mammals and sharks from Japanese costal waters," Environ. Sci. Technol., 39, 3430-3434(2005). https://doi.org/10.1021/es050199l
  9. Wan, Y., Wei, Q., Hu, J., Jin. X., Zhang, Z., Zhen, H. and Liu, J., "Levels, tissue distribution, and age-related accumulation of synthetic musk fragrances in Chinese sturgeon (Acipenser sinensis): comparison to organochlorines," Environ. Sci. Technol., 41, 424-430(2007). https://doi.org/10.1021/es061771r
  10. Schreurs, R. H., Sonneveld, E., van der Saag, P. T., Van der Burg, B. and Seinen, W., "Examination of the in vitro (anti)estrogenic, (anti)androgenic and (anti)dioxin-like activities of tetralin, indane and isochroman derivatives using receptor-specific bioassays," Toxicol. Lett., 156, 261-275 (2005). https://doi.org/10.1016/j.toxlet.2004.11.014
  11. Schreurs, R. H., Sonneveld, E., Jansen, J. H., Seinen, W. and Van der Burg, "Interaction of polycyclic musks and UV filters with the estrogen receptor (ER), androgen receptor (AR) and progesterone (PR) in reporter gene bioassays," Toxicol. Sci., 83, 264-272(2005).
  12. Mori, T., Iida, M., Ishibashi, H., Kohra, S., Takao, Y., Takemasa, T. and Arizono, K., "Hormonal activity of polycyclic musks evaluated by reporter gene assay," Environ. Sci., 14, 195-202(2007).
  13. Bizarro, C., Ros, O., Vallejo, A., Prieto, A., Etxebarria, N., Cajaraville, M. P. and Ortiz-Zarragoitia, M., "Intersex condition and molecular markers of endocrine disruption in relation with burdens of emerging pollutants in thicklip grey mullets (Chelon labrosus) from Basque estuaries (South- East Bay of Biscay)," Mar. Environ. Res., 96, 19-28(2014). https://doi.org/10.1016/j.marenvres.2013.10.009
  14. Seo, C. D., Son, H. J., Lee, I. S. and Oh, J. E., "Detection of synthetic musk compounds (SMCs) in Nakdong river basin," J. Kor. Soc. Envir. Eng., 32(6), 615-624(2010).
  15. Lee, I., Lee, C., Heo, S. and Lee, J., "Occurrence of synthetic musk compounds in surface and waste waters in Korea," J. Kor. Soc. Envir. Eng., 33(11), 821-826(2011). https://doi.org/10.4491/KSEE.2011.33.11.821
  16. Lee, I., Kim, U., Oh, J., Choi, M. and Hwang, D., "Comprehensive monitoring of synthetic musk compounds from freshwater to coastal environments in Korea: With consideration of ecological concerns and bioaccumulation," Sci. Total Environ., 470-471, 1502-1508(2014). https://doi.org/10.1016/j.scitotenv.2013.07.070
  17. Román, I. P., Chisvert, A. and Canals, A., "Dispersive solidphase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatography-mass spectrometry for UV-filter determination in winter samples," J. Chromatogr. A, 1218, 2467-2375(2011). https://doi.org/10.1016/j.chroma.2011.02.047
  18. Negreira, N., Rodriguez, I., Ramil, M. and Cela, E. R. R., "Sensitive determination of salicylate and benzophenone type UV filters in water samples using solid-phase microextraction, derivatization and gas chromatography tandem mass spectrometry," Anal. Chim. Acta, 638, 36-44(2009). https://doi.org/10.1016/j.aca.2009.02.015
  19. Liu, H., Liu, L., Xiong, Y., Yang, X. and Luan, T., "Simultaneous determination of UV filters and polycyclic musks in aqueous samples by solid-phase microextraction and gas chromatography-mass spectrometry," J. Chromatogr. A, 1217, 6747-6753(2010). https://doi.org/10.1016/j.chroma.2010.06.004
  20. Rodil, R. and Moeder, M., "Development of a method for the determination of UV filters in water samples using stir bar sorptive extraction and thermal desorption-gas chromatography- mass spectrometry," J. Chromatogr. A, 1179, 81-88(2008). https://doi.org/10.1016/j.chroma.2007.11.090
  21. Silva, A. R. M. and Nogueira, J. M. F., "New approach on trace analysis of triclosan in personal care products, biological and environmental matrices," Talanta, 74, 1498-1504(2008). https://doi.org/10.1016/j.talanta.2007.09.040
  22. Gilart, N., Marce, R. M., Borrull, F. and Fontanals, N., "New coatings for stir-bar sorptive extraction of polar emerging organic contaminants," Trends Anal. Chem., 54, 11-23(2014). https://doi.org/10.1016/j.trac.2013.10.010
  23. Balk, F. and Ford, R. A., "Environmental risk assessment for the polycyclic musks AHTN and HHCB in the EU-I. Fate and exposure assessment," Toxicol. Lett., 111, 57-79(1999). https://doi.org/10.1016/S0378-4274(99)00169-1
  24. Paasivirta, J., Sinkkonen, S., Rantalainen, A. L., Broman, D. and Zebuhr, Y., "Temperature dependent properties of environmentally important synthetic musks," Environ. Sci. Pollut. Res. Int., 9(5), 345-355(2002). https://doi.org/10.1007/BF02987579
  25. Vallecillos, L., Pocurull, E. and Borrull, F., "Fully automated determination of macrocyclic musk fragrances in wastewater by microextraction by packed sorbents and large volume injection gas chromatography-mass spectrometry," J. Chromatogr. A, 1264, 87-94(2012). https://doi.org/10.1016/j.chroma.2012.09.049
  26. Scognamiglio, J., Letizia, C. S., Politano, V. T. and Api, A. M., "Fragrance material review on 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone (OTNE)," Food Chem. Toxicol., 62, S120-S132(2013). https://doi.org/10.1016/j.fct.2013.08.056
  27. Silva, A. R. M. and Nogueira, J, M. F., "New approach on trace analysis of triclosan in personal care products, biological and environmental matrices," Talanta, 74, 1498-1504 (2008). https://doi.org/10.1016/j.talanta.2007.09.040
  28. Nguyen, K. T. N., Scapolla, C., Di Carro, M. and Magi, E., "Rapid and selective determination of UV filters in seawater by liquid chromatography-tandem mass spectrometry combined with stir bar sorptive extraction," Talanta, 85, 2375-2384(2011). https://doi.org/10.1016/j.talanta.2011.07.085
  29. Allard, S., Charrois, J. W. A., Joll, C. A. and Heitz, A., "Simultaneous analysis of 10 trihalomethanes at nanogram per liter levels in water using solid-phase microextraction and gas chromatography mass-spectrometry," J. Chromatogr. A, 1238, 15-21(2012). https://doi.org/10.1016/j.chroma.2012.03.020

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