Analysis of UV Filters in Water using Stir Bar Sorptive Extraction (SBSE) and GC/MS-MS

교반막대 추출법과 GC/MS-MS를 이용한 수중의 자외선 차단제 분석

Seo, Chang-Dong;Son, Hee-Jong;Jung, Jong-Moon;Choi, Jin-Taek;Jang, Seong-Ho

  • Received : 2014.03.19
  • Accepted : 2014.04.16
  • Published : 2014.06.30


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 seven UV filters 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 < 12.9%). The extraction efficiencies were above 84% for all the compounds. The limits of detections (LOD) and limits of quantification (LOQ) were 2.1~8.6 ng/L and 6.8~27.5 ng/L, respectively. The developed method offers the ability to detect 8 UV filters 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 7 UV filters except of benzophenone (BP). The method developed in the present study has the advantage of being rapid, simple, high-sensitive and both user and environmentally friendly.


UV filters;Sunscreen agents;Stir bar sorptive extraction (SBSE);Gas chromatography-tandem mass spectrometry (GC/MS-MS);Water samples


  1. Santos, A. J. M., Miranda, M. S., Esteves da Silva, J. C. G., 2012, The degradation products of UV filters in aqueous and chlorinated aqueous solutions, Water Res., 46, 3167-3176.
  2. Zucchi, S., Bluthgen, N., Ieronimo, A., Fent, K., 2011, The UV-absorber benzophenone-4 alters transcripts of genes involved in hormonal pathways in zebrafish (Danio rerio) eleuthero-embryos and adult males, Toxicol. Appl. Pharmacol., 250, 137-146.
  3. Poiger, T., Buser, H. R., Balmer, M. E., Bergqvist, P. A., Muller, M. D., 2004, Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes, Chemosphere, 55, 951-963.
  4. Rodil, R., Moeder, M., 2008, 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.
  5. Rodil, R., Quintana, J. B., Concha-Grana, E., Lopez- Mahia, P., Muniategui-Lorenzo, S., Prada-Rodriguez, D., 2012, Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain), Chemosphere, 86, 1040-1049.
  6. Roman, I. P., Chisvert, A., Canals, A., 2011, Dispersive solid-phase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatographymass spectrometry for UV-filter determination in winter samples, J. Chromatogr. A, 1218, 2467-2375.
  7. Schlumpf, M., Cotton, B., Conscience, M., Haller, V., Steinmann, B., Lichtensteiger, W., 2001, In vitro and in vivo estrogenicity of UV screens, Environ. Health Perspect., 109, 239-244.
  8. Shaath, N. A., 2010, Ultraviolet filters, Photochem. Photobiol. Sci., 9(4), 464-469.
  9. Silva, A. R. M., Nogueira, J, M. F., 2008, New approach on trace analysis of triclosan in personal care products, biological and environmental matrices, Talanta, 74, 1498-1504.
  10. Silva, A. R. M., Portugal, F. C. M., Nogueira, J, M. F., 2008, Advances in stir bar sorptive extraction for the determination of acidic pharmaceuticals in environmental water matrices: comparison between polyurethane and polydimethylsiloxane polymeric phases, J. Chromatogr. A, 1209, 10-16.
  11. Kupper, T., Plagellat, C., Brandli, R. C., de Alencastro, L. F., Grandjean, D., Tarradellas, J., 2006, Fate and removal of polycyclic musks, UV filters and biocides during wastewater treatment, Water Res., 40, 2603-2612.
  12. Gasparro, F. P., Mitchnick, M., Nash, J. F., 1998, A review of sunscreen safety and efficacy, Photochem. Photobiol., 68, 243-256.
  13. Gilart, N., Marce, R. M., Borrull, F., Fontanals, N., 2014, New coatings for stir-bar sorptive extraction of polar emerging organic contaminants, Trends Anal. Chem., 54, 11-23.
  14. Giokas, D. L., Salvador, A., Chisvert, A., 2007, UV filters: from sunscreens to human body and the environment, Trends Anal. Chem., 26, 360-374.
  15. Liu, H., Liu, L., Xiong, Y., Yang, X., Luan, T., 2010, 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.
  16. Negreira, N., Rodriguez, I., Ramil, M., Cela, E. R. R., 2009, 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.
  17. Nguyen, K. T. N., Scapolla, C., Di Carro, M., Magi, E., 2011, 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.
  18. Peck, A. M., 2006, Analytical methods for the determination of persistant ingredients of personal care products in environmental matrices, Anal Bionanal. Chem. 386, 907-939.
  19. Plagellat, C., Kupper, T., Furrer, R., Alencastro, L. F., Grandjean, D., Tarradellas, J., 2006, Concentrations and specific loads of UV filters in sewage sludge originating from a monitoring network in Switzerland, Chemosphere., 62, 915-925.
  20. Buser, H. R., Balmer, M. E., Schmid, P., Kohler, M., 2006, Occurrence of UV filters 4-methylbenzylidene camphor and octocrylene in fish from various swiss rivers with inputs from wastewater treatment plants, Environ. Sci. Technol., 40, 1427-1431.
  21. Allard, S., Charrois, J. W. A., Joll, C. A., Heitz, A., 2012, Simultaneous analysis of 10 trihalomethanes at nanogram per liter levels in water using solid-phase microextraction and gas chromatography massspectrometry, J. Chromatogr. A, 1238, 15-21.
  22. Balmer, B. E., Buser, H. R., Muller, M. D., Poiger, T., 2005, Occurrence of some organic UV filters in wastewater, in surface waters, and in fish from Swiss lakes, Environ. Sci. Technol., 39, 953-962.
  23. Bluthgen, N., Zucchi, S., Fent, K., 2012, Effects of the UV filter benzophenone-3 (oxybenzone) at low concentrations in zebrafish (Danio rerio), Toxicol. Appl. Pharmacol., 263, 184-194.
  24. Fent, K., Kunz, P. Y., Gomez, E., 2008, UV filters in the aquatic environment induce hormonal effects and affect fertility and reproduction in fish, Chimia, 62, 368-375.
  25. Fent, K., Zenker, A., Rapp, M., 2010, Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland, Environ. Pollut., 158, 1817-1824.
  26. Gago-Ferreo, P., Diaz-Cruz, M. S., 2012, An overview of UV-absorbing compounds (organic UV filters) in aquatic biota, Anal. Bioanal. Chem., 404, 2597-2610.
  27. Garbicova, K., Fedorova, G., Burkina, V., Steinbach, C., Schmidt-Posthaus, H., Zlabek, V., Kroupova, H. K., Garbic, R., Randak, T., 2013, Presence of UV filters in surface water and the effects of phenylbenzimile sulfonic acid on rainbow trout(Oncorhynchus mykiss) following a chronic toxicity test, Ecotoxicol. Envoron. Safety, 96, 41-47.
  28. Gasparro, F. P., 2000, Sunscreens, skin photobiology, and skin cancer: The need for UVA protection and evaluation of efficacy, Environ. Health Perspect., 108, 71-78.

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