An environmentally friendly strategy for determining organic ultraviolet filters in seawater using liquid-phase microextraction with liquid chromatography–tandem mass spectrometry

  • Ping-Chang Ku
  • Ting-Yu Liu
  • Shu Hui Lee
  • Te-An Kung
  • Wei-Hsien WangEmail author
Research Article


Benzophenone-3, benzophenone-8, and 4-methylbenzylidene camphor are used in sunscreens because they can protect the skin from UV radiation. The widespread use of organic UV filters may mean that they directly or indirectly enter seawater during recreational activities or through sewage discharge. In this study, a simple and efficient method using 1-octanol:isooctane (2:8, v/v) as an extraction solvent and liquid chromatography–electrospray tandem mass spectrometry was developed to measure trace levels of organic UV filters in seawater samples. This proposed method proved to be a highly sensitive, low-cost, and green analytical tool that requires minimal sample preparation. The method was validated and it exhibited favorable performance as well as acceptable accuracy (67 to 115%), precision (2.1 to 7.3%), coefficients of determination (0.9952 < R2 < 0.9987), sensitivity (limits of quantification [3.3 to 5.7 ng L−1]), and an acceptable matrix effect (87 to 99%). This methodology was successfully applied to analyze seawater taken from Kenting National Park located in the Hengchun Peninsula of southern Taiwan. Benzophenone-3 was detected at all sampling sites and at a higher concentration than the other organic UV filters. The highest concentration of benzophenone-3 was 514.6 ng L−1 in a sample collected from Baisha Beach.


Organic ultraviolet filter Green extraction solvent Mass spectrometry Seawater Kenting National Park 


Author contributions

Conception and design of study: Wei-Hsien Wang; acquisition of data: Te-An Kung, Shu-Hui Lee, Ting-Yu Liu, Ping-Chang Ku; analysis and/or interpretation of data: Ting-Yu Liu, Wei-Hsien Wang, Ping-Chang Ku; drafting the manuscript: Wei-Hsien Wang, Te-An Kung; revising the manuscript critically for important intellectual content: Wei-Hsien Wang, Te-An Kung.

Funding information

This research was supported by grants from the Ministry of Science and Technology [grant number MOST 106–2611-M-110-014].

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

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  1. Allinson M, Kameda Y, Kimura K, Allinson G (2018) Occurrence and assessment of the risk of ultraviolet filters and light stabilizers in Victorian estuaries. Environ Sci Pollut Res Int 25:12022–12033. CrossRefGoogle Scholar
  2. Archana G, Dhodapkar R, Kumar A (2016) Offline solid-phase extraction for preconcentration of pharmaceuticals and personal care products in environmental water and their simultaneous determination using the reversed phase high-performance liquid chromatography method. Environ Monit Assess 188:512–510. CrossRefGoogle Scholar
  3. Archer E, Petrie B, Kasprzyk-Hordern B, Wolfaardt GM (2017) The fate of pharmaceuticals and personal care products (PPCPs), endocrine disrupting contaminants (EDCs), metabolites and illicit drugs in a WWTW and environmental waters. Chemosphere 174:437–446. CrossRefGoogle Scholar
  4. Armenta S, Garrigues S, de la Guardia M (2015) The role of green extraction techniques in green analytical chemistry. Trac-trend Anal Chem 71:2–8. CrossRefGoogle Scholar
  5. Benede JL, Chisvert A, Salvador A, Sanchez-Quiles D, Tovar-Sanchez A (2014) Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry. Anal Chim Acta 812:50–58. CrossRefGoogle Scholar
  6. Benede JL, Chisvert A, Giokas DL, Salvador A (2016) Determination of ultraviolet filters in bathing waters by stir bar sorptive-dispersive microextraction coupled to thermal desorption-gas chromatography-mass spectrometry. Talanta 147:246–252. CrossRefGoogle Scholar
  7. Bialk-Bielinska A, Kumirska J, Palavinskas R, Stepnowski P (2009) Optimization of multiple reaction monitoring mode for the trace analysis of veterinary sulfonamides by LC-MS/MS. Talanta 80:947–953. CrossRefGoogle Scholar
  8. Brausch JM, Rand GM (2011) A review of personal care products in the aquatic environment: environmental concentrations and toxicity. Chemosphere 82:1518–1532. CrossRefGoogle Scholar
  9. Celano R, Piccinelli AL, Campone L, Rastrelli L (2014) Ultra-preconcentration and determination of selected pharmaceutical and personal care products in different water matrices by solid-phase extraction combined with dispersive liquid-liquid microextraction prior to ultra high pressure liquid chromatography tandem mass spectrometry analysis. J Chromatogr A 1355:26–35. CrossRefGoogle Scholar
  10. Chisvert A, Leon-Gonzalez Z, Tarazona I, Salvador A, Giokas D (2012) An overview of the analytical methods for the determination of organic ultraviolet filters in biological fluids and tissues. Anal Chim Acta 752:11–29. CrossRefGoogle Scholar
  11. Chisvert A, Benede JL, Salvador A (2018) Current trends on the determination of organic UV filters in environmental water samples based on microextraction techniques - a review. Anal Chim Acta 1034:22–38. CrossRefGoogle Scholar
  12. Chung WH, Tzing SH, Ding WH (2015) Optimization of dispersive micro solid-phase extraction for the rapid determination of benzophenone-type ultraviolet absorbers in aqueous samples. J Chromatogr A 1411:17–22. CrossRefGoogle Scholar
  13. Emnet P, Gaw S, Northcott G, Storey B, Graham L (2015) Personal care products and steroid hormones in the Antarctic coastal environment associated with two Antarctic research stations, McMurdo Station and Scott Base. Environ Res 136:331–342. CrossRefGoogle Scholar
  14. Ferguson P, Harding M (2011) Green chemistry considerations for sample preparation. In: Nickerson B (ed) Sample preparation of pharmaceutical dosage forms. Springer, New York, pp 333–354CrossRefGoogle Scholar
  15. Filippou O, Bitas D, Samanidou V (2017) Green approaches in sample preparation of bioanalytical samples prior to chromatographic analysis. J Chromatogr B 1043:44–62. CrossRefGoogle Scholar
  16. Fisch K, Waniek JJ, Schulz-Bull DE (2017) Occurrence of pharmaceuticals and UV-filters in riverine run-offs and waters of the German Baltic Sea. Mar Pollut Bull 124:388–399. CrossRefGoogle Scholar
  17. Gago-Ferrero P, Diaz-Cruz MS, Barcelo D (2013) Multi-residue method for trace level determination of UV filters in fish based on pressurized liquid extraction and liquid chromatography-quadrupole-linear ion trap-mass spectrometry. J Chromatogr A 1286:93–101. CrossRefGoogle Scholar
  18. Garcia-Galan MJ, Diaz-Cruz S, Barcelo D (2013) Multiresidue trace analysis of sulfonamide antibiotics and their metabolites in soils and sewage sludge by pressurized liquid extraction followed by liquid chromatography-electrospray-quadrupole linear ion trap mass spectrometry. J Chromatogr A 1275:32–40. CrossRefGoogle Scholar
  19. Guart A, Calabuig I, Lacorte S, Borrell A (2014) Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS). Environ Sci Pollut Res Int 21:2846–2855. CrossRefGoogle Scholar
  20. Jeon HK, Chung Y, Ryu JC (2006) Simultaneous determination of benzophenone-type UV filters in water and soil by gas chromatography-mass spectrometry. J Chromatogr A 1131:192–202. CrossRefGoogle Scholar
  21. Jimenez-Diaz I, Zafra-Gomez A, BallesterosO NA (2014) Analytical methods for the determination of personal care products in human samples: an overview. Talanta 129:448–458. CrossRefGoogle Scholar
  22. Kapelewska J, Kotowska U, Wisniewska K (2016) Determination of personal care products and hormones in leachate and groundwater from polish MSW landfills by ultrasound-assisted emulsification microextraction and GC-MS. Environ Sci Pollut Res Int 23:1642–1652. CrossRefGoogle Scholar
  23. Kim S, Choi K (2014) Occurrences, toxicities, and ecological risks of benzophenone-3, a common component of organic sunscreen products: a mini-review. Environ Int 70:143–157. CrossRefGoogle Scholar
  24. Kim JW, RamaswamyBR CKH, Isobe T, Tanabe S (2011) Multiresidue analytical method for the determination of antimicrobials, preservatives, benzotriazole UV stabilizers, flame retardants and plasticizers in fish using ultra high performance liquid chromatography coupled with tandem mass spectrometry. J Chromatogr A 1218:3511–3520. CrossRefGoogle Scholar
  25. Kung TA, Tsai CW, Ku BC, Wang WH (2015) A generic and rapid strategy for determining trace multiresidues of sulfonamides in aquatic products by using an improved QuEChERS method and liquid chromatography-electrospray quadrupole tandem mass spectrometry. Food Chem 175:189–196. CrossRefGoogle Scholar
  26. Kung TA, Lee SH, Yang TC, Wang WH (2018) Survey of selected personal care products in surface water of coral reefs in Kenting National Park, Taiwan. Sci Total Environ 635:1302–1307. CrossRefGoogle Scholar
  27. Lalovic B, Durkic T, Vukcevic M, Jankovic-Castvan I, Kalijadis A, Lausevic Z, Lausevic M (2017) Solid-phase extraction of multi-class pharmaceuticals from environmental water samples onto modified multi-walled carbon nanotubes followed by LC-MS/MS. Environ Sci Pollut Res Int 24:20784–20793. CrossRefGoogle Scholar
  28. Liew CSM, Li X, Zhang H, Lee HK (2018) A fully automated analytical platform integrating water sampling-minisale-liquid-liquid extraction-full evaporation dynamic headspace concentration-gas chromatography-mass spectrometry for the analysis of ultraviolet filters. Anal Chim Acta 1006:33–41. CrossRefGoogle Scholar
  29. Liu Q, Chen Z, Wei D, Du Y (2014) Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process. J Environ Sci 26:440–447. CrossRefGoogle Scholar
  30. Marta-Sanchez AV, Caldas SS, Schneider A, Cardoso S, Primel EG (2018) Trace analysis of parabens preservatives in drinking water treatment sludge, treated, and mineral water samples. Environ Sci Pollut Res Int 25:14460–14470. CrossRefGoogle Scholar
  31. Petrie B, Youdan J, Barden R, Kasprzyk-Hordern B (2016) Multi-residue analysis of 90 emerging contaminants in liquid and solid environmental matrices by ultra-high-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 1431:64–78. CrossRefGoogle Scholar
  32. Rodil R, Quintana JB, Lo’pez-Mahı’a P, Muniategui-Lorenzo S, Prada-Rodrı’guez D (2008) Multiclass determination of sunscreen chemicals in water samples by liquid chromatography-tandem mass spectrometry. Anal Chem 80:1307–1315. CrossRefGoogle Scholar
  33. Sanchez Rodriguez A, Rodrigo Sanz M, Betancort Rodriguez JR (2015) Occurrence of eight UV filters in beaches of gran Canaria (Canary Islands): an approach to environmental risk assessment. Chemosphere 131:85–90. CrossRefGoogle Scholar
  34. Sorensen JP, Lapworth DJ, Nkhuwa DC, Stuart ME, Gooddy DC, Bell RA, Chirwa M, Kabika J, Liemisa M, Chibesa M, Pedley S (2015) Emerging contaminants in urban groundwater sources in Africa. Water Res 72:51–63. CrossRefGoogle Scholar
  35. Suzuki T, Kitamura S, Khota R, Sugihara K, Fujimoto N, Ohta S (2005) Estrogenic and antiandrogenic activities of 17 benzophenone derivatives used as UV stabilizers and sunscreens. Toxicol Appl Pharmacol 203:9–17. CrossRefGoogle Scholar
  36. Tarazona I, Chisvert A, Leon Z, Salvador A (2010) Determination of hydroxylated benzophenone UV filters in sea water samples by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry. J Chromatogr A 1217:4771–4778. CrossRefGoogle Scholar
  37. The European Parliament and the Council of the European Union (2009) Regulation (EC) No. 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic productsGoogle Scholar
  38. Tsui MM, Leung HW, Wai TC, Yamashita N, Taniyasu S, Liu W, Lam PKS, Murphy MB (2014) Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries. Water Res 67:55–65. CrossRefGoogle Scholar
  39. USEPA (2003) Method 8000C-determinative chromatographic separations. US Environmental Protection Agency 8000 series methods, Washington, DCGoogle Scholar
  40. Wu MH, Li J, Xu G, Ma LD, Li JJ, Li JS, Tang L (2018) Pollution patterns and underlying relationships of benzophenone-type UV-filters in wastewater treatment plants and their receiving surface water. Ecotoxicol Environ Saf 152:98–103. CrossRefGoogle Scholar
  41. Zhang Y, Lee HK (2013) Determination of ultraviolet filters in environmental water samples by temperature-controlled ionic liquid dispersive liquid-phase microextraction. J Chromatogr A 1271:56–61. CrossRefGoogle Scholar
  42. Zhang T, Sun H, Qin X, Wu Q, Zhang Y, Ma J, Kannan K (2013) Benzophenone-type UV filters in urine and blood from children, adults, and pregnant women in China: partitioning between blood and urine as well as maternal and fetal cord blood. Sci Total Environ 461-462:49–55. CrossRefGoogle Scholar
  43. Zhang Y, Li H, Zhang J, Shao B (2019) Determination of alternaria toxins in drinking water by ultra-performance liquid chromatography tandem mass spectrometry. Environ Sci Pollut Res Int 26:22485–22493. CrossRefGoogle Scholar
  44. Zhao H, Wei D, Li M, Du Y (2013) Substituent contribution to the genotoxicity of benzophenone-type UV filters. Ecotoxicol Environ Saf 95:241–246. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  • Ping-Chang Ku
    • 1
  • Ting-Yu Liu
    • 1
  • Shu Hui Lee
    • 2
  • Te-An Kung
    • 3
  • Wei-Hsien Wang
    • 1
    Email author
  1. 1.Department of Marine Biotechnology and ResourcesNational Sun Yat-Sen UniversityKaohsiungTaiwan
  2. 2.Center of General EducationNational Kaohsiung University of Science and TechnologyKaohsiungTaiwan
  3. 3.Department of Agricultural ChemistryNational Taiwan UniversityTaipeiTaiwan

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