Analytical and Bioanalytical Chemistry

, Volume 407, Issue 26, pp 8137–8150 | Cite as

Fabric phase sorptive extraction followed by UHPLC-MS/MS for the analysis of benzotriazole UV stabilizers in sewage samples

  • Sarah Montesdeoca-Esponda
  • Zoraida Sosa-Ferrera
  • Abuzar KabirEmail author
  • Kenneth G. Furton
  • José Juan Santana-RodríguezEmail author
Research Paper


A fast and sensitive sample preparation strategy using fabric phase sorptive extraction followed by ultra-high-performance liquid chromatography and tandem mass spectrometry detection has been developed to analyse benzotriazole UV stabilizer compounds in aqueous samples. Benzotriazole UV stabilizer compounds are a group of compounds added to sunscreens and other personal care products which may present detrimental effects to aquatic ecosystems. Fabric phase sorptive extraction is a novel solvent minimized sample preparation approach that integrates the advantages of sol–gel derived hybrid inorganic–organic nanocomposite sorbents and the flexible, permeable and hydrophobic surface chemistry of polyester fabric. It is a highly sensitive, fast, efficient and inexpensive device that can be reused and does not suffer from coating damage, unlike SPME fibres or stir bars. In this paper, we optimized the extraction of seven benzotriazole UV filters evaluating the majority of the parameters involved in the extraction process, such as sorbent chemistry selection, extraction time, back-extraction solvent, back-extraction time and the impact of ionic strength. Under the optimized conditions, fabric phase sorptive extraction allows enrichment factors of 10 times with detection limits ranging from 6.01 to 60.7 ng L−1 and intra- and inter-day % RSDs lower than 11 and 30 % for all compounds, respectively. The optimized sample preparation technique followed by ultra-high-performance liquid chromatography and tandem mass spectrometry detection was applied to determine the target analytes in sewage samples from wastewater treatment plants with different purification processes of Gran Canaria Island (Spain). Two UV stabilizer compounds were measured in ranges 17.0–60.5 ng mL−1 (UV 328) and 69.3–99.2 ng mL−1 (UV 360) in the three sewage water samples analysed.


Benzotriazole UV stabilizers Fabric phase sorptive extraction UHPLC-MS/MS Sewage samples Personal care products Emerging pollutants Green sample preparation 



Sarah Montesdeoca-Esponda thanks the University of Las Palmas de Gran Canaria for her position as support staff for research.

Conflicts of interest

The authors declare no conflict of interest.


  1. 1.
    Spietelun A, Marcinkowski Ł, de la Guardia M, Namieśnik J (2013) Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry. J Chromatogr A 1321:1–13. doi: 10.1016/j.chroma.2013.10.030 CrossRefGoogle Scholar
  2. 2.
    Pedrouzo M, Borrull F, Marcé RM, Pocurull E (2010) Stir-bar-sorptive extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry for simultaneous analysis of UV filters and antimicrobial agents in water samples. Anal Bioanal Chem 397:2833–2839. doi: 10.1007/s00216-010-3743-3 CrossRefGoogle Scholar
  3. 3.
    Montesdeoca Esponda S, Torres Padrón ME, Sosa Ferrera Z, Santana Rodríguez JJ (2009) Solid-phase microextraction with micellar desorption and HPLC-fluorescence detection for the analysis of fluoroquinolones residues in water samples. Anal Bioanal Chem 394:927–935. doi: 10.1007/s00216-009-2629-8 CrossRefGoogle Scholar
  4. 4.
    Mahugo-Santana C, Sosa-Ferrera Z, Torres-Padrón ME, Santana-Rodríguez JJ (2011) Application of new approaches to liquid-phase microextraction for the determination of emerging pollutants. TrAC Trends Anal Chem 30:731–748. doi: 10.1016/j.trac.2011.01.011 CrossRefGoogle Scholar
  5. 5.
    Huang Z, Lee HK (2012) Materials-based approaches to minimizing solvent usage in analytical sample preparation. TrAC Trends Anal Chem 39:228–244. doi: 10.1016/j.trac.2012.05.007 CrossRefGoogle Scholar
  6. 6.
    Xu J, Zheng J, Tian J et al (2013) New materials in solid-phase microextraction. TrAC Trends Anal Chem 47:68–83. doi: 10.1016/j.trac.2013.02.012 CrossRefGoogle Scholar
  7. 7.
    Ho TD, Canestraro AJ, Anderson JL (2011) Ionic liquids in solid-phase microextraction: a review. Anal Chim Acta 695:18–43. doi: 10.1016/j.aca.2011.03.034 CrossRefGoogle Scholar
  8. 8.
    Souza Silva EA, Risticevic S, Pawliszyn J (2013) Recent trends in SPME concerning sorbent materials, configurations and in vivo applications. TrAC Trends Anal Chem 43:24–36. doi: 10.1016/j.trac.2012.10.006 CrossRefGoogle Scholar
  9. 9.
    Alizadeh N, Mohammadi A, Tabrizchi M (2008) Rapid screening of methamphetamines in human serum by headspace solid-phase microextraction using a dodecylsulfate-doped polypyrrole film coupled to ion mobility spectrometry. J Chromatogr A 1183:21–28. doi: 10.1016/j.chroma.2008.01.020 CrossRefGoogle Scholar
  10. 10.
    Bagheri H, Ayazi Z, Naderi M (2013) Conductive polymer-based microextraction methods: a review. Anal Chim Acta 767:1–13. doi: 10.1016/j.aca.2012.12.013 CrossRefGoogle Scholar
  11. 11.
    Kabir A, Furton KG, Malik A (2013) Innovations in sol–gel microextraction phases for solvent-free sample preparation in analytical chemistry. TrAC Trends Anal Chem 45:197–218. doi: 10.1016/j.trac.2012.11.014 CrossRefGoogle Scholar
  12. 12.
    Kumar A, Gaurav MAK et al (2008) A review on development of solid phase microextraction fibers by sol–gel methods and their applications. Anal Chim Acta 610:1–14. doi: 10.1016/j.aca.2008.01.028 CrossRefGoogle Scholar
  13. 13.
    Kumar R, Gaurav H et al (2014) Efficient analysis of selected estrogens using fabric phase sorptive extraction and high performance liquid chromatography-fluorescence detection. J Chromatogr A 1359:16–25. doi: 10.1016/j.chroma.2014.07.013 CrossRefGoogle Scholar
  14. 14.
    Kabir A, Furton KG (2014) Fabric phase sorptive extractors (FPSE), US Patent Application: 14,216,121 March 17, 2014Google Scholar
  15. 15.
    Kabir A (2015) Fabric phase sorptive extraction media: a highly effective forensic sample collection and storage device. AAFS 2015 67th Annu. Sci. MeetGoogle Scholar
  16. 16.
    Samanidou V, Galanopoulos L-D, Kabir A, Furton KG (2015) Fast extraction of amphenicols residues from raw milk using novel fabric phase sorptive extraction followed by high-performance liquid chromatography-diode array detection. Anal Chim Acta 855:41–50. doi: 10.1016/j.aca.2014.11.036 CrossRefGoogle Scholar
  17. 17.
    Roldán-Pijuán M, Lucena R, Cárdenas S et al (2015) Stir fabric phase sorptive extraction for the determination of triazine herbicides in environmental waters by liquid chromatography. J Chromatogr A 1376:35–45. doi: 10.1016/j.chroma.2014.12.027 CrossRefGoogle Scholar
  18. 18.
    Racamonde I, Rodil R, Quintana JB, Sieira BJ, Kabir A, Furton KG, Cela R (2015) Fabric phase sorptive extraction: a new sorptive microextraction technique for the determination of non-steroidal anti-inflammatory drugs from environmental water samples. Anal Chim Acta 865:22–30CrossRefGoogle Scholar
  19. 19.
    Kim J-W, Isobe T, Malarvannan G et al (2012) Contamination of benzotriazole ultraviolet stabilizers in house dust from the Philippines: implications on human exposure. Sci Total Environ 424:174–181. doi: 10.1016/j.scitotenv.2012.02.040 CrossRefGoogle Scholar
  20. 20.
    Balmer ME, Buser H-RR, Müller MD et al (2005) Occurrence of some organic UV filters in wastewater, in surface waters, and in fish from Swiss Lakes. Environ Sci Technol 39:953–962CrossRefGoogle Scholar
  21. 21.
    Kim J-W, Chang K-H, Isobe T, Tanabe S (2011) Acute toxicity of benzotriazole ultraviolet stabilizers on freshwater crustacean (Daphnia pulex). J Toxicol Sci 36:247–251. doi: 10.2131/jts.36.247 CrossRefGoogle Scholar
  22. 22.
    Casado J, Rodríguez I, Ramil M, Cela R (2013) Polyethersulfone solid-phase microextraction followed by liquid chromatography quadrupole time-of-flight mass spectrometry for benzotriazoles determination in water samples. J Chromatogr A 1299:40–47. doi: 10.1016/j.chroma.2013.05.061 CrossRefGoogle Scholar
  23. 23.
    Liu Y-S, Ying G-G, Shareef A, Kookana RS (2012) Occurrence and removal of benzotriazoles and ultraviolet filters in a municipal wastewater treatment plant. Environ Pollut 165:225–232. doi: 10.1016/j.envpol.2011.10.009 CrossRefGoogle Scholar
  24. 24.
    Gago-Ferrero P, Díaz-Cruz MS, Barceló D (2011) Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants. Chemosphere 84:1158–1165. doi: 10.1016/j.chemosphere.2011.04.003 CrossRefGoogle Scholar
  25. 25.
    Zhang Z, Ren N, Li Y-F et al (2011) Determination of benzotriazole and benzophenone UV filters in sediment and sewage sludge. Environ Sci Technol 45:3909–3916. doi: 10.1021/es2004057 CrossRefGoogle Scholar
  26. 26.
    Carpinteiro I, Abuín B, Rodríguez I et al (2010) Headspace solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the sensitive determination of benzotriazole UV stabilizers in water samples. Anal Bioanal Chem 397:829–839. doi: 10.1007/s00216-010-3584-0 CrossRefGoogle Scholar
  27. 27.
    Segro SS, Malik A (2008) Solvent-resistant sol–gel polydimethyldiphenylsiloxane coating for on-line hyphenation of capillary microextraction with high-performance liquid chromatography. J Chromatogr A 1205:26–35. doi: 10.1016/j.chroma.2008.07.073 CrossRefGoogle Scholar
  28. 28.
    Chong SL, Wang D, Hayes JD et al (1997) Sol–gel coating technology for the preparation of solid-phase microextraction fibers of enhanced thermal stability. Anal Chem 69:3889–3898CrossRefGoogle Scholar
  29. 29.
    Rao AV, Bhagat SD, Hirashima H, Pajonk G (206AD) Synthesis of flexible silica aerogels using methyltrimethoxysilane (MTMS) precursor. J Colloid Interface Sci 300:279–285Google Scholar
  30. 30.
    Tomšič B, Lavrič PK, Simončič B et al (2011) Sol–gel technology for functional finishing of PES fabric by stimuli-responsive microgel. J Sol-Gel Sci Technol 61:463–476. doi: 10.1007/s10971-011-2647-9 Google Scholar
  31. 31.
    Gelest I (2013) Silicon compounds: silanes and silicons: a survey of properties and chemistry, 3rd edn. Morrisville, PA, 19067, USAGoogle Scholar
  32. 32.
    Guido E, Alongi J, Colleoni C et al (2013) Thermal stability and flame retardancy of polyester fabrics sol–gel treated in the presence of boehmite nanoparticles. Polym Degrad Stab 98:1609–1616. doi: 10.1016/j.polymdegradstab.2013.06.021 CrossRefGoogle Scholar
  33. 33.
    Shirey R Improvements in SPME reproducibility through enhancements in the fiber manufacturing process. Report (The Tech Newsl from Supleco) 22.4:7–8Google Scholar
  34. 34.
    Carpinteiro I, Ramil M, Rodríguez I, Nogueira JMF (2012) Combining stir-bar sorptive extraction and large volume injection-gas chromatography–mass spectrometry for the determination of benzotriazole UV stabilizers in wastewater matrices. J Sep Sci 35:459–467. doi: 10.1002/jssc.201100448 CrossRefGoogle Scholar
  35. 35.
    Serôdio P, Nogueira JM (2004) Multi-residue screening of endocrine disrupters chemicals in water samples by stir bar sorptive extraction-liquid desorption-capillary gas chromatography–mass spectrometry detection. Anal Chim Acta 517:21–32. doi: 10.1016/j.aca.2004.04.045 CrossRefGoogle Scholar
  36. 36.
    Prieto A, Basauri O, Rodil R et al (2010) Stir-bar sorptive extraction: a view on method optimisation, novel applications, limitations and potential solutions. J Chromatogr A 1217:2642–2666. doi: 10.1016/j.chroma.2009.12.051 CrossRefGoogle Scholar
  37. 37.
    Do Rosário PMA, Nogueira JMF (2006) Combining stir bar sorptive extraction and MEKC for the determination of polynuclear aromatic hydrocarbons in environmental and biological matrices. Electrophoresis 27:4694–4702. doi: 10.1002/elps.200600210 CrossRefGoogle Scholar
  38. 38.
    Montesdeoca-Esponda S, del Toro-Moreno A, Sosa-Ferrera Z, Santana-Rodríguez JJ (2013) Development of a sensitive determination method for benzotriazole UV stabilizers in enviromental water samples with stir bar sorption extraction and liquid desorption prior to ultra-high performance liquid chromatography with tandem mass spectrometry. J Sep Sci 36:2168–2175. doi: 10.1002/jssc.201300191 CrossRefGoogle Scholar
  39. 39.
    Montesdeoca-Esponda S, Sosa-Ferrera Z, Santana-Rodríguez JJ (2012) On-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection for the determination of benzotriazole UV stabilizers in coastal marine and wastewater samples. Anal Bioanal Chem 403:867–876. doi: 10.1007/s00216-012-5906-x CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Sarah Montesdeoca-Esponda
    • 1
  • Zoraida Sosa-Ferrera
    • 1
  • Abuzar Kabir
    • 2
    Email author
  • Kenneth G. Furton
    • 2
  • José Juan Santana-Rodríguez
    • 1
    Email author
  1. 1.Departamento de QuímicaUniversidad de Las Palmas de G.C.Las Palmas de Gran CanariaSpain
  2. 2.International Forensic Research Institute, Department of Chemistry and BiochemistryFlorida International UniversityMiamiUSA

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