Characterization of nitrophenols in river, lake, and field water samples using dispersive liquid–liquid microextraction

  • W.-T. Wang
  • P.-S. Chen
  • S.-D. HuangEmail author
Original Paper


Nitrophenols, a group of poorly degradable pollutants, are produced by chemical industries such as those for dyes, agriculture, and medicine. Two approaches, namely (1) surfactant-assisted dispersive liquid–liquid microextraction (SADLLME) and (2) up-and-down-shaker-assisted dispersive liquid–liquid microextraction (UDSA-DLLME), were applied to detect four nitrophenols in river, lake, and field water. Both methods used ultra-high-performance liquid chromatography with photodiode array detection (UPLC-PDA). Under optimum conditions, the linear ranges were 1–1000 μg L−1 for SADLLME and 2–1000 μg L−1 for UDSA-DLLME. The correlation coefficients of the calibration curve were all above 0.9966. The limits of detection (LODs) ranged from 0.1 to 2.6 μg L−1. The precisions of determination of spiked analytes were 3.0–6.4% (intraday) and 8.7–14.6% (interday). For the analysis of the three water samples, the relative recoveries ranged from 93.1 to 103% with SADLLME, and from 90.5 to 107% with UDSA-DLLME. Compared with the vortex-assisted method and the method aided by ultrasound emulsification, UDSA-DLLME had better precision, and SADLLME had better sensitivity and lower LODs. The proposed methods offer high sensitivity and minimal consumption of organic solvent. They are alternatives for determining nitrophenols in aqueous samples.


Dispersive liquid–liquid microextraction Nitrophenols Shaker-assisted Surfactant Ultra-high-performance liquid chromatography–photodiode array 



The authors wish to thank the Ministry of Science and Technology of Taiwan (NSC 99-2113-M-007-004-MY3) for financial support.


  1. Agency for Toxic Substances and Disease Registry (1992) US Department of Health and Human Services, Public Health Service. Atlanta, USAGoogle Scholar
  2. Arthur CL, Pawliszyn J (1990) Solid-phase microextraction with thermal-desorption using fused-silica optical fibers. Anal Chem 62:2145–2148CrossRefGoogle Scholar
  3. Behbahani M, Esrafili A, Bagheri S, Radfar S, Bojdi MK, Bagheri A (2014) Modified nanoporous carbon as a novel sorbent before solvent-based de-emulsification dispersive liquid-liquid microextraction for ultra-trace detection of cadmium by flame atomic absorption spectrophotometry. Measurement 51:174–181CrossRefGoogle Scholar
  4. Berijani S, Sadigh M, Pournamdari E (2016) Homogeneous liquid–liquid microextraction for determination of organophosphorus pesticides in environmental water samples prior to gas chromatography-flame photometric detection. J Chromatogr Sci 54:1061–1067CrossRefGoogle Scholar
  5. Chen P-S, Haung W-Y, Huang S-D (2014) Analysis of triazine herbicides using an up-and-down-shaker-assisted dispersive liquid–liquid microextraction coupled with gas chromatography–mass spectrometry. J Chromatogr B 955–956:116–123CrossRefGoogle Scholar
  6. Chung RJ, Leong MI, Huang SD (2012) Determination of nitrophenols using ultrahigh pressure liquid chromatography and a new manual shaking-enhanced, ultrasound-assisted emulsification microextraction method based on solidification of a floating organic droplet. J Chromatogr A 1246:55–61CrossRefGoogle Scholar
  7. Daneshfar A, Khezeli T (2014) Cloud point-dispersive liquid–liquid microextraction for extraction of organic acids from biological samples. J Surfactants Deterg 17:1259–1267CrossRefGoogle Scholar
  8. El-Sheikh AH, Alzawahreh AM, Sweileh JA (2011) Preparation of an efficient sorbent by washing then pyrolysis of olive wood for simultaneous solid phase extraction of chloro-phenols and nitro-phenols from water. Talanta 85:1034–1042CrossRefGoogle Scholar
  9. Farahani H, Norouzi P, Dinarvand R, Ganjali MR (2007) Development of dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry as a simple, rapid and highly sensitive method for the determination of phthalate esters in water samples. J Chromatogr A 1172:105–112CrossRefGoogle Scholar
  10. Farajzadeh MA, Djozan D, Bakhtiyari RF (2010) Use of a capillary tube for collecting an extraction solvent lighter than water after dispersive liquid-liquid microextraction and its application in the determination of parabens in different samples by gas chromatography–flame ionization detection. Talanta 81:1360–1367CrossRefGoogle Scholar
  11. Farajzadeh MA, Yadeghari A, Khoshmaram L (2017) Combination of dispersive solid phase extraction and dispersive liquid–liquid microextraction for extraction of some aryloxy pesticides prior to their determination by gas chromatography. Microchem J 131:182–191CrossRefGoogle Scholar
  12. Guo L, Lee HK (2012) Low-density solvent based ultrasound-assisted emulsification microextraction and on-column derivatization combined with gas chromatography-mass spectrometry for the determination of carbamate pesticides in environmental water samples. J Chromatogr A 1235:1–9CrossRefGoogle Scholar
  13. Haftka JJH, Hammer J, Hermens JLM (2015) Mechanisms of neutral and anionic surfactant sorption to solid-phase microextraction fibers. Environ Sci Technol 49:11053–11061CrossRefGoogle Scholar
  14. He Y, Kang YJ (2006) Single drop liquid-liquid-liquid microextraction of methamphetamine and amphetamine in urine. J Chromatogr A 1133:35–40CrossRefGoogle Scholar
  15. He Y, Lee HK (1997) Liquid-phase microextraction in a single drop of organic solvent by using a conventional microsyringe. Anal Chem 68:4636–4640. Accessed 29 Apr 2017
  16. Hu L, Qian H, Yang X, Li S, Zhang S, Lu R, Zhou W, Gao H (2016) Effervescence-assisted dispersive liquid–liquid microextraction based on the solidification of a floating ionic liquid with a special collection method for the rapid determination of benzoylurea insecticides in water samples. RSC Adv 6:95283–95291CrossRefGoogle Scholar
  17. Jiang X, Lee HK (2004) Solvent bar microextraction. Anal Chem 76:5591–5596CrossRefGoogle Scholar
  18. Li Y, Chen PS, Huang SD (2013) Water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid-liquid microextraction for the determination of organochlorine pesticides in aqueous samples. J Chromatogr A 1300:51–57CrossRefGoogle Scholar
  19. Li J, Roh SH, Shaodong J, Hong JY, Lee DK, Shin BK, Park JH, Lee J, Kwon SW (2017) Solid-phase extraction assisted dispersive liquid–liquid microextraction based on solidification of floating organic droplet to determine sildenafil and its analogues in dietary supplements. J Sep Sci 40:3120–3129CrossRefGoogle Scholar
  20. Liu X, Shen Z, Wang P, Liu C, Zhou Z, Liu D (2014) Effervescence assisted on-site liquid phase microextraction for the determination of five triazine herbicides in water. J Chromatogr A 1371:58–64CrossRefGoogle Scholar
  21. Mei M, Huang X, Yu J, Yuan D (2015) Sensitive monitoring of trace nitrophenols in water samples using multiple monolithic fiber solid phase microextraction and liquid chromatographic analysis. Talanta 134:89–97CrossRefGoogle Scholar
  22. Nagaraju D, Huang S-D (2007) Determination of triazine herbicides in aqueous samples by dispersive liquid–liquid microextraction with gas chromatography–ion trap mass spectrometry. J Chromatogr A 1161:89–97CrossRefGoogle Scholar
  23. Ormsby M (2005) Analysis of laminated documents using solid-phase microextraction. JAIC 44:13–26Google Scholar
  24. Pedersen-Bjergaard S, Rasmussen KE (1999) Liquid-liquid-liquid microextraction for sample preparation of biological fluids prior to capillary electrophoresis. Anal Chem 71:2650–2656CrossRefGoogle Scholar
  25. Qian LL, He YZ (2006) Funnelform single-drop microextraction for gas chromatography-electron-capture detection. J Chromatogr A 1134:32–37CrossRefGoogle Scholar
  26. Rasmussen KE, Pedersen-Bjergaard S, Krogh M, Ugland HG, Grønhaug T (2000) Development of a simple in-vial liquid-phase microextraction device for drug analysis compatible with capillary gas chromatography, capillary electrophoresis and high-performance liquid chromatography. J Chromatogr A 873:3–11CrossRefGoogle Scholar
  27. Regueiro J, Llompart M, Garcia-Jares C, Garcia-Monteagudo JC, Cela R (2008) Ultrasound-assisted emulsification–microextraction of emergent contaminants and pesticides in environmental waters. J Chromatogr A 1190:27–38CrossRefGoogle Scholar
  28. Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S (2006) Determination of organic compounds in water using dispersive liquid–liquid microextraction. J Chromatogr A 1116:1–9CrossRefGoogle Scholar
  29. Sadeghian F, Ebrahimi P, Shakeri A, Jamali MR (2016) Extraction of citrus paradisi volatile components by headspace single-drop microextraction and statistical modeling. J Chromatogr Sci 54:1263–1269CrossRefGoogle Scholar
  30. Saraji M, Bakhshi M (2005) Determination of phenols in water samples by single-drop microextraction followed by in-syringe derivatization and gas chromatography-mass spectrometric detection. J Chromatogr A 1098:30–36CrossRefGoogle Scholar
  31. Saraji M, Marzban M (2010) Determination of 11 priority pollutant phenols in wastewater using dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-diode-array detection. Anal Bioanal Chem 396:2685–2693CrossRefGoogle Scholar
  32. Shrivas K, Dewangan K (2015) Surfactant-assisted dispersive liquid–liquid microextraction for sensitive spectrophotometric determination of iron in food and water samples and comparison with atomic absorption spectrometry. J Surfactants Deterg 18:1137–1144CrossRefGoogle Scholar
  33. Shu MW, Leong MI, Fuh MR, Huang SD (2012) Determination of endocrine-disrupting phenols in water samples by a new manual shaking-enhanced, ultrasound-assisted emulsification microextraction method. Analyst 137:2143–2150CrossRefGoogle Scholar
  34. Stahl DC, Tilotta DC (2001) Screening method for nitroaromatic compounds in water based on solid-phase microextraction and infrared spectroscopy. Environ Sci Technol 35:3507–3512CrossRefGoogle Scholar
  35. Tahmasebi E, Yamini Y, Seidi S, Rezazadeh M (2013) Extraction of three nitrophenols using polypyrrole-coated magnetic nanoparticles based on anion exchange process. J Chromatogr A 1314:15–23CrossRefGoogle Scholar
  36. Wei SY, Leong MI, Li Y, Huang SD (2011) Development of liquid phase microextraction based on manual shaking and ultrasound-assisted emulsification method for analysis of organochlorine pesticides in aqueous samples. J Chromatogr A 1218:9142–9148CrossRefGoogle Scholar
  37. Yiantzi E, Psillakis E, Tyrovola K, Kalogerakis N (2010) Vortex-assisted liquid–liquid microextraction of octylphenol, nonylphenol and bisphenol-A. Talanta 80:2057–2062CrossRefGoogle Scholar
  38. You J, Pehkonen S, Landrum PF, Lydy MJ (2007) Desorption of hydrophobic compounds from laboratory-spiked sediments measured by tenax absorbent and matrix solid-phase microextraction. Environ Sci Technol 41:5672–5678CrossRefGoogle Scholar
  39. Zargar B, Parham H, Hatamie A (2016) Hollow fiber liquid based microextraction of nalidixic acid in urine samples using aliquat 336 as a carrier combined with high-performance liquid chromatography. J Chromatogr Sci 54:257–263Google Scholar
  40. Zhou SN, Oakes KD, Servos MR, Pawliszyn J (2008) Application of solid-phase microextraction for in vivo laboratory and field sampling of pharmaceuticals in fish. Environ Sci Technol 42:6073–6079CrossRefGoogle Scholar
  41. Zhu L, Zhu L, Lee HK (2001) Liquid–liquid–liquid microextraction of nitrophenols with a hollow fiber membrane prior to capillary liquid chromatography. J Chromatogr A 924:407–414CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2018

Authors and Affiliations

  1. 1.Department of ChemistryNational Tsing Hua UniversityHsinchuTaiwan
  2. 2.Department and Graduate Institute of Forensic MedicineNational Taiwan UniversityTaipeiTaiwan

Personalised recommendations