Ionic liquid intercalated clay sorbents for micro solid phase extraction of steroid hormones from water samples with analysis by liquid chromatography–tandem mass spectrometry

• A novel ionic liquid modified clay sorbents was developed for hormone analysis.
• μ-SPE procedure was applied prior to LC–MS/MS detection of hormones.
• A sensitive method for estradiol, estrone, estriol and ethnyl estradiol in water.
• Parameters affecting the μ-SPE procedure were screened by Plackett–Burmann design.
• Box–Behnken response surface method was used for latter optimization.

Clay material plays an important role in the transport and retention of many compounds in the soil, therefore, clay based sorbents are promising alternatives for selective sorption of organic pollutants. In the present work, different chain length ionic liquids (ILs) namely, 1-methyl-3-octyl-imidazolium bromide, 1-methyl-3-undecyl-imidazolium bromide and 1-methyl-3-octadecyl-imidazolium bromide were intercalated in the galleries of montmorillonite (MMT) clay. Then, this novel nanofiller surface was utilized in micro extraction of estrogenic hormones for the first time. A fast procedure where sonication-assisted emulsification microextraction combined with vortex assisted micro-solid phase extraction (μ-SPE) was developed for the LC–MS/MS analysis of estrone (E1), 17β-estradiol (E2), estriol (E3) and ethynylestradiol (EE2). The parameters related to the μ-SPE procedure namely; pH, sorbent amount, extraction solvent type and volume, sonication and vortex time, sample volume and salt effect on the extraction efficiency were screened by applying Plackett–Burmann design. The selected parameters were then optimized by using Box–Behnken design. The method was validated for the determination of estrogenic hormone residues in river water samples. Linear calibration plots were obtained for all hormones whose regression coefficients were larger than 0.98. RSD values were found less than 10% for three levels of concentration. LOD levels were calculated as; 0.012, 0.062, 0.018 and 0.693 ng L−1 for E1, E2, E3 and EE2, respectively. Recovery values were calculated in the range of 86.9–97.7%. Considering large sample volumes required for attaining low limits of these hormones, present method provides an ease for analyst as 10 mL of the sample is adequate for achieving the same sensitivity.