Adsorptive Microextraction Research Articles

Metal–organic framework MIL-53(Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass spectrometry

In this paper, the potential applications of metal-organic framework (MOF) materials as fiber coatings for the solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs) in water samples were explored. Fibers coated with MIL-53(Al, Cr, Fe) materials were fabricated by an adhesive method for SPME. The quantitation was performed by gas chromatography-tandem mass spectrometry (GC-MS/MS) using the multiple reaction monitoring mode. Among the three MIL-53(M) coatings, MIL-53(Al) showed the highest extraction efficiency towards PAHs under the current fabrication procedure. Under optimized conditions, the MIL-53(Al)-coated fiber showed good precision (relative standard deviation <12.5%), low detection limits (0.10 ng L(-1) to 0.73 ng L(-1), S/N = 3), and good linearity (R(2) > 0.98) for aqueous solutions containing 16 PAH . The fiber also offered high thermal and chemical stability. The method developed based on MIL-53(Al) SPME-GC-MS/MS was successfully applied in the analysis of real water samples. Based on the simulation results, the PAHs were adsorbed on MIL-53(Al) primarily through the hydrophobic and π-π interactions between PAHs and the organic linker of the material. The results presented in this paper indicate that water-stable MOF materials have great potential for the SPME of aromatic compounds in water samples.

Silica-modified magnetic nanoparticles functionalized with cetylpyridinium bromide for the preconcentration of metals after complexation with 8-hydroxyquinoline

Magnetically driven separation technology has received considerable attention in recent decade for its great potential application. In this study, we investigate the application of silica-modified magnetite nanoparticles (NPs) coated with a cationic surfactant as adsorbent for microextraction and determination of trace amounts of Cu(II), Ni(II), Co(II), Cd(II), Pb(II) and Mn(II) from environmental water samples. The synthesized silica-coated NPs in combination with cetylpyridinium bromide have the ability to adsolubilize the metal ions after complexation with 8-hydroxyquinoline. The NPs bearing the target metals are easily separated from the aqueous solution by applying an external magnetic field and the complexed metals were desorbed using acidic methanol. The desorbed analytes are introduced into the graphite furnace of an atomic absorption spectrometer. The effect of pH, complexing agent, amount of cetylpyridinium bromide, microextraction time, desorption conditions, ionic strength on extraction efficiency of the metal ions are investigated and optimized. Under the optimized conditions, the detection limits for Cu(II), Ni(II), Co(II), Cd(II), Pb(II) and Mn(II) are 4.7, 9.1, 9.5, 2.3, 7.4 and 15.3 ng L −1, respectively and the relative standard deviations ( n = 6) are less than 3.6%. The accuracy of the method was evaluated by recovery measurements on the spiked samples and good recoveries (93–113%) with low RSDs were achieved.

Synthesis and application of a novel solid-phase microextraction adsorbent: Hollow fiber supported carbon nanotube reinforced sol–gel for determination of phenobarbital

A novel solid-phase microextraction technique using a hollow fiber-supported sol–gel combined with multi-walled carbon nanotubes was employed in the determination of phenobarbital in wastewater. In this new technique, a silica-based, organic–inorganic polymer containing functionalized multi-walled carbon nanotubes (MWCNTs) was prepared with sol–gel technology via the reaction of tetraethylorthosilicate (TEOS) with an acidic catalyst (HCl). This sol was injected into a polypropylene hollow fiber segment for in situ gelation. This device operated in direct immersion sampling mode. The experimental setup is simple and affordable, and the device is disposable, so there is no risk of cross-contamination or carry-over. Parameters affecting extraction such as pH of the aqueous solution, ageing and extraction times, aqueous sample volume, agitation speed and carbon nanotube amount were optimized. Linearity was observed over a range of 0.50–5000 ng mL −1, with an estimation coefficient ( r 2) higher than 0.982. The limit of detection (LOD) was 0.32 ng mL −1 ( n = 5), and repeatability (RSD% = 2.9) was from the average of three levels of analyte concentrations (1, 1000 and 4500 ng mL −1) with three replicates for each within a single day. Finally, a pre-concentration factor of 2100 was obtained for phenobarbital.

Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination of low-level concentrations of butyltin compounds in seawater

Carbon nanotubes are a kind of new carbon-based nanomaterials, which have drawn great attention in many application fields. The potential of single-walled carbon nanotubes (SWCNTs) as solid-phase microextraction (SPME) adsorbent for the preconcentration of environmental pollutants has been investigated in recent years. In the present study, the feasibility of SWCNTs as SPME adsorbent for the determination of monobutyltin, dibutyltin and tributyltin in seawater samples was studied. To achieve this aim, the potential factors affecting the SPME efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. The developed method showed good performance according to the ICH (International Conference on Harmonization of Technical Requirements for Analytical Methods) criteria. The acquired calibration curves were linear ( r ≥ 0.992) over the concentration range from ≤12 to 2000 ng L −1. For all of the analytes, the limit of detection at signal-to-noise ratio of 3 was below 5 ng L −1. Furthermore, in comparison with the commercial carboxen/polydimethylsiloxane fiber, the developed SWCNT fiber showed better thermal stability (over 350 °C) and longer life span (over 150 times). The application of the proposed method in environmental analyses was shown by analyzing seawater samples from the harbors on the Persian Gulf for butyltin residues. Some of the butyltins were detected in the analyzed samples. Results of the present study demonstrate the feasibility of the SWCNTs as SPME adsorbent for the determination of butyltins in seawater samples.