ABSTRACT
Novel solid-phase microextraction coatings based on the use of multiwalled carbon nanotube-cyclodextrin (MWCNT-CD) nanocomposites were developed for the determination of 16-priority polycyclic aromatic hydrocarbons at ultratrace levels in snow samples. The performance of both ß- and γ-CD was tested to increase the detection capabilities towards the heaviest and most lipophilic compounds, i.e., five- and six-ring PAHs. To facilitate the interactions of MWCNTs with CDs, an oxidation procedure using both HNO3 and H2O2 was applied, obtaining superior results using MWCNTs-H2O2-γ-CD fiber. Detection and quantitation limits below 0.7 and 2.3 ng/L, RSD lower than 21%, and recoveries of 88(± 2)-119.8(± 0.4)% proved the reliability of the developed method for the determination of PAHs at ultratrace levels. The complexation capability of the γ-CD was also demonstrated in solution by NMR and fluorescence spectroscopy studies and at solid state by XRD analysis. Finally, snow samples collected in the ski area of Dolomiti di Brenta were analyzed, showing a different distribution of the 16 priority PAHs, being naphthalene, phenanthrene, fluoranthene, and pyrene the only compounds detected in all the analyzed samples.
ABSTRACT
A very sensitive and selective solid-phase microextraction-gas chromatography-mass spectrometry method based on the use of a deep cavity BenzoQxCavitand as innovative coating was developed and validated for the simultaneous determination of the 16 US-EPA priority pollutants polycyclic aromatic hydrocarbons (PAHs) in snow samples at ultra-trace levels. The presence of a 8.3 Å deep hydrophobic cavity allowed the engulfment of all the 16 PAHs, providing enhanced selectivity also in presence of interfering aromatic pollutants at high concentration levels. Validation proved the reliability of the method for the determination of the investigated compounds achieving detection limits in the 0.03-0.30 ng/L range, good precision, with relative standard deviations <18% and recovery rates in the 90.8(±2.1)%-109.6(±1.0)%. The detection of low-molecular weight PAHs in snow samples from Antarctica and Alps confirms the widespread occurrence of these compounds, thus assessing the impact of anthropogenic activities onto the environment.
Subject(s)
Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Gas Chromatography-Mass Spectrometry/methods , Limit of Detection , Polycyclic Aromatic Hydrocarbons/analysis , Reproducibility of Results , Snow , Solid Phase Microextraction/methods , Water Pollutants, Chemical/analysisABSTRACT
The occurrence of emerging contaminants is becoming of increasing importance to assess the impact of anthropogenic activities onto the environment. The present study reports for the first time the development and validation of an efficient method for the simultaneous determination of fragrance materials in water samples based on the use of a novel multiwalled carbon nanotubes (MWCNTs)-based solid-phase microextraction coating. Helical MWCNTs were selected as adsorbent material due to their outstanding extraction performance. The multicriteria method of desirability functions allowed the optimization of the experimental conditions in terms of extraction time and extraction temperature. Validation proved the reliability of the method for the determination of the analytes at ultra-trace levels, obtaining detection limits in the 0.2-13 ng/L range, good precision, with relative standard deviations lower than 20% and recovery rates in the 80 ± 12%-111 ± 11%. Superior enrichment factors compared to commercial fibers were also calculated. Finally, applicability to real sample analysis was demonstrated.
ABSTRACT
A tetraquinoxaline cavitand functionalized with methylenoxy bridges at the upper rim is proposed as selective solid-phase microextraction (SPME) coating for the determination of BTEX at trace levels in air. The SPME fibers were characterized in terms of film thickness, morphology, thermal stability and extraction capabilities. An average coating thickness of 35 (±4) µm, a thermal stability up to 350 °C and a good fiber-to-fiber and batch-to-batch repeatability with RSD lower than 15% were obtained. Excellent enrichment factors ranging from 360-700 × 10(3) were obtained for the investigated compounds. Finally, method validation proved the capabilities of the developed coating for the selective sampling of BTEX, achieving LOD values in the 0.4-1.2 ng m(-3) range.
