Silver nanoparticle aggregates on metal fibers for solid phase microextraction-surface enhanced Raman spectroscopy detection of polycyclic aromatic hydrocarbons

Solid phase microextraction (SPME), a solvent free technique for sample preparation, has been successfully coupled with GC, GC-MS, and HPLC for environmental analysis. In this work, a method combining solid phase microextraction with surface enhanced Raman spectroscopy (SERS) is developed for detection of polycyclic aromatic hydrocarbons (PAHs). Silver nanoparticle aggregates were deposited on the Ag-Cu fibers via layer-by-layer deposition, which were modified with propanethiol (PTH). The SERS-active SPME fiber was immersed in water directly to extract PAHs and then detected using a portable Raman spectrometer. The pronounced valence vibration of the C-C bond at 1030 cm(-1) was chosen as an internal standard peak for the constant concentration of PTH. The RSD values of the stability and the uniformity of the SERS-active SPME fiber are 2.97% and 5.66%, respectively. A log-log plot of the normalized SERS intensity versus fluoranthene concentration showed a linear relationship (R-2 = 0.95). The detection limit was 7.56 x 10(-10) M and the recovery rate of water samples was in the range of 95% to 115%. The method can also be applied to detection of PAH mixtures, and each component of the mixtures can be distinguished by Raman characteristic peaks. The SERS-active SPME fiber could be further confirmed by GC-MS.