The potential of solid–liquid extraction fluorescence line narrowing spectroscopy is evaluated for screening polycyclic aromatic hydrocarbons in aqueous samples. Octadecyl silica membranes are used with the dual purpose of sample preconcentration and solid substrate for spectroscopic measurements. 4.2 K fluorescence line narrowed spectra are directly recorded from the membrane with the aid of a fiber-optic probe. The experimental procedure is free from organic solvents and takes less than 5 min per sample. With 10 mL of water sample, the limits of detection are at the parts-per-billion level. Qualitative analysis is based on wavelength time matrices, which provide a unique format for compound identification based on spectral and lifetime data. The selectivity of this approach is demonstrated with the unambiguous determination of naphthalene in a heavily contaminated water sample.
