Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.