Towards in situ detection of PAH trace in seawater using SERS-active sensors

This paper reports the development of a sensor based on surface-enhanced Raman scattering (SERS) for analyses in seawater. Polycyclic aromatic hydrocarbons (PAHs) are targeted by these sensors and their detection in situ summons up chemical synthesis and optical development. Firstly, a relevant synthesis of SERS active substrates based on gold nanostructures is presented. Different kinds of substrates have been synthesized under variable experimental conditions to modify some parameters such as i) gold shape, size and distribution and such as ii) chemical functionalization: (i) gold nanoparticles were prepared either by chemical reduction of HAuCl4 or by physical deposition. (ii) Substrates were functionalized by hydrophobic films to allow nonpolar molecules pre-concentration. Low concentration from ppb to ppm of PAHs were detected with a Raman microscope designed for lab experiments. Sensors exhibit strong enhancement of Raman scattering from molecules adsorbed on the films. Spectra were recorded for two PAHs (naphthalene and pyrene) in artificial sea-water with limits of detection of 10ppb for both with a short integration time (10s) and a low incident laser power (~0.1mW). Active substrate surface morphology was characterized with scanning electron microscopy (SEM) measurements. Secondly, an home-made in situ Raman spectrometer was developed and has been connected to a micro-fluidic system. This system was designed to host SERS-active sensors in order to ensure measurements with a flow cell. This original configuration of in situ Raman spectroscopy was then achieved. Such a device is now ready to use to confirm the PAH detection at ppb levels during the offshore experiments thanks to SERS sensors.

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