Innovative Raman spectroscopic concepts for in situ monitoring of chemicals in seawater

Optical sensors based on Raman spectroscopy are suitable for a rapid identification and quantification of pollutants such as Polycyclic Aromatic Hydrocarbons (PAHs). Additionally, Surface enhanced Raman spectroscopy (SERS) has gained increasing attention as a powerful technique for in-situ monitoring of these substances in seawater to achieve limits of detection (LODs) in the sub-nmol/l range. A low-cost method based on electroless plating solution of chloroauric acid (HAuCl4) and hydrogen peroxide (H2O2) was developed in our group to construct a gold island film as SERS substrate to achieve a well reproducible, high sensitive and seawater resistant SERS sensor. The substrates show good resistance against seawater determined by long-term stability tests carried out over 12 weeks of storage of the substrates in artificial seawater. The investigations show that the substrates still have about 50 % of their initial activity after 4 weeks of storage and about 15 % after two months. This type of substrate is reproducible with variability in the SERS intensities of about 8 %. Shifted excitation Raman difference spectroscopy (SERDS) was applied by using a microsystem diode laser emitting at 784.3 nm and 784.8 nm to remove the fluorescence interference and to improve the Raman signals. This combination of SERS and SERDS yields a limit of detection of 1 nmol/l for pyrene which was selected as representative PAH. These quantitative results show that the designed SERS substrates are suitable for the in-situ monitoring of PAHs in the marine environment.