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Electrochemical SERS Detection of Chlorinated Hydrocarbons in Aqueous Solutions

Volume 48, Number 10 (Oct. 1994) Page 1265-1271

Storey, John M.E.; Shelton, Robert D.; Barber, Tye E.; Wachter, Eric A.


An in situ method for the determination of trichloroethylene (TCE), perchloroethylene (PCE), chloroform (CHCI3), and carbon tetrachloride (CCI4 in aqueous solution is described. The method is based on ESERS—a combination of electrochemical methods and surface-enhanced Raman scattering (SERS). Electrochemistry prepares the surface of a copper electrode for SERS and concentrates the analyte on the surface. The formation of common reaction products for chloroalkanes and for chloroalkenes prevents unequivocal differentiation within a specific class of chlorinated hydrocarbons. However, spectroscopic selectivity between the chloroalkane and chloroalkene classes is excellent, while differences in electrochemical response provide a secondary means for differentiating analyte class. Sensitivity was found to be: <1 ppm for TCE; 15 ppm for PCE; 15 ppm for CHCI3; and 10 ppm for CCI4. Application of the method to groundwater contaminated with TCE has been demonstrated. In combination with a fiber-optic waveguide, the ESERS technique offers potential for remote detection of chlorinated hydrocarbons in groundwater and remediation process streams.