Determination of photoirradiated tetracyclines in water by high-performance liquid chromatography with chemiluminescence detection based reaction of rhodamine B with cerium (IV)

A simple, selective and sensitive method has been developed for the simultaneous determination of tetracycline, oxytetracycline, chlorotetracycline, demeclocycline, doxycycline and meclocycline based on reversed-phase high-performance liquid chromatography with chemiluminescence detection. The procedure was based on the chemiluminescent enhancement by photoirradiated tetracyclines of the cerium (IV)–rhodamine B system in sulphuric acid medium. The six tetracyclines were separated on an Aquasil-C18 column with a gradient elution using a mixture of acetonitrile and 0.1 mol L−1 phosphate buffer as mobile phase, photoderivatized using a photoreactor consisting of a tube reactor coil of PFA and a 8W Xenon lamp. Under the optimized conditions, the method was validated with respect to linearity, precision, limits of detection and quantification and accuracy. The relative standard deviation (RSD) on intra-day precision was below 10% and detection limits ranged between 0.12 and 0.34 μg L−1. The proposed method has been successfully applied to the determination of tetracyclines in surface water samples. A possible mechanism of the chemiluminescence in the system is discussed.