High-performance liquid chromatography–post-column chemiluminescence determination of aminopolycarboxylic acids at low concentration levels using tris(2,2′-bipyridyl)ruthenium(III)

A simple, selective and sensitive method for the determination of aminopolycarboxylic acids [diethylenetriaminepentaacetic acid (DTPA), S,S-ethylenediamine N,N′-disuccinic acid (EDDS), ethylenediaminetetraacetate (EDTA) and nitrilotriacetate (NTA)] has been developed using high-performance liquid chromatography with chemiluminescence detection. The aminopolycarboxylic acids were separated on a C18 reversed-phase column with an aqueous sulfuric acid mobile phase at a pH lower than 1.5. The eluate was mixed with tris(2,2′-bipyridyl)ruthenium(III), which was on-line generated by photooxidation of the ruthenium(II) complex in the presence of peroxydisulfate, and the generated chemiluminescence was detected. Calibration graphs, based on standard solutions, were linear over the range 8 × 10−9 to 4 × 10−5 M. The detection limits at a signal-to-noise ratio of 3 ranged from 9 × 10−10 to 8 × 10−8 M. The relative standard deviations of intra- and inter-day precision were below 1.3% and 2.1%, respectively. This HPLC system was successfully applied to the determination of aminopolycarboxylic acids in three different types of water samples. The low pH of the mobile phase limits interference from metal ions in natural waters. When such interference occurs, a cation-exchange column can be used to suppress it. The lowest amounts measurable were: 75 pg for NTA, 0.7 ng for EDDS, 0.8 ng for DTPA and 12 ng for EDTA. The method was also applied for the EDTA assay in canned foods.