Determination of ethylenediaminetetraacetic acid in nuclear waste by high-performance liquid chromatography coupled with electrospray mass spectrometry

EDTA is a chelating agent that has been used in decontamination processes. Its quantification is required for nuclear waste management because it affects the mobility of radionuclides and metals in environment and, thus, can harm the safety of the storage. Ion-pair chromatography coupled with electrospray mass spectrometry detection is a convenient method for quantitative analysis of EDTA but EDTA should be present as a single anionic chelate form. However, radioactive liquid wastes contain high concentrations of heavy metals and salts and consequently, EDTA is present as several chelates. Speciation studies were carried out to choose a metal cation to be added in excess to the solution to obtain a major chelate form. Fe is the predominant cation and Fe(III)–EDTA is thermodynamically favored but these speciation studies showed that ferric hydroxide precipitated above pH 2. Consequently, it was not possible to quantify EDTA as Fe(III)–EDTA complex. Therefore, Ni2+ was chosen but its use implied pretreatment with a base of the solution to eliminate Fe. Deuterated EDTA was used as tracer in order to validate the whole procedure, from the treatment with a base to the final analysis by HPLC–ESI-MS. This analytical method was successfully applied for EDTA quantification in two real effluents resulting from a nuclear liquid waste process. A recovery rate between 60 and 80% was obtained. The limit of detection of this method was determined at 34 × 10−9 mol L−1.

► We make speciation studies to determine the behavior of EDTA in complex matrix.
► Fe precipitates at pH lower than 2 in nuclear waste.
► Ni is the cation for EDTA quantification by HPLC–ESI-MS.
► The method proved to be accurate and precise for the analysis in nuclear waste.