Direct determination of dibutyl and monobutyl phosphate in a tributyl phosphate/nitric aqueous-phase system by electrospray mass spectrometry

Abstract

Electrospray ionization mass spectrometry was tested for its potential use in the quantification of monobutyl phosphate (H2MBP) and dibutyl phosphate (HDBP), two degradation products of tributyl phosphate (TBP), the extractant used in the nuclear fuel reprocessing known as the PUREX process. Detection and quantification of these phosphate esters by electrospray in positive and negative ionization mode are reported in this study. This fast and reliable method, which does not require any preliminary sample extraction, appears to be very attractive for process control. Negative ionization mode gave abundant [M - H]- ions for both HDBP and H2MBP products. Thus, the concentration of H2MBP between 0.1 and 10 g/L in concentrated aqueous nitrate solutions can be precisely determined. Moreover, the concentration of HDBP up to 1 g/L in a TBP matrix was evaluated in this mode. For HDBP concentrations below 1 g/L, detection in the positive ionization mode appeared to be attractive. TBP and HDBP cluster detection allowed quantitative HDBP determination. Indeed, small amounts of HDBP in commercial TBP (60 mg/L) could be directly quantified using the specific [2TBP, HDBP + H]+ cluster at m/z 743.