Gas chromatography/mass spectrometry comprehensive analysis of organophosphorus, brominated flame retardants, by-products and formulation intermediates in water.

A multiresidue method based on gas chromatography coupled to quadrupole mass spectrometry was developed to determine organophosphorus flame retardants, polybromodiphenyl ethers (BDEs 28, 47, 99, 100, 153, 154, 183 and 209), new brominated flame retardants, bromophenols, bromoanilines, bromotoluenes and bromoanisoles in water. Two ionization techniques (electron ionization--EI, and electron capture negative ionization--ECNI) and two acquisition modes (selected ion monitoring--SIM, and selected reaction monitoring--SRM) were compared as regards to mass spectral characterization, sensitivity and quantification capabilities. The highest sensitivity, at expenses of identification capacity, was obtained by GC-ECNI-MS/SIM for most of the compounds analyzed, mainly for PBDEs and decabromodiphenyl ethane while GC-EI-MS/MS in SRM was the most selective technique and permitted the identification of target compounds at the pg level, and identification capabilities increased when real samples were analyzed. This method was further used to evaluate the presence and behavior of flame retardants within a drinking water treatment facility. Organophosphorus flame retardants were the only compounds detected in influent waters at levels of 0.32-0.03 μg L⁻¹, and their elimination throughout the different treatment stages was evaluated.