Determination of aromatic amines in aqueous extracts of polyurethane foam using hydrophilic interaction liquid chromatography and mass spectrometry. 
A method is presented for the determination of aromatic amines in aqueous extracts of polyurethane (PUR) foam.  The method is based on the extraction of PUR foam using aqueous acetic acid (0.1%, w/v) followed by determination of extracted aromatic amines using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry (MS/MS) with positive electrospray ionisation.  The injections of volumes up to 5 μL of aqueous solutions were made possible by on-column focusing with partially filled loop injections.  The fragmentation patterns for 2,4- and 2,6-toluene diamine (TDA) and 4,4'-methylene dianiline (MDA) were clarified by performing a hydrogen-deuterium exchange study.  TDA and MDA were determined using trideuterated 2,4- and 2,6-TDA and dideuterated 4,4'-MDA as internal standards.  Linear calibration graphs were obtained over the range 0.025-0.5 μg mL(-1) with correlation coefficients >0.996 and the instrumental detection limit for each compound was <50 fmol.  The stability of the amines was influenced by the matrix, so their concentrations decreased over time.  Agreement was observed between the results of analyses of PUR foam extracts by HILIC-MS/MS and results obtained by ethyl chloroformate derivatisation and reversed phase (RP) liquid chromatography-mass spectrometry (LC-MS/MS).  TDA was observed to be unstable in extracts of foam but not in pure solutions.