Air sampling with Empore solid phase extraction membranes and online single-channel desorption/liquid chromatography/mass spectrometry analysis: Determination of volatile and semi-volatile organophosphate esters

A method for determining organophosphate esters in air samples using C8 Empore solid phase extraction (SPE) membranes has been developed. After the sampling the analytes trapped in the membrane are completely desorbed with methanol, using an extraction cell connected online to the organic modifier channel of a HPLC gradient pump. The addition of water to the mobile phase prior to analytical chromatography ensures that the analytes are refocused and efficiently separated. Sampling with Empore SPE membranes enables the collection of analytes in both the vapour phase and particulate matter. During the air sampling procedure no losses were observed after 24 h of sampling, yielding a total volume of 14.4 m3, even for the most volatile compound used in this investigation (trimethylphosphate). Complete desorption was observed for all the organophosphate esters and recoveries were greater than 95%, with a relative standard deviation of less than 8%. The limits of detection ranged between 0.4 and 19 pg/m3. The effect of particulate matter on the extraction efficiency was investigated in detail by spiking the membranes with reference standard material. It was also found that the SPE membranes could be stored for at least 5 days at room temperature without any evidence of loss. The efficacy of the method was verified using real samples from different common indoor environments. Interestingly, significant quantities of several phosphate esters were found in a NIST standard reference material (urban dust, SRM 1649a).