Optimisation of a selective method for the determination of organophosphorous triesters in outdoor particulate samples by pressurised liquid extraction and large-volume injection gas chromatography-positive chemical ionisation-tandem mass spectrometry

A selective analytical method for the determination of nine organophosphate triesters and triphenylphosphine oxide (TPPO) in outdoor particulate matter is presented. It involves a fully automated pressurised liquid extraction (PLE) step, integrating an alumina clean-up process, and subsequent determination by large-volume injection gas chromatography-positive chemical ionisation-tandem mass spectrometry (LVI-GC-PCI-MS/MS). The extraction variables (solvent, amount of adsorbent, temperature, time and number of cycles) were optimised using a multicriteria strategy which implements a desirability function that maximises both extraction and clean-up efficiencies while searching for the best-compromise PLE conditions. The final method affords quantification limits of between 0.01 and 0.3 mu g g(-1) and recoveries of > 80%, with the exceptions of the most polar analytes, TCEP and TPPO (similar to 65%) for both urban dust and PM10 samples. Moreover, the method permitted the levels of these compounds in dust deposited outdoors (between LOD and 0.5 mu g g(-1) for TEHP) and PM10 samples (between LOD and 2.4 mu g m(-3) for TiBP) to be measured and reported for the first time.