A green approach for organophosphate ester determination in airborne particulate matter: Microwave-assisted extraction using hydroalcoholic mixture coupled with solid-phase microextraction gas chromatography-tandem mass spectrometry.

Particulate matter (PM) is among the most dangerous air pollutants, and there is a growing concern related to the effects of airborne particles on human health. Their harmful effects can be derived are directly linked to the size of particles themselves and the associated pollutants after they have been taken up by inhalation. In this work was developed a new analytical method for the quantification of organophosphorus esters (OPE) bound to airborne PM. The proposed protocol provides for the microwave-assisted extraction (MAE) of the analytes from the PM followed by solid-phase microextraction gas chromatography-tandem mass spectrometry determination (SPME-GC-MS/MS). Unlike to the traditional protocol, which provides for the use of tedious Soxhlet extraction with environmentally damaging organic solvents, the proposed method allows for a reliable quantification by using an eco-friendly hydroalcoholic mixture (water/ethanol; 50:50, v/v). The method was developed using as target compounds ten organophosphate esters, namely tripropyl phosphate (TPP), tri-n-butyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tributoxyethyl phosphate (TBEP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tricresyl phosphate (TCP). The extraction performance of five SPME fibers was evaluated and the DVB/CAR/PDMS coating demonstrated to be the most suitable for the extraction of the target analytes. Experimental Design was used for the multivariate optimization of the parameters affecting the MAE process as well as the SPME extraction, and the optimal working conditions were determined by using Derringer's desirability function. The developed method was validated in terms of linearity, sensitivity (LLOQ values of 0.5 ng/mL for TDCPP and 0.1 ng/mL for the other analytes), matrix effect (81-117%), intra and inter day accuracy (83-115% and 80-115%, respectively), and precision (repeatability and reproducibility in the range 1.0-12.4% and 2.3-15.2%, respectively). The satisfactory performances reached make the proposed protocol a green and high-throughput alternative for OPE quantification in particulate matter.