Occurrence of organic phosphates in particulate matter of the vehicle exhausts and outdoor environment – A case study

The occurrence and concentrations of a wide range of organic phosphates (OPEs) in vehicle's exhaust (VPM), ambient air particulate matter (APM), and soil of various urban environments were researched. VPM comes from passenger cars, commercial vehicles, marine and bus engines emitted in New European Driving Cycle tests whereas APM was sampled in several sites of the Upper Silesia region (Poland). APM and VPM collected on filters and soil from the same locations as APM sampling sites were extracted with dichloromethane and extracts analyzed by gas chromatography-mass spectrometry. The OPEs found include aryl phosphates such as triphenyl phosphate (TPhP) and tricresyl phosphate (TCP), alkyl phosphates - triethyl phosphate (TEP), tripropyl phosphate (TPP), tributyl phosphate (TBP) and tri(butoxyethyl)phosphate (TBEP), and alkylchlorinated phosphates including tris-(2-chloroisopropyl) phosphate (TCiPP) and tris(2-chloroethyl) phosphate (TCEP). Occurrence and concentrations of these compounds in the PM investigated are highly variable. It was found that total concentrations in APM are directly related to traffic density in particular sites of the urban environment and a style of a vehicle driving. The highest emission of OPEs was found at a crossroad and city center sites where traffic is the densest and vehicles stops and starts are frequent. Village and residential areas were less exposed to OPEs emission. Since OPEs concentrations show exponential correlations to each other also human exposure to these compounds increases exponentially with increasing traffic density. High TEP and TBP level is tentatively proposed as an indicator of emission from petrol-fueled cars. Concentrations of OPEs in some soil are related to their emission to the air and resistance to degradation of a particular compound since only the most resistant TCiPP and TPhP were identified in soil extracts.