Polycyclic aromatic hydrocarbon concentrations in gas and particle phases and source determination in atmospheric samples from a semiurban area of Dourados, Brazil.

A headspace solid-phase microextraction (HS-SPME) procedure that employs a PDMS/DVB fiber was developed for the analysis of gas-phase polycyclic aromatic hydrocarbons (PAHs) collected in polyurethane foam (PUF) by gas chromatography (GC) mass spectrometry. The method exhibited good linearity (R (2) > 0.99) and repeatability (4.9-25 %) as well as an impressive detection limit that ranged from 1.1 to 3.3 ng. Twenty-two air samples were collected by high-volume samplers from January to November 2007 in a semiurban area of Dourados (Brazil) and were analyzed for their content of total suspended particulates and PAHs. The PAHs were extracted from the PUF samples using the developed procedure (HS-SPME), and PAHs adsorbed on particulate matter were extracted with dichloromethane/methanol (4:1 [v/v]) in an ultrasonic bath. The values of the total daily concentrations of 16 PAHs determined in the samples ranged from 0.375 to 8.407 ng m(-3). In addition, diagnostic ratios were calculated, showing that the PAHs in the atmosphere at the sampling site originated predominantly from vehicle emissions and the combustion of grass and wood. Hierarchical cluster analysis and principal component analysis were performed as well, the results of which indicated (1) the same sources of PAH identified by the diagnostic ratios and (2) that the sampling days could be categorized into three groups depending on the atmospheric conditions. GC retention indices were also used to identify PAHs, biphenyl (phenylbenzene), and heterocyclic organic compounds (benzofurans) in some of the samples.