An extraction procedure based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) approach has been developed and used for analysis of particle-bound nitrated and oxygenated PAH derivatives (NPAH and OPAH, respectively). Several analytical conditions, for example GC injection temperature and MS detection settings, were optimized. This analytical procedure enabled simultaneous GC-NICIMS quantification of 32 NPAH and 32 OPAH (or other oxygenated compounds), including typical components of secondary organic aerosol (SOA) formed by photooxidation of PAH (e.g. 2-formyl-trans-cinnamaldehyde and 6H-dibenzo[b,d]pyran-6-one). The QuEChERS-like approach was optimized, including the nature of the extraction solvent, the sorbent used for clean-up, and extraction time. The final extraction procedure was based on brief mechanical agitation (vortex mixing for 1.5 min), with 7 mL acetonitrile as solvent. Because dispersive solid-phase extraction (d-SPE) did not provide satisfactory results, SPE using SiO2 was selected for sample purification. Identical results were obtained when the QuEChERS-like and traditional pressurised solvent extraction (PLE) procedures were compared for analysis of fortified ambient air particle samples. The procedure was validated by analysis of two aerosol standard reference materials (NIST SRM 1649b (urban dust) and SRM 2787 (fine particulate matter, <10 μm)). For numerous NPAH and OPAH, this is the first report of their quantification in both SRMs. Compared with other extraction methods, including PLE, the QuEChERS-like procedure resulted in increased productivity and reduced extraction cost. This paper shows that QuEChERS-like extraction procedures can be suitably adapted for molecular chemical characterization of aerosol samples and could be extended to other categories of compound.
Meconium is the earliest stool of newborns, and is a complex matrix that reflects the degree of exposure of the fetus to xenobiotics. To investigate fetal exposure to volatile organic compounds, an analytical method was developed to identify and quantify BTEX (benzene, toluene, ethylbenzene, and o,m,p-xylene) and two chlorinated solvents (trichloroethylene and tetrachloroethylene) in meconium. Headspace-solid-phase microextraction coupled with gas chromatography-mass spectrometry was selected because it is simple, sensitive, can be automated, and requires no extensive sample preparation. Several extraction variables were optimized (fiber type, incubation time, temperature of fiber, and use of salt). Because meconium is a complex matrix, quantification by SPME was considered carefully because of potential interference, for example competitive adsorption. Calibration in water was compared with calibration in meconium using external and internal methods (with isotope-labeled compounds). In meconium, limits of quantification were determined to be in the range 0.064-0.096 ng g(-1) for the investigated compounds. All target compounds were determined in "real-case" meconium samples.
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