Searching for anthropogenic contaminants in human breast adipose tissues using gas chromatography-time-of-flight mass spectrometry.

The potential of gas chromatography-time-of-flight mass spectrometry (GC-TOF MS) for screening anthropogenic organic contaminants in human breast adipose tissues has been investigated. Initially a target screening was performed for a list of 125 compounds which included persistent halogen pollutants [organochlorine (OC) pesticides, polychlorinated biphenylss (PCBs), polybrominated diphenyl ethers (PBDEs)], polyaromatic hydrocarbons (PAHs), alkylphenols, and a notable number of pesticides from the different fungicide, herbicide and insecticide families. Searching for target pollutants was done by evaluating the presence of up to five representative ions for every analyte, all measured at accurate mass (20-mDa mass window). The experimental ion abundance ratios were then compared to those of reference standards for confirmation. Sample treatment consisted of an extraction with hexane and subsequent normal-phase (NP) High performance liquid chromatography (HPLC) or SPE cleanup. The fat-free LC fractions were then investigated by GC-TOF MS.Full-spectral acquisition and accurate mass data generated by GC-TOF MS also allowed the investigation of nontarget compounds using appropriate processing software to manage MS data. Identification was initially based on library fit using commercial nominal mass libraries. This was followed by comparing the experimental accurate masses of the most relevant ions with the theoretical exact masses with calculations made using the elemental composition calculator included in the software.The application of both target and nontarget approaches to around 40 real samples allowed the detection and confirmation of several target pollutants including p,p'-DDE, hexachlorobenzene (HCB), and some polychlorinated biphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Several nontarget compounds that could be considered anthropogenic pollutants were also detected. These included 3,5-di-tert-butyl-4-hydroxy-toluene (BHT) and its metabolite 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO), dibenzylamine, N-butyl benzenesulfonamide (N-BBSA), some naphthalene-related compounds and several PCBs isomers not included in the target list. As some of the compounds detected are xenoestrogens, the methodology developed in this paper could be useful in human breast cancer research. (c) 2008 John Wiley & Sons, Ltd.