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

Abstract

The potential of 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 (OC pesticides, PCBs, PBDEs), 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 HPLC or SPE clean-up. 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 non-target 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 non-target approaches to around 40 real samples allowed the detection and confirmation of several target pollutants including p,p'-DDE, HCB, and some PCBs and PAHs. Several non-target 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, some naphthalene-related compounds and several PCBs isomers not 3 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.4

Current use of high-resolution mass spectrometry in the environmental sciences

“…Despite its excellent features, however, this technique has rarely been used for determination of organic contaminants [10,29]. Almost all applications deal with persistent organic pollutants and other priority GC-amenable compounds in environmental [30,31] and biological [32,33] samples. A few applications are focussed on doping and drug control [29,34,35].…”

Application of Gas Chromatography-Quadrupole-Time-of-Flight-Mass Spectrometry for Post-Target Analysis of Volatile Compounds in Fructus Amomi

“…21,22,24 This procedure enables the detection and reliable identification of the compounds in complicated matrices and has widespread application in analyzing trace-level organic compounds in the environment, food safety and toxicology. 20,[23][24][25] In the analysis of volatile natural products, conventional qualitative approaches (mass spectral search and retention index) based on GC-MS do not fully exploit the abundant full-spectrum information provided by GC-HR-ToF-MS. The detection of trace-level compounds is frequently interrupted by co-elute and/or other backgrounds.…”

Metabolome profiling reveals adaptive evolution of Saccharomyces cerevisiae during repeated vacuum fermentations

“…GC-TOF-MS was a well-established analytical technique within the field of metabolomics (Noctor et al 2007;Wiklund et al 2008;Hernández et al 2009). It was applied here to detect the intracellular metabolites of S. cerevisiae in adaptive evolution during repeated vacuum fermentations.…”