Development of sample extraction and clean-up strategies for target and non-target analysis of environmental contaminants in biological matrices

Baduel, Christine, Mueller, Jochen F., Tsai, Henghang and Gomez Ramos, Maria Jose (2015) Development of sample extraction and clean-up strategies for target and non-target analysis of environmental contaminants in biological matrices. Journal of Chromatography A, 1426 33-47. doi:10.1016/j.chroma.2015.11.040


Author Baduel, Christine
Mueller, Jochen F.
Tsai, Henghang
Gomez Ramos, Maria Jose
Title Development of sample extraction and clean-up strategies for target and non-target analysis of environmental contaminants in biological matrices
Journal name Journal of Chromatography A   Check publisher's open access policy
ISSN 1873-3778
0021-9673
Publication date 2015-09-04
Year available 2015
Sub-type Article (original research)
DOI 10.1016/j.chroma.2015.11.040
Open Access Status Not yet assessed
Volume 1426
Start page 33
End page 47
Total pages 15
Place of publication Amsterdam, Netherlands
Publisher Elsevier
Language eng
Subject 1602 Analytical Chemistry
1303 Biochemistry
1605 Organic Chemistry
Abstract Recently, there has been an increasing trend towards multi-targeted analysis and non-target screening methods as a means to increase the number of monitored analytes. Previous studies have developed biomonitoring methods which specifically focus on only a small number of analytes with similar physicochemical properties. In this paper, we present a simple and rapid multi-residue method for simultaneous extraction of polar and non-polar organic chemicals from biological matrices, containing up to 5% lipid content. Our method combines targeted multi-residue analysis using gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) and a multi-targeted analysis complemented with nontarget screening using liquid chromatography coupled to a quadrupole time of flight mass spectrometry (LC-QTOF-MS/MS). The optimization of the chemical extraction procedure and the effectiveness of different clean-up methods were evaluated for two biological matrices: fish muscle (lipid content similar to 2%) and breast milk (similar to 4%). To extract a wide range of chemicals, the partition/extraction procedure used for the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was tested as the initial step for the extraction of 77 target compounds covering a broad compound domain. All the target analytes have different physico-chemical properties (log Kow ranges from -0.3 to 10) and cover a broad activity spectrum: from polar pesticides, pharmaceuticals, personal care products (PPCPs) to highly lipophilic chemicals such as polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochloride pesticides (OCPs). A number of options were explored for the clean-up of lipids, proteins and other impurities present in the matrix. Zirconium dioxide-based sorbents as dispersive solid-phase extraction (d-SPE) and protein-lipid removal filter cartridges (Captiva ND Lipids) provided the best results for GC-MS and LC-MS analysis respectively. The method was fully validated for samples of fish muscle and breast milk through the evaluation of recoveries, matrix effects, limit of quantification, linearity and precision (inter-day and intra-day). Mean recoveries (n = 5) were between 70 and 120% with relative standard deviations (RSD) less than 20% in most of the cases. GC-MS/MS LOQs ranged from 0.08 to 3 mu g/kg and LC-QTOF-MS/MS LOQs ranged from 0.2 to 9 mu g/kg. The developed strategy was successfully applied for analysis of real samples; 22 target analytes were found in the breast milk samples and 10 in the fish samples. Non-target analysis allowed the detection and identification of an additional 14 contaminants and metabolites in the samples. (C) 2015 Elsevier B.V. All rights reserved.
Formatted abstract
Recently, there has been an increasing trend towards multi-targeted analysis and non-target screening methods as a means to increase the number of monitored analytes. Previous studies have developed biomonitoring methods which specifically focus on only a small number of analytes with similar physico-chemical properties. In this paper, we present a simple and rapid multi-residue method for simultaneous extraction of polar and non-polar organic chemicals from biological matrices, containing up to 5% lipid content. Our method combines targeted multi-residue analysis using gas chromatography triple quadrupole mass spectrometry (GC-QqQ-MS/MS) and a multi-targeted analysis complemented with non-target screening using liquid chromatography coupled to a quadrupole time of flight mass spectrometry (LC-QTOF-MS/MS). The optimization of the chemical extraction procedure and the effectiveness of different clean-up methods were evaluated for two biological matrices: fish muscle (lipid content ∼2%) and breast milk (∼4%). To extract a wide range of chemicals, the partition/extraction procedure used for the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was tested as the initial step for the extraction of 77 target compounds covering a broad compound domain. All the target analytes have different physico-chemical properties (log Kow ranges from −0.3 to 10) and cover a broad activity spectrum; from polar pesticides, pharmaceuticals, personal care products (PPCPs) to highly lipophilic chemicals such as polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochloride pesticides (OCPs). A number of options were explored for the clean-up of lipids, proteins and other impurities present in the matrix. Zirconium dioxide-based sorbents as dispersive solid-phase extraction (d-SPE) and protein-lipid removal filter cartridges (Captiva ND Lipids) provided the best results for GC-MS and LC-MS analysis respectively. The method was fully validated for samples of fish muscle and breast milk through the evaluation of recoveries, matrix effects, limit of quantification, linearity and precision (inter-day and intra-day). Mean recoveries (n = 5) were between 70 and 120% with relative standard deviations (RSD) less than 20% in most of the cases. GC-MS/MS LOQs ranged from 0.08 to 3 μg/kg and LC-QTOF-MS/MS LOQs ranged from 0.2 to 9 μg/kg. The developed strategy was successfully applied for analysis of real samples; 22 target analytes were found in the breast milk samples and 10 in the fish samples. Non-target analysis allowed the detection and identification of an additional 14 contaminants and metabolites in the samples.
Keyword Targeted/non-targeted screening
Breast milk
Fish muscle
GC-MS/MS
LC-QTOF
QuEChERS
Q-Index Code C1
Q-Index Status Provisional Code
Grant ID LE 140100129
FF 120100546
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
National Research Centre for Environmental Toxicology Publications
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 16 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 17 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 15 Dec 2015, 10:58:34 EST by System User on behalf of Scholarly Communication and Digitisation Service