Simultaneous Determination of 20 Pharmacologically Active Substances in Cow's Milk, Goat's Milk, and Human Breast Milk by Gas Chromatography–Mass Spectrometry

Abstract

This paper reports a systematic approach to the development of a method that combines continuous solid-phase extraction and gas chromatography-mass spectrometry for the simultaneous determination of 20 pharmacologically active substances including antibacterials (chloramphenicol, florfenicol, pyrimethamine, thiamphenicol), nonsteroideal anti-inflammatories (diclofenac, flunixin, ibuprofen, ketoprofen, naproxen, mefenamic acid, niflumic acid, phenylbutazone), antiseptic (triclosan), antiepileptic (carbamazepine), lipid regulator (clofibric acid), β-blockers (metoprolol, propranolol), and hormones (17α-ethinylestradiol, estrone, 17β-estradiol) in milk samples. The sample preparation procedure involves deproteination of the milk, followed by sample enrichment and cleanup by continuous solid-phase extraction. The proposed method provides a linear response over the range of 0.6-5000 ng/kg and features limits of detection from 0.2 to 1.2 ng/kg depending on the particular analyte. The method was successfully applied to the determination of pharmacologically active substance residues in food samples including whole, raw, half-skim, skim, and powdered milk from different sources (cow, goat, and human breast).

Determination of Hormones Residues in Milk by Gas Chromatography-Mass Spectrometry

“…The obtained values for the selected compounds are comparable with those presented by other authors who have applied methods using GC (Azzouz et al 2011) and slightly higher relative to the values resulting using LC techniques coupled to tandem mass spectrometry (Chen et al 2011;Kaklamanos and Theodoridis 2013;Malone et al 2010;Yan et al 2009). …”

“…The application of stable deuterium-labelled analogues of hormones as internal standards compensated the loss of analytes during sample preparation. Comparable values of recovery to those obtained were presented for different hormones in milk by other authors (Azzouz et al 2011;Chen et al 2011;Kaklamanos and Theodoridis 2013;Shao et al 2005).…”

“…The GC-based analytical methods in combination with MS are frequently used to identify volatile substances, which due to the step of derivatisation make it easy for reducing the polarity of the molecules, and increasing the thermal stability of the compounds is expectedly required (Azzouz et al 2011;Choi et al 2002). …”

“…However, accumulation of some drug residues in milk reducing its quality may pose a risk to the human population of different groups especially for infants and children (Cirkva and Št'astnỳ 2013;Courant et al 2008;Gamba et al 2009). Contaminated milk from the epidemiological point of view can be the cause of allergic reactions, hormone-dependent diseases and potential risk factor for cancer in humans (Azzouz et al 2011;Ganmaa and Sato 2005;Khaniki 2007). …”

“…A few reports relate to the analytical methods based on gas chromatography (Azzouz et al 2011;Choi et al 2002) or liquid chromatography (Chen et al 2011;Kaklamanos and Theodoridis 2013;Malone et al 2010;Ortelli et al 2009) techniques were developed and used for the determination of residues of the selected hormones in milk. The aim of the study was to develop a reliable multiresidue, screening, GC-MS-based method for the determination of hormones from three different, in terms of structures and properties, groups: synthetic stilbenes (diethylstilbestrol, dienestrol, hexestrol), steroids (17α/17β-19-nortestosterone, 17α/17β-trenbolone, methyltestosterone, 17β-boldenone, methylboldenone, 17β-testosterone, 17β-estradiol, medroxyprogesterone 17-acetate) and RALs (zeranol, taleranol, α-zearalenol, β-zearalenol, zearalanone) in milk samples.…”