Determination of methenamine residues in edible animal tissues by HPLC-MS/MS using a modified QuEChERS method: Validation and pilot survey in actual samples
Introduction
Methenamine is a kind of medicine, which is used for the therapy of urinary tract infection (Musher & Griffith, 1974) and nephropathy (Jian, 2010). The mechanism of treatment is that formaldehyde has antibacterial activity, and formaldehyde is derived from methenamine under acidic urine condition (Ariens, Hanselaar, Henderson, & Simonis, 1982). Because it is effective and relatively cheap, methenamine is widely utilized to control disease of livestock in farming practices. However, veterinary drug may be accumulated in edible animal tissues when it is continuously used to the livestock. Serious drug residues in animal-derived food may cause antibiotic resistance or allergic reactions in humans (Lombardo-Agüí, García-Campaña, Cruces-Blanco, & Gámiz-Gracia, 2015). Formaldehyde that derived from methenamine has carcinogenicity, acute and chronic toxicity (Ariens et al., 1982). Methenamine is not approved for use as food additive in the USA, Russia, Australia, or New Zealand (Commonwealth of Australia, 2011, Wikipedia, 2014). Nowadays, the public begin to concern about methenamine as the residue of veterinary drug in animal-derived food, which may cause potential harm to public health. Therefore, in order to monitor methenamine residues in edible animal tissues, it is indispensable to develop a sensitive and effective analytical method.
There are some analytical methods used to determine methenamine in pharmaceutical or environmental field, such as analysis of methenamine and its derivatives in medicine using ion-exchange HPLC (Pavitrapok & Williams, 2006), or determination of methenamine in river water by liquid chromatograph-tandem mass spectrometer (Kakimoto, Motegi, & Nojiri, 2013). There are a few published methods for the determination of methenamine in foods. In a recent study, an analytical method has been established to determine methenamine in dairy products, and solid phase extraction method was used for purification (Xu et al., 2015). At present, a more convenient method is popularly utilized in sample pretreatment field. This method is called QuEChERS (quick, easy, cheap, effective, rugged, and safe). Since the QuEChERS method was first developed (Anastassiades, Lehotay, Stajnbaher, & Schenck, 2003), it has been extensively applied to analyze pesticides and veterinary drugs residues in various matrices. Recently, a QuEChERS method has been successfully used to determine sulphonamides in animal tissues, with anhydrous magnesium sulfate for drying the remaining water in the extract, and PSA sorbents for purification (Abdallah, Arnaudguilhem, Jaber, & Lobinski, 2014). Anhydrous sodium sulfate and octadecylsilane (C18) sorbents have been also used to dry the remaining water and purify veterinary drugs residues in different muscle tissues (Kang et al., 2014). However, there was little application of the QuEChERS method on the determination of methenamine in edible animal tissues.
The aim of this study was to develop a QuEChERS method, which was suitable to analyze methenamine in edible animal tissues. Thus, the effect of sulfate and sorbent was investigated in this experiment. High performance liquid chromatography (HPLC) coupled with tandem mass spectrometry (MS/MS) is a rapid and precise technique for determination of chemical residues. However, there is matrix effect (ME) in quantitative LC-MS/MS analysis. In order to compensate ME, the isotope dilution mass spectrometry technique is an effective method (Lee, Kim, & Kim, 2013). Therefore, a reference material labeled with stable isotopes was used as an internal standard to quantify the methenamine by HPLC-MS/MS in this work. The method was validated for linearity, precision, accuracy, LOD and LOQ.
Section snippets
Reagents and materials
The reagents were analytical reagent grade unless otherwise specified. Methenamine (purity ≥ 99%) and methenamine-13C615N4 (purity ≥ 97%) were purchased from Sigma–Aldrich (St. Louis, USA). HPLC grade acetonitrile (ACN) and n-hexane were from Merck KGaA (Darmstadt, Germany). Formic acid (purity ≥ 98%) and ammonium acetate (purity ≥ 98%) were from Acros Organics (New Jersey, USA). Anhydrous magnesium sulfate (MgSO4) and anhydrous sodium sulfate (Na2SO4) were from Sinopharm Chemical Reagent Co.,
Optimization of HPLC-MS/MS conditions
The composition of the mobile phase can influence the response values of analytes in LC-MS/MS detection (Guan, Tang, Chen, Xu, & Li, 2013). In this study, three kinds of mobile phase system were used: the first system was water-ACN; the second system was 5.0 mmol/L of ammonium acetate in water-ACN; the third system was 0.1% of formic acid and 5.0 mmol/L of ammonium acetate in water-ACN. The results indicated that the response values of methenamine and methenamine-13C615N4 were the highest in
Conclusions
In this study, a QuEChERS method was applied to extract methenamine residue from edible animal tissues, and analyzed by HPLC-MS/MS with the ESI positive mode. A series of purification and chromatographic conditions were also optimized. The results manifested that Na2SO4 and PSA were the appropriate materials for drying the remaining water and purifying the methenamine in animal tissues, and this pre-treatment method was convenient and effective. Under the optimized conditions, the linearity,
Acknowledgments
This work received the support of the Health Department of Yunnan Province on Formulation of Food Safety Standards, item number: YH [2014] DB004.
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