Development and validation of a method for determination of residues of 15 pyrethroids and two metabolites of dithiocarbamates in foods by ultra-performance liquid chromatography–tandem mass spectrometry

Abstract

This paper reports a novel approach for the detection, confirmation, and quantification of 15 selected pyrethroid pesticides, including pyrethins, and two metabolites of dithiocarbamates in foods by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS-MS). The proposed method makes use of a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure that combines isolation of the pesticides and sample cleanup in a single step. Analysis of pyrethroids and dithiocarbamate metabolites was performed by UPLC-MS-MS operated with electrospray and atmospheric pressure chemical ionization, respectively. Two specific precursor-product ion transitions were acquired per target compound in multiple reaction monitoring (MRM) mode. Such acquisition achieved the minimum number of identification points according to European Commission (EC) document no. SANCO/10684/2009, thus fulfilling the EC point system requirement for identification of contaminants in samples. The method was validated with a variety of food samples. Calibration curves were linear and covered from 1 to 800 μg kg(-1) in the sample for all target compounds. Average recoveries, measured at mass fractions of 10 and 100 μg kg(-1) for pyrethroids and 5 and 50 μg kg(-1) for dithiocarbamate metabolites, were in the range of 70-120% for all target compounds with relative standard deviations below 20%. Method limits of quantification (MLOQ) were 10 μg kg(-1) and 5 μg kg(-1) for pyrethroids and dithiocarbamate metabolites, respectively. The method has been successfully applied to the analysis of 600 food samples in the course of the first Hong Kong total diet study with pyrethroids and metabolites of dithiocarbamates being the pesticides determined.

Liquid Chromatography-Mass Spectrometry in the Analysis of Pesticide Residues in Food

“…Isocratic elution is used sporadically (Chung and Lam 2012). The advantage of gradient elution is the possibility of achieving the optimum conditions of separation by decreasing the polarity of the mobile phase.…”

“…The additives to LC/ MS mobile phases are restricted to volatile compounds; nonvolatile compounds such as phosphorous salts have to be avoided. The non-polar octadecylsilane phase (C 18 ) (Gómez-Pérez et al 2015;Fillatre et al 2014;AguileraLuiz et al 2011;Chung and Lam 2012;Gilbert-Lopez et al 2012;Sinha et al 2012) is commonly used as the stationary phase; the medium-polar octylsilane phase is used much more rarely (C 8 ) (Lozano et al 2012;Nunez et al 2012;Kmellar et al 2011;Ferrer et al 2011). Columns with sorbent particle diameters of 3, 3.5, 4, and 5 μm are available from a range of manufacturers, the most popular being: Zorbax (Rajski et al 2013;Lozano et al 2012;Lee et al 2009a, b;Radisic et al 2009), Atlantis (Tran et al 2012;Tseng et al 2009;Romero-Gonzalez et al 2006), Luna (Camino-Sanchez et al 2010;Lehotay et al 2010), Polaris (Anagnostopoulos et al 2012), and Phenomenex (Fillatre et al 2014).…”

“…Short columns with the particle diameter not larger than 2 μm, first proposed by Waters in 2004 as BEH C 18 , with the particle diameter of 1.7 μm (Swartz 2005), are gaining increasing popularity. In this group of sorbents, the abovementioned column BEH C 1 8 (Sivaperumal et al 2015;Chung and Lam 2012;Chen et al 2011;Mastovska et al 2010) and Zorbax C 18 , with the particle diameter of 1.8 μm, from Agilent Technology (Perez-Ortega et al 2012;Stachniuk and Fornal 2013;Sinha et al 2012), are the most popular in the analysis of pesticide residues in food. Reduced particle diameter necessitates the use of increasingly higher pressures.…”

“…Its sample purity requirements are not stringent, and it enables a simultaneous analysis of substances that vary considerably in polarity. The popularity of the method is confirmed by the increasing number of publications dedicated to the applications of LC-MS in the determination of contaminants, including pesticides, in food (Sivaperumal et al 2015;Gómez-Pérez et al 2015;Martinez-Dominguez et al 2015;Golge and Kebak 2015;Fillatre et al 2014;Esturk et al 2014;Oshita and Jardim 2014;González-Curbelo et al 2014;Rajski et al 2013;Arienzo et al 2013;Stachniuk and Fornal 2013;Sinha et al 2012;Gilbert-Lopez et al 2012;Lozano et al 2012;Chung and Lam 2012;BoteroCoy et al 2012;Tian 2011;Pareja et al 2011;Kmellar et al 2011;Aguilera-Luiz et al 2011;Chen et al 2011;Lehotay et al 2010;Zhang et al 2010;Camino-Sanchez et al 2010;Kamel et al 2010;Brutti et al 2010). In pesticide residue analysis, similarly to the analysis of other food contaminants, there is a distinct tendency to develop fast multiresidue methods.…”

Optical sensing of 3-phenoxybenzoic acid as a pyrethroid pesticides exposure marker by surface imprinting polymer capped on manganese-doped zinc sulfide quantum dots

“…Several other methods have been reported in the analysis of pyrethroid metabolites. These include high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS) [29,30], gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) [31][32][33][34] and immunoassay based methods [35,36]. Although, these methods have an advantage to quantify 3-PBA in several matrices, but they are not compatible for on-field sensing and monitoring applications.…”