Simultaneous analysis of 310 pesticide multiresidues using UHPLC-MS/MS in brown rice, orange, and spinach

다국어 초록 (Multilingual Abstract)

<P><B>Abstract</B></P> <P>In this study, we developed a multiresidue method for the analysis of 310 pesticides in representative agricultural produce (brown rice, orange, and spinach) using ultra high performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) combined with a modified QuEChERS procedure. The optimal mobile phase composition (Methanol containing 5 mM ammonium formate and 0.1% formic acid) produced high sensitivity and reliable results. Also, the relationship between injection volume and repeatability of peak area was investigated. Most of the target pesticides had a limit of quantitation under 10 ng g<SUP>−1</SUP>, and correlation coefficients (<I>r</I> <SUP>2</SUP>) > 0.99 in matrix-matched standards within the range of 1–100 ng g<SUP>−1</SUP>. To validate the optimized method, recovery tests were performed with each of the crops at 10 and 50 ng g<SUP>−1</SUP> spiking levels (<I>n</I> = <I>5</I>). Satisfactory recoveries were achieved showing that 86.8–88.7% (at 10 ng g<SUP>−1</SUP>) and 91.9–96.1% (at 50 ng g<SUP>−1</SUP>) of the pesticides met the validation criteria (recoveries in the range of 70–120% and relative standard deviation ≤ 20%). Fifteen compounds were found to show a loss of recovery due to adsorption by primary and secondary amine or graphite carbon black. In the case of brown rice, 86.1% of pesticides showed an insignificant matrix effect (<±20%), while 35.2% and 41.6% of pesticides in orange and spinach were in that range, respectively. Sixteen apple samples from local markets were analyzed to evaluate the applicability of the optimized method. Nineteen pesticides were detected, of which the concentrations were lower than the maximum residue limit.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The protocol can analyze large number of pesticides (310 analytes) with modified QuEChERS and LC-MS/MS. </LI> <LI> A relationship between injection volumes and repeatability in LC-MS/MS analysis. </LI> <LI> Mobile phase compositions were compared for best sensitivity in LC-MS/MS. </LI> <LI> The method is reproducible and sensitive. </LI> <LI> It was successfully used to determine pesticide residues in market samples. </LI> </UL> </P>