Simultaneous determination of three acidic herbicide residues in food crops using HPLC and confirmation via LC‐MS/MS

Abstract

2,4-D, dicamba and 4-CPA with auxin-like activity have been intensively used in agriculture, for the control of unwanted broadleaf weeds. An analytical method involving HPLC coupled with UVD was developed for the simultaneous analysis of these three analytes in Chinese cabbage, apple and pepper fruits (representative non-fatty samples) and brown rice and soybean (representative fatty samples) using liquid-liquid partitioning and column cleanup procedures. The residues were confirmed via tandem mass spectrometry (MS/MS) in ion electrospray ionization (ESI) mode. The standard curves were linear over the range of the tested concentrations (0.25-10 microg/mL), as shown by a marked linearity in excess of 0.9999 (r(2) ). The average recoveries (mean, n = 3) ranged from 94.30 to 102.63 in Chinese cabbage, from 94.76 to 108.47 in apple, from 97.52 to 102.27 in pepper, from 76.19 to 101.90 in brown rice, and from 74.60 to 107.39 in soybean. The relative standard deviations (RSDs) were <9% in all tested matrices. The limits of detection and quantitation were 0.006 and 0.02 mg/kg, respectively. Samples purchased from local markets were analyzed to evaluate the applicability of the methods developed herein. The concentration of the 2,4-D residue was measured at 0.102 mg/kg in the soybean sample; however, this level is exactly the same MRL set by the Korea Food and Drug Administration. This developed method deserves full and complete consideration, as it clearly displays the sensitivity, accuracy and precision required for residue analysis of 2,4-D, dicamba and 4-CPA in food crops.

Factors Influencing Dislodgeable 2, 4-D Plant Residues from Hybrid Bermudagrass (Cynodon dactylon L. x C. transvaalensis) Athletic Fields

“…All reagents and solvents used for residue analyses were HPLC grade. Total 2,4-D residue in/on turfgrass vegetation was quantified with modifications to methods by Shin et al [ 40 ]. Processed vegetation (5 g) was mixed with water (100–120 mL) in a high-speed homogenizer [9000 rpm (VIRTIS 45 Homogenizer; The VIRTIS Co., Gardiner, NY, USA)] for 2 min.…”

Determination of cyantraniliprole and its major metabolite residues in vegetable and soil using ultra‐performance liquid chromatography/tandem mass spectrometry

“…HPLC‐MS, especially HPLC‐MS/MS has proven to be a powerful technique for the analysis of pesticides and drugs at trace concentration levels because of its high selectivity, precision and sensitivity (Beale et al , ; Dong et al , ; Shin et al , ; Wang et al , ). Among the several ionization modes, electrospray ionization (ESI) has proven to be a reliable, robust and sensitive (Dong et al , ; Nevado et al , ; Pico et al , ; Siqueira et al , ).…”

Critical and systematic evaluation of data for estimating human exposures to 2,4-dichlorophenoxyacetic acid (2,4-D) – quality and generalizability

“…However, nine of these publications did not contain data relevant for human exposure assessment, either because they were primarily methodological papers that used a limited number of samples with no information on source or field handling of food items (Anastassiades and Schwack 1998;Lancas, Rissato, and Galhiane 1999;Lancas, Rissato, and Mozeto 1996;Vdovenko et al 2013), because the items measured were in a form not relevant to direct consumption (e.g. wheat straw) (Cessna and Hunter 1993;Gowen, Wiersma, and Tai 1976;Lancas, Rissato, and Galhiane 1999;Lancas, Rissato, and Mozeto 1996), because no primary concentration data were provided (Gartrell et al 1985;Shin et al 2011) or because 2,4-D results were not included (Whitmore et al 1994).…”