Residues and Dietary Risk Assessments of 2,4‑D Isooctyl Ester, Metribuzin, Acetochlor, and 2‑Ethyl-6-methylaniline in Corn or Soybean Fields

Since 2,4-dichlorophenoxy acetic acid (2,4-D) was discovered in the 1940s, 2,4-D and its derivatives remain among most commonly used herbicides in the world. There have been recent increases in using 2,4-D products in a combination with other herbicides such as metribuzin and acetochlor to control noxious weeds. However, accurate analysis of 2,4-D isooctyl ester remains to be improved due to long analysis time and rapid conversion of the ester to acid (i.e., under-reporting residues). In this work, a simple hydrolysis procedure was introduced to provide a quantitative hydrolytic rate of the ester (>95%) and did not affect the other pH-sensitive compounds. Analysis parameters and sample pretreatments were optimized for improved selectivity and accuracy. The hydrolysis-QuEChERS (quick, easy, cheap, effective, rugged, and safe) technique for multidetermination of 2,4-D isooctyl ester, metribuzin, acetochlor, and 2-ethyl-6-methylaniline in corn and soybeans via high performance liquid chromatography–tandem mass spectrometry was established. The method had average recoveries of 74–109% with relative standard deviations ≤13.5% and limits of quantifications (LOQs) of 0.05 mg/kg. The terminal residues of these compounds found in real edible matrixes were less than the corresponding LOQs at harvest time. The risk quotients were far below 100%, indicating a low health risk to consumers.