Validation of a Multi-Residue Analysis Method for 287 Pesticides in Citrus Fruits Mandarin Orange and Grapefruit Using Liquid Chromatography–Tandem Mass Spectrometry

Abstract

Since the introduction of the positive list system (PLS) for agricultural products in the Republic of Korea, the demand for a quick, easy multi-residue analysis method increased continuously. Herein, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique combined with liquid chromatography–tandem mass spectrometry was employed to optimize a method for the multi-residue analysis of 287 pesticide residues in mandarin orange and grapefruit. Method validation was conducted in terms of selectivity, limit of quantitation (LOQ), linearity, accuracy, precision, and matrix effect. All the compounds at low spiking levels (1, 2.5, 5, or 10 mg/kg) could be quantified at LOQs lower than 0.01 mg/kg (PLS level). The linearity of the matrix-matched calibration curve for each compound is in the range 0.5–50 μg/L, and its coefficient of determination (R2) is >0.990. Satisfactory recovery values of 70–120% with a relative standard deviation of ≤20% are obtained for all compounds in the mandarin orange and grapefruit samples. A negligible matrix effect (−20–20%) is observed for more than 94.8% and 85.4% of the pesticides in mandarin orange and grapefruit, respectively. Therefore, this analytical method can contribute to pesticide residue analyses of citrus fruits for routine laboratory testing.

Exploring the Potential of Microextraction in the Survey of Food Fruits and Vegetable Safety

“…Consequently, it was able to extract a broader range of pesticides and achieved recovery levels of 60-120% (RSD values of 2-28%) and LODs of 0.5-1 µg kg −1 . The use of QuEChERS/dSPE as an extraction approach for multi-residue analysis has become very popular and many more examples can be found in the literature [89][90][91][92][93]. Woldetsadik et al [94] used QuEChERS/HS-SPME coupled with GC-MS for the determination of DDT congeners and four HCH isomers in khat samples.…”

“…This is essentially a clean-up procedure that can follow different extraction procedures, although its sole use has been already reported [118,119]. Eventually, dSPE's most popular use is associated with QuEChERS, a procedure that we included both in Table 1, devoted to conventional extraction procedures [88][89][90][91][92][93]107,108], as well as in Table 2, that presents microextraction approaches. The reason for this is that the miniaturization of QuEChERS (µQuEChERS) is being pursued by different researchers and the examples presented in Table 2 are variations of the original protocol downscaled to a microextraction format.…”

Multivariate Assessment and Risk Ranking of Pesticide Residues in Citrus Fruits

“…The cumulative chronic (HIc) and cumulative acute risk (HIa) are calculated according to Equation (11):…”

The non-edible and disposable parts of oyster mushroom, as novel adsorbent for quantitative removal of atrazine and its degradation products from synthetic wastewater

“…In addition to their potential toxicity, persistence, and water solubility, pesticides are utilized extensively, which raises concerns about their analysis in natural waters [ 12 ]. They have been determined from a number of environmental matrices such as water [ 4 , 8 , 13 ], fruit [ 14 ], honey [ 15 ], fish [ 16 ], crops [ 17 ], leafy vegetables [ 18 , 19 ], tobacco [ 20 , 21 ], coconut [ 22 ], fruit-based soft drinks [ 23 , 24 ], soil [ 25 , 26 ], and ambient air [ 27 , 28 ]. The determinations of pesticides and their metabolites in the aforementioned sample types are indications of the seriousness of the problem in the environment.…”