Critical Assessment of Clean-Up Techniques Employed in Simultaneous Analysis of Persistent Organic Pollutants and Polycyclic Aromatic Hydrocarbons in Fatty Samples

Interference of residual lipids is a very common problem in ultratrace analysis of contaminants in fatty matrices. Therefore, quick and effective clean-up techniques applicable to multiple groups of analytes are much needed. Cartridge and dispersive solid-phase extraction (SPE and dSPE) are often used for this purpose. In this context, we evaluated the lipid clean-up efficiency and performance of four commonly used sorbents—silica, C18, Z-Sep, and EMR-lipid—for the determination of organic pollutants in fatty fish samples (10%) extracted using ethyl acetate or the QuEChERS method. Namely, 17 polychlorinated biphenyls (PCBs), 22 organochlorine pesticides (OCPs), 13 brominated flame retardants (BFRs), 19 per- and polyfluoroalkyl substances (PFAS), and 16 polycyclic aromatic hydrocarbons (PAHs) were determined in this study. The clean-up efficiency was evaluated by direct analysis in real time coupled with time-of-flight mass spectrometry (DART-HRMS). The triacylglycerols (TAGs) content in the purified extracts were significantly reduced. The EMR-lipid sorbent was the most efficient of the dSPE sorbents used for the determination of POPs and PAHs in this study. The recoveries of the POPs and PAHs obtained by the validated QuEChERS method followed by the dSPE EMR-lipid sorbent ranged between 59 and 120%, with repeatabilities ranging between 2 and 23% and LOQs ranging between 0.02 and 1.50 µg·kg−1.

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg−1), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.

Method validation for determination of nine pesticides in okra and their mitigation using different solutions

In this paper we optimized QuEChERS method for extraction of nine pesticides viz. acephate, acetamiprid, chlorpyrifos, cypermethrin, imidacloprid, thiamethoxam, profenofos (insecticides), carbendazim and tebuconazole (fungicides) and performed their quantitative estimation in okra crop by HPLC-UV and GC-ECD. Decontamination treatments namely washing with running tap water, soaking in lukewarm water (50–60°C), soaking in solutions of 1% NaCl, 5% NaHCO3, 2% CH3COOH, 0.01% KMnO4 and three commercial formulations were also done for ten minutes every time, to calculate the extent of pesticide removal from okra. Results revealed that the proposed extraction method was efficient, inexpensive, accurate, rapid and precise and can suitably be used for the simultaneous quantitative determination of the above pesticides. The standard curve was linear over the concentration range of 0.05–5μg g-1 with R2 close to one (0.999). Soaking of okra in 2% acetic acid and then washing proved as the best decontamination treatments for all the pesticides. It showed the highest relative decontaminating capacity in comparison to the other solutions tested. Since the pesticide residues are usually present in higher amount in vegetables being consumed, it is of utmost importance to keep an eye over the use of pesticides to protect the crops.

Chlorfenapyr and Methomyl Deterioration on Spinach Plants and Their Residual Effects in Vitro on Egyptian cotton Leafworm (Spodoptera littoralis)

Field trials conducted to determine the degradation of chlorfenapyr and methomyl insecticides in/on spinach leaves. Spinach plants sprayed with chlorfenapyr (Challenger Super™ 24% SC) and methomyl (Neomyl™ 90% SP) at the rates of 50 cm3/100 L water and 715 g/ ha, respectively. The QuEChERS method used for the extraction and clean-up of the samples. Residue amounts determined at 2 h, 2, 4, 6, 9, 13 and 16 days after application by UHPLC-UV. The mean of recovery percentages was 98.78 and 99.05 % for chlorfenapyr and methomyl, respectively. The initial deposits of chlorfenapyr and methomyl on/in spinach leaves, two hours after a single application of the insecticides were 23.17 and 235.37 mg/kg, respectively. The percentages of dissipation of chlorfenapyr were 37.68, 55.29, 69.45, 84.45 and 96.83% for 2, 4, 6, 9 and 16 days after application. The corresponding dissipation percentages of methomyl were 38.27, 56.01, 71.44, 84.34 and 97.81%. The rates of degradation (k values) were 0.212 and 0.223, while the corresponding half-life times (t0.5) were 3.27 and 3.11 days with chlorfenapyr and methomyl, respectively. It could be recommended that single application of chlorfenapyr on Spinach plants at the early ages followed by single application of methomyl at least 17 days before harvest.