Uncovering the Dissipation of Chlorantraniliprole in Tomatoes: Identifying Transformation Products (TPs) and Coformulants in Greenhouse and Laboratory Studies by UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS

Abstract

The present study addressed the dissipation of the insecticide chlorantraniliprole in tomatoes treated with Altacor 35 WG under laboratory and greenhouse conditions, as well as the identification of transformation products (TPs) and coformulants, performing suspect screening analysis. Analyses were performed by ultra-high-performance liquid and gas chromatography coupled to quadrupole-Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS). In all cases, chlorantraniliprole was fitted to a biphasic kinetic model, with R 2 values greater than 0.99. Dissipation was noticeably faster in greenhouse studies, in which even 96% dissipation was achieved over 53 days. One TP, IN-F6L99, was tentatively identified in both greenhouse and laboratory studies and was semiquantified by using chlorantraniliprole as the analytical standard, yielding a top value of 354 μg/kg for laboratory studies, whereas values for greenhouse studies fell under the limit of quantitation (LOQ). Finally, a total of 15 volatile coformulants were identified by GC-Q-Orbitrap-MS.

Monitoring of Volatile Additives from Plant Protection Products in Tomatoes Using HS-SPME-GC-HRMS: Targeted and Suspect Approaches

“…A targeted study was carried out to identify the most frequently identified additives in the incurred samples. The 21 additives already detected in previous studies with similar PPP formulations were acquired and searched in tomato samples collected from the greenhouse after the first and second application. ,− However, only 3 of them were detected in the treated samples, for both treatments, 1,2,4-trimethylbenzene, pentamethylbenzene and biphenyl.1,2,4-trimethylbenzene and biphenyl had been detected in Topas PPP at a concentration of 1.91 and 0.01 g/L, respectively, and 1,2,4-trimethylbenzene and pentamethylbenzene were detected when Altacor PPP was sprayed over tomato cultivation, but they were neither confirmed nor quantified . In this study, they were detected with concentrations for both PPPs treatments between 0.42 and 160.14 μg/kg.…”

“… 10 , 17 − 19 However, only 3 of them were detected in the treated samples, for both treatments, 1,2,4-trimethylbenzene, pentamethylbenzene and biphenyl.1,2,4-trimethylbenzene and biphenyl had been detected in Topas PPP at a concentration of 1.91 and 0.01 g/L, respectively, 17 and 1,2,4-trimethylbenzene and pentamethylbenzene were detected when Altacor PPP was sprayed over tomato cultivation, but they were neither confirmed nor quantified. 19 In this study, they were detected with concentrations for both PPPs treatments between 0.42 and 160.14 μg/kg. These compounds are derived from benzene, and they could exhibit irritated, toxic, and narcotic effects.…”

“…In that study, 7 targeted coformulants were quantified in tomato samples at low concentrations, ranging from 1 to 70 μg/kg, showing the preconcentration capacity of this technique. Besides, a recently published article also employed HS-SPME and GC-HRMS to putatively identify 15 additives in tomato samples treated with the PPP Altacor …”

“…Besides, a recently published article also employed HS-SPME and GC-HRMS to putatively identify 15 additives in tomato samples treated with the PPP Altacor. 19 …”

“…These two last articles and the article of Balmer et al, 16 constitute the only three published studies where additive fate was determined. However, only in the studies of Balmer et al 16 and Maldonado-Reina et al., 19 the dissipation was evaluated under field conditions. In those studies, it was observed that the amount of coformulants declines fast, although it was also indicated that for some cultivations, such as parsley and celery, certain additives remain at high concentrations 2 weeks after treatment, highlighting the need for control of these substances.…”