Characterization of the composition of plant protection products in different formulation types employing suspect screening and unknown approaches

Abstract

BACKGROUND Plant protection products (PPPs) are used extensively in agriculture to control crops. These PPPs, which may be found in different types of formulations, are composed of a designated pesticide (active principle) and other inactive ingredients as co‐formulants. They perform specific functions in the formulation, as solvents, preservatives or antifreeze agents, among others. RESULTS A research technique based on ultra‐high‐performance liquid chromatography (UHPLC) coupled to a Quadrupole‐Orbitrap mass analyzer was successfully applied to characterize the composition of six different PPPs in terms of the presence of co‐formulants and types of formulations: emulsifiable concentrate (EC), emulsion in water (EW), suspension concentrate and water‐dispersible granule. These PPPs (FLINT MAX, MASSOCUR 12.5 EC, IMPACT EVO, TOPAS, LATINO and IMPALA STAR) had antifungal activity, containing one triazole compound as active principle (tebuconazole, penconazole, myclobutanil, flutriafol or fenbuconazole, respectively). Non‐targeted approaches, applying suspect and unknown analysis, were carried out and ten compounds were identified as potential co‐formulants. Six (glyceryl monostearate, 1‐monopalmitin, dimethyl sulfoxide, N,N‐dimethyldecanamide, hexaethylene glycol and 1,2‐benzisothiazol‐3(2H)‐one) were confirmed by injecting analytical standards. Finally, these compounds were quantified in the PPPs. CONCLUSION The current study allowed for detecting co‐formulants in a wide range of concentrations, between 0.04 (dimethyl sulfoxide) and 19.00 g L−1 (glyceryl monostearate), highlighting the feasibility of the proposed analytical methodology. Moreover, notable differences among the types of formulations of PPPs were achieved, revealing that EC and EW were the formulations that contained the largest number of co‐formulants (four out of six detected compounds). © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Characteristic response of formulation ingredients revealed by ultra high performance liquid chromatography‐electrospray ionization‐high resolution mass spectrometry‐based untargeted screening of pesticides in soil

“…Given that the FIs are mostly polymers, 5–10 the first interpretation to be given is that these different ions separated by this gap are serial polymeric compounds with consecutively an additional monomer and that the 44.0262 corresponds to the monoisotopic mass of the ‐C 2 H 4 O‐ oxirane, the monomer in question. To confirm this interpretation, first, extracted ion chromatograms (EICs) of all these ions were drawn.…”

“…Given that the FIs are mostly polymers, [5][6][7][8][9][10] the first interpretation to be given is that these different ions separated by this gap are serial polymeric compounds with consecutively an additional monomer and T A B L E 1 Residues groups to be investigated.…”

“…The interest in analyzing this component is however growing, particularly by using mass spectrometry (MS) technology. [5][6][7][8][9][10] This technology allows detecting, characterizing, and quantifying these compounds with relatively high accuracy and sensitivity, especially when coupled to separation techniques such as chromatography.…”

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

“…Despite their possible health effects, they have barely been studied in real samples and published articles are mainly focused on their analysis in PPPs. − For their analysis, two techniques have been employed, gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) and liquid chromatography (LC) coupled to HRMS. When LC-HRMS is employed, a dilution of the PPPs and direct injection is commonly used, identifying 10 (6 of them confirmed) and 78 (9 of them confirmed) coformulants. LC was also used in the study of Balmer et al.…”

“…11−13 For their analysis, two techniques have been employed, gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) and liquid chromatography (LC) coupled to HRMS. When LC-HRMS is employed, a dilution of the PPPs and direct injection is commonly used, identifying 10 (6 of them confirmed) 14 and 78 (9 of them confirmed) 15 coformulants. LC was also used in the study of Balmer et al to determine the dissipation of PPP additives under field conditions.…”