Efficacy of the traditional and nano-forms of thiocyclam and chlorantraniliprole against Spodoptera littoralis and Agrotis ipsilon and analysis of their residues in tomato fruits

International Journal of Tropical Insect Science (2024) 44:657–667 https://doi.org/10.1007/s42690-024-01169-w ORIGINAL RESEARCH ARTICLE Efficacy of the traditional and nano-forms of thiocyclam and chlorantraniliprole against Spodoptera littoralis and Agrotis ipsilon and analysis of their residues in tomato fruits Moataz A. M. Moustafa1 EL-Desoky S. Ibrahim1 · Hassan A. EL-Gammal2 · Nawal Abdulaziz Alfuhaid3 · Adrien Fonagy4 · Received: 31 May 2023 / Accepted: 11 January 2024 / Published online: 19 February 2024 © The Author(s) 2024 Abstract For effective pest control, nano-insecticides have recently been proposed as a promising alternative to traditional ones. Thus, this study aimed to compare the efficacy of the traditional and nano-forms of thiocyclam (a natural toxin-based insecticide) and chlorantraniliprole (a diamide insecticide) against two major insect pests, the cotton leafworm, Spodoptera littoralis (Boisd.), and the black cutworm, Agrotis ipsilon (Hufnagel). The residue levels of the two insecticides in tomato fruits were also assessed. The results showed that chlorantraniliprole was more effective against both insects than thiocyclam, and the nano-forms were more effective than the traditional ones. This higher insecticidal activity of chlorantraniliprole could be attributed to its novel action by binding tightly to ryanodine receptors in insects. The study also optimized and validated an analytical method for residue determination of thiocyclam and chlorantraniliprole in tomato fruits using QuEChERS method and LC-MS/MS. Percentage recovery ranged from 70 to 104%, with good precision and expanded uncertainty of up to ± 23%. The half-life times of thiocyclam and its nano-form in tomatoes were 0.38 and 0.57 days, respectively, compared to 0.7 and 0.38 days for chlorantraniliprole and its nano-form. On the other hand, the calculated pre-harvest intervals for thiocyclam and its nano-form, using the EU maximum residue limit, were 7 and 3 days, respectively, compared to 1 day for both forms of chlorantraniliprole. Keywords Spodoptera littoralis · Agrotis ipsilon · Efficacy · Nano-insecticides · Dissipation · LC-MS/MS · Tomato fruits Introduction Adrien Fonagy Moataz A. M. Moustafa 1 Department of Economic Entomology and Pesticides, Faculty of Agriculture, Cairo University, 12613 Giza, Egypt 2 Pesticide Analysis Department, Central Agricultural Pesticide Laboratory, Giza, Egypt 3 Department of Biology, College of Science and Humanities, Prince Sattam Bin Abdulziz University, 11942 Al-Kharj, Saudi Arabia 4 Plant Protection Institute, Centre for Agricultural Research, Eötvös Lóránd Research Network (ELKH), 1022 Budapest, Hungary The family Noctuidae is the most diverse group within Lepidoptera, comprising a vast number of species that have a significant impact on the agricultural ecosystem (Caccia et al. 2014). Examples include the cotton leafworm, Spodoptera littoralis (Boisd.), and the black cutworm, Agrotis ipsilon (Hufnagel). Both insects are considered significant pests as they attack various crops during their seedling or vegetative stages (Ladhari et al. 2013). The primary method for controlling S. littoralis or A. ipsilon has been the application of chemical insecticides (Awad et al. 2022; Moustafa et al. 2022a). However, the frequent and intensive use of these insecticides has resulted in the development of resistance to nearly all insecticide groups employed to control these pests (Abo-Elghar et al. 2005; Xu et al. 2016; Fouad et al. 2022; Moustafa et al. 2023a). 13 658 International Journal of Tropical Insect Science (2024) 44:657–667 This challenge led researchers to devote significant effort to develop alternative strategies for controlling these insects. These include (1) the use of botanical insecticides including plant extracts and essential oils (Khan et al. 2017; Moustafa et al. 2021a, 2023b; El-Shourbagy et al. 2023), which do not harm ecosystems (Rajendran and Sriranjini 2008), (2) bioinsecticides, such as microbial and fermentation products (Moustafa et al. 2022a), and (3) novel chemical insecticides (Moustafa et al. 2021b, 2023c). Thiocyclam is based on the natural toxin of the marine worm Lumbriconereis heteropoda (Marenzeller). It has shown efficacy against coleoptera and lepidoptera pests (Ware and Whitacre 2004). The insecticide resistance action committee has classified thiocyclam as class 14 (IRAC 2022), which blocks the Nicotinic acetylcholine receptor (nAChR). Chlorantraniliprole, on the other hand, is a promising new insecticide belonging to the diamide group that has demonstrated effectiveness against several lepidopteran insect pests (Lahm et al. 2005; Lanka et al. 2013). It has been classified as class 28 by IRAC (2022) and is known to modulate the function of the ryanodine receptor (Guo et al. 2013). Environmental factors (Moustafa et al. 2018) or chemical reactions (Sanz-Asensio et al. 1997) may contribute to the degradation of insecticides. Therefore, dissipation studies are crucial in determining the pre-harvest interval (PHI) and ensuring that residue levels remain below the maximum residue limits (MRL) in food and environmental samples from each growing area under open field conditions (Malhat et al. 2012; El-Sheikh and Ashour 2022). Nanotechnology offers a promising approach to countering the potential environmental impact of chemical insecticides (Bhattacharyya et al. 2010; Bharani and Namasivayam 2017) by improving their toxicity against insect pests (Kah 2015). Additionally, nanotechnology is being conceived as a rapidly evolving field that has the potential to reform agriculture and food systems (Namasivayam et al. 2018). Nano-insecticides are defined as pesticide formulations consisting of nano-sized engineered structures with insecticidal properties (Kah and Hofmann 2014; Yan et al. 2021). They are considered a potential alternative solution to reduce the Table 1 Tested insecticides and their rate of application 2022) Group of Common name Rate of Insecticides application (a.i/hectare) Nereistoxin Thiocyclam 595 g/h Nano-Thiocyclam 59.5 g/h Diamide Chlorantraniliprole 28.56 g/h Nano-Chlorantraniliprole 2.856 g/h a.i.= active ingredient 13 (Awad et al. Trade name (a.i%) Evisect.S 50% SP Coragen 20% SC environmental footprint of chemical insecticides (Yan et al. 2021). However, the increasing interest in nano-insecticides has raised questions about their toxicity, fate, and biodegradation (Chaturvedi et al. 2014). Based on a previous study by Awad et al. (2022), both chlorantraniliprole and thiocyclam, as well as their nanoforms, have been identified as important candidates for the development of efficient nano-insecticides for controlling A. ipsilon. In the current study, field experiments were conducted to compare the effectiveness of thiocyclam, chlorantraniliprole, and their nano-forms against S. littoralis and A. ipsilon. Additionally, the dissipation of both insecticides and their nano-forms (...truncated)